WorldWideScience

Sample records for reaction orders activation

  1. Iron-Induced Activation of Ordered Mesoporous Nickel Cobalt Oxide Electrocatalyst for the Oxygen Evolution Reaction.

    Science.gov (United States)

    Deng, Xiaohui; Öztürk, Secil; Weidenthaler, Claudia; Tüysüz, Harun

    2017-06-28

    Herein, ordered mesoporous nickel cobalt oxides prepared by the nanocasting route are reported as highly active oxygen evolution reaction (OER) catalysts. By using the ordered mesoporous structure as a model system and afterward elevating the optimal catalysts composition, it is shown that, with a simple electrochemical activation step, the performance of nickel cobalt oxide can be significantly enhanced. The electrochemical impedance spectroscopy results indicated that charge transfer resistance increases for Co 3 O 4 spinel after an activation process, while this value drops for NiO and especially for CoNi mixed oxide significantly, which confirms the improvement of oxygen evolution kinetics. The catalyst with the optimal composition (Co/Ni 4/1) reaches a current density of 10 mA/cm 2 with an overpotential of a mere 336 mV and a Tafel slope of 36 mV/dec, outperforming benchmarked and other reported Ni/Co-based OER electrocatalysts. The catalyst also demonstrates outstanding durability for 14 h and maintained the ordered mesoporous structure. The cyclic voltammograms along with the electrochemical measurements in Fe-free KOH electrolyte suggest that the activity boost is attributed to the generation of surface Ni(OH) 2 species that incorporate Fe impurities from the electrolyte. The incorporation of Fe into the structure is also confirmed by inductively coupled plasma optical emission spectrometry.

  2. Effect of ordering of PtCu₃ nanoparticle structure on the activity and stability for the oxygen reduction reaction.

    Science.gov (United States)

    Hodnik, Nejc; Jeyabharathi, Chinnaiah; Meier, Josef C; Kostka, Alexander; Phani, Kanala L; Rečnik, Aleksander; Bele, Marjan; Hočevar, Stanko; Gaberšček, Miran; Mayrhofer, Karl J J

    2014-07-21

    In this study the performance enhancement effect of structural ordering for the oxygen reduction reaction (ORR) is systematically studied. Two samples of PtCu3 nanoparticles embedded on a graphitic carbon support are carefully prepared with identical initial composition, particle dispersion and size distribution, yet with different degrees of structural ordering. Thus we can eliminate all coinciding effects and unambiguously relate the improved activity of the ORR and more importantly the enhanced stability to the ordered nanostructure. Interestingly, the electrochemically induced morphological changes are common to both ordered and disordered samples. The observed effect could have a groundbreaking impact on the future directions in the rational design of active and stable platinum alloyed ORR catalysts.

  3. Reaction Order Ambiguity in Integrated Rate Plots

    Science.gov (United States)

    Lee, Joe

    2008-01-01

    Integrated rate plots are frequently used in reaction kinetics to determine orders of reactions. It is often emphasised, when using this methodology in practice, that it is necessary to monitor the reaction to a substantial fraction of completion for these plots to yield unambiguous orders. The present article gives a theoretical and statistical…

  4. Temporal Frequency Modulates Reaction Time Responses to First-Order and Second-Order Motion

    Science.gov (United States)

    Hutchinson, Claire V.; Ledgeway, Tim

    2010-01-01

    This study investigated the effect of temporal frequency and modulation depth on reaction times for discriminating the direction of first-order (luminance-defined) and second-order (contrast-defined) motion, equated for visibility using equal multiples of direction-discrimination threshold. Results showed that reaction times were heavily…

  5. The oxygen evolution reaction on cobalt Part I. Reaction order experiments and impedance measurements

    NARCIS (Netherlands)

    Kobussen, A.G.C.; Willems, H.; Wit, J.H.W. de; Broers, G.H.J.

    1984-01-01

    It was found that the oxygen evolution reaction on cobalt in concentrated KOH solutions can be described differently for low and high overpotentials. In the overpotential range from 150 to 280 mV, the reaction has a Tafel slope of approximately 40 mV and a reaction order with respect to the KOH

  6. Complete active space second order perturbation theory (CASPT2) study of N({sup 2}D) + H{sub 2}O reaction paths on D{sub 1} and D{sub 0} potential energy surfaces: Direct and roaming pathways

    Energy Technology Data Exchange (ETDEWEB)

    Isegawa, Miho; Liu, Fengyi [Fukui Institute for Fundamental Chemistry, Kyoto University, 34-4 Takano Nishihiraki-cho, Kyoto 606-8103 (Japan); Maeda, Satoshi [Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810 (Japan); Morokuma, Keiji, E-mail: morokuma@fukui.kyoto-u.ac.jp [Fukui Institute for Fundamental Chemistry, Kyoto University, 34-4 Takano Nishihiraki-cho, Kyoto 606-8103 (Japan); Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322 (United States)

    2014-10-21

    We report reaction paths starting from N({sup 2}D) + H{sub 2}O for doublet spin states, D{sub 0} and D{sub 1}. The potential energy surfaces are explored in an automated fashion using the global reaction route mapping strategy. The critical points and reaction paths have been fully optimized at the complete active space second order perturbation theory level taking all valence electrons in the active space. In addition to direct dissociation pathways that would be dominant, three roaming processes, two roaming dissociation, and one roaming isomerization: (1) H{sub 2}ON → H–O(H)N → H–HON → NO({sup 2}Π) + H{sub 2}, (2) cis-HNOH → HNO–H → H–HNO → NO + H{sub 2}, (3) H{sub 2}NO → H–HNO → HNO–H → trans-HNOH, are confirmed on the D{sub 0} surface.

  7. Integrating reaction and analysis: investigation of higher-order reactions by cryogenic trapping

    Directory of Open Access Journals (Sweden)

    Skrollan Stockinger

    2013-09-01

    Full Text Available A new approach for the investigation of a higher-order reaction by on-column reaction gas chromatography is presented. The reaction and the analytical separation are combined in a single experiment to investigate the Diels–Alder reaction of benzenediazonium-2-carboxylate as a benzyne precursor with various anthracene derivatives, i.e. anthracene, 9-bromoanthracene, 9-anthracenecarboxaldehyde and 9-anthracenemethanol. To overcome limitations of short reaction contact times at elevated temperatures a novel experimental setup was developed involving a cooling trap to achieve focusing and mixing of the reactants at a defined spot in a fused-silica capillary. This trap functions as a reactor within the separation column in the oven of a gas chromatograph. The reactants are sequentially injected to avoid undefined mixing in the injection port. An experimental protocol was developed with optimized injection intervals and cooling times to achieve sufficient conversions at short reaction times. Reaction products were rapidly identified by mass spectrometric detection. This new approach represents a practical procedure to investigate higher-order reactions at an analytical level and it simultaneously provides valuable information for the optimization of the reaction conditions.

  8. Liquid-Crystalline Ionic Liquids as Ordered Reaction Media for the Diels-Alder Reaction.

    Science.gov (United States)

    Bruce, Duncan W; Gao, Yanan; Canongia Lopes, José Nuno; Shimizu, Karina; Slattery, John M

    2016-11-02

    Liquid-crystalline ionic liquids (LCILs) are ordered materials that have untapped potential to be used as reaction media for synthetic chemistry. This paper investigates the potential for the ordered structures of LCILs to influence the stereochemical outcome of the Diels-Alder reaction between cyclopentadiene and methyl acrylate. The ratio of endo- to exo-product from this reaction was monitored for a range of ionic liquids (ILs) and LCILs. Comparison of the endo:exo ratios in these reactions as a function of cation, anion and liquid crystallinity of the reaction media, allowed for the effects of liquid crystallinity to be distinguished from anion effects or cation alkyl chain length effects. These data strongly suggest that the proportion of exo-product increases as the reaction media is changed from an isotropic IL to a LCIL. A detailed molecular dynamics (MD) study suggests that this effect is related to different hydrogen bonding interactions between the reaction media and the exo- and endo-transition states in solvents with layered, smectic ordering compared to those that are isotropic. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. On the ambiguity of the reaction rate constants in multivariate curve resolution for reversible first-order reaction systems.

    Science.gov (United States)

    Schröder, Henning; Sawall, Mathias; Kubis, Christoph; Selent, Detlef; Hess, Dieter; Franke, Robert; Börner, Armin; Neymeyr, Klaus

    2016-07-13

    If for a chemical reaction with a known reaction mechanism the concentration profiles are accessible only for certain species, e.g. only for the main product, then often the reaction rate constants cannot uniquely be determined from the concentration data. This is a well-known fact which includes the so-called slow-fast ambiguity. This work combines the question of unique or non-unique reaction rate constants with factor analytic methods of chemometrics. The idea is to reduce the rotational ambiguity of pure component factorizations by considering only those concentration factors which are possible solutions of the kinetic equations for a properly adapted set of reaction rate constants. The resulting set of reaction rate constants corresponds to those solutions of the rate equations which appear as feasible factors in a pure component factorization. The new analysis of the ambiguity of reaction rate constants extends recent research activities on the Area of Feasible Solutions (AFS). The consistency with a given chemical reaction scheme is shown to be a valuable tool in order to reduce the AFS. The new methods are applied to model and experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Distributed order reaction-diffusion systems associated with Caputo derivatives

    Science.gov (United States)

    Saxena, R. K.; Mathai, A. M.; Haubold, H. J.

    2014-08-01

    This paper deals with the investigation of the solution of an unified fractional reaction-diffusion equation of distributed order associated with the Caputo derivatives as the time-derivative and Riesz-Feller fractional derivative as the space-derivative. The solution is derived by the application of the joint Laplace and Fourier transforms in compact and closed form in terms of the H-function. The results derived are of general nature and include the results investigated earlier by other authors, notably by Mainardi et al. ["The fundamental solution of the space-time fractional diffusion equation," Fractional Calculus Appl. Anal. 4, 153-202 (2001); Mainardi et al. "Fox H-functions in fractional diffusion," J. Comput. Appl. Math. 178, 321-331 (2005)] for the fundamental solution of the space-time fractional equation, including Haubold et al. ["Solutions of reaction-diffusion equations in terms of the H-function," Bull. Astron. Soc. India 35, 681-689 (2007)] and Saxena et al. ["Fractional reaction-diffusion equations," Astrophys. Space Sci. 305, 289-296 (2006a)] for fractional reaction-diffusion equations. The advantage of using the Riesz-Feller derivative lies in the fact that the solution of the fractional reaction-diffusion equation, containing this derivative, includes the fundamental solution for space-time fractional diffusion, which itself is a generalization of fractional diffusion, space-time fraction diffusion, and time-fractional diffusion, see Schneider and Wyss ["Fractional diffusion and wave equations," J. Math. Phys. 30, 134-144 (1989)]. These specialized types of diffusion can be interpreted as spatial probability density functions evolving in time and are expressible in terms of the H-function in compact forms. The convergence conditions for the double series occurring in the solutions are investigated. It is interesting to observe that the double series comes out to be a special case of the Srivastava-Daoust hypergeometric function of two variables

  11. Temperature dependence of third order ion molecule reactions. The reaction H+3 + 2H2 = H+5 + H2

    International Nuclear Information System (INIS)

    Hiraoka, K.; Kebarle, P.

    1975-01-01

    The rate constants k 1 for Reaction (1): H + 3 +2H 2 = H + 5 +H 2 were measured in the temperature range 100--300 degreeK. The temperature dependence of k 1 has the form k 1 proportionalT - /subn/, where n=2.3. Pierce and Porter have reported a much stronger negative temperature dependence with n=4.6. The difference arises from a determination of k 1 at 300 degreeK obtained by Arifov and used by Porter. The present k 1 (300 degreeK) =9times10 -30 (cm 6 molecules -2 center-dotsec -1 ). This is more than an order of magnitude larger than the Arifov value. The temperature dependence of third body dependent association reactions like (1) is examined on the basis of the energy transfer theory and the recently proposed trimolecular complex transition state theory by Meot-Ner, Solomon, Field, and Gershinowitz. The temperature dependence of the rate constant for the reverse reaction (-1) is obtained from k 1 and the previously determined temperature dependence of the equilibria (1). k/sub -//sub 1/ gives a good straight line Arrhenius plot leading to k/sub -//sub 1/ =8.7times10 -6 exp(-8.4/RT) cm 3 molecules -1 center-dotsec -1 . The activation energy is in kcal/mole. The preexponential factor is much larger than the rate constant for Langevin collisions. This is typical for pyrolysis of ions involving second order activation

  12. Birth Order and Activity Level in Children.

    Science.gov (United States)

    Eaton, Warren O.; And Others

    1989-01-01

    Studied 7,018 children between birth and 7 years and 81 children of 5-8 years to test the hypothesis that birth order is negatively related to motor activity level. Activity level declined linearly across birth position, so that early-borns were rated as more active than later-borns. (RJC)

  13. Application of tracer isotope in kinetic study of first order ion exchange reaction

    International Nuclear Information System (INIS)

    Lokhande, R.S.; Singare, P.U.

    1998-01-01

    Analysis of first order ion exchange reaction rates at different temperatures (27 deg- 48 degC) and particularly at low concentration of potassium iodide solution (electrolyte) ranging from 0.005 M to 0.040 M is carried out by application of radioactive tracer isotope 131 I. With increase in concentration of electrolyte, amount of iodide ion exchanged in millimoles increases. Specific reaction rates of ion exchange reaction are calculated for different temperatures and for different amount of ion exchange resins. It is observed that with increase in temperature, reaction rate increases but the increase is more pronounced for increase in amount of ion exchange resins. For 0.005 M solution of electrolyte, the reaction rate increases from 0.121 min -1 at 27 degC to 0.178 min -1 at 48 degC. For 0.005 M solution of electrolyte the reaction rate increases from 0.121 min -1 at 27 degC to 0.178 min 1 at 48 degC. For 0.005 M solution of electrolyte at 27 degC the reaction rate increases from 0.121 min -1 for 1.0 g of resin to 0.368 min -1 for 5.0 g of resin. From the reaction rates calculated at different temperatures, energy of activation in kJ/mole is calculated. It is observed that for 0.005 M solution of electrolyte, energy of activation is 4.62 kJ/mole which decreases to 2.87 kJ/mole for increase in concentration of electrolyte to 0.100 M. (author)

  14. A Kinetic Study of the Diels-Alder Reaction. An Experiment Illustrating Simple Second-Order Reaction Kinetics.

    Science.gov (United States)

    Silvestri, Michael G.; Dills, Charles E.

    1989-01-01

    Describes an organic chemistry experiment for teaching the basic concepts of chemical kinetics. Provides background information about first- and second-order reactions, experimental procedures of the Diels-Alder reaction between cyclopentadiene and dimethyl fumarate, and the experimental results. (YP)

  15. Reaction kinetics, reaction products and compressive strength of ternary activators activated slag designed by Taguchi method

    NARCIS (Netherlands)

    Yuan, B.; Yu, Q.L.; Brouwers, H.J.H.

    2015-01-01

    This study investigates the reaction kinetics, the reaction products and the compressive strength of slag activated by ternary activators, namely waterglass, sodium hydroxide and sodium carbonate. Nine mixtures are designed by the Taguchi method considering the factors of sodium carbonate content

  16. Selective and regular localization of accessible Pt nanoparticles inside the walls of an ordered silica: Application as a highly active and well-defined heterogeneous catalyst for propene and styrene hydrogenation reactions

    KAUST Repository

    Boualleg, Malika

    2011-12-01

    We describe here an original methodology related to the "build-the-bottle-around-the-ship" approach yielding a highly ordered silica matrix containing regularly distributed Pt nanoparticles (NPs) located inside the silica walls, Pt@{walls}SiO2. The starting colloidal solution of crystalline Pt nanoparticles was obtained from Pt(dba)2 (dba = dibenzylidene acetone) and 3-chloropropylsilane. The resulting nanoparticles (diameter: 2.0 ± 0.4 nm determined by HRTEM) resulted hydrophilic. The NPs present in the THF colloidal solution were incorporated inside the walls of a highly ordered 2D hexagonal mesoporous silica matrix via sol-gel process using a templating route with tetraethylorthosilicate, TEOS, as the silica source, and block copolymer (EthyleneOxide) 20(PropyleneOxide)70(EthyleneOxide)20 (Pluronic P123) as the structure-directing agent. Low-temperature calcination of the crude material at 593 K led to the final solid Pt@{walls}SiO2. Characterization by IR, HRTEM, BF-STEM and HAADF-STEM, SAXS, WAXS, XRD, XPS, H2 chemisorption, etc. of Pt@{walls}SiO2 confirmed the 2D hexagonal structuration and high mesoporosity (870 m2/g) of the material as well as the presence of stable 2-nm-sized crystalline Pt(0) NPs embedded inside the walls of the silica matrix. The material displayed no tendency to NPs sintering or leaching (Pt loading 0.3 wt.%) during its preparation. Pt@{walls}SiO2 was found to be a stable, selective and highly active hydrogenation catalyst. The catalytic performances in propene hydrogenation were tested under chemical regime conditions in a tubular flow reactor (278 K, propene/H2/He = 20/16/1.09 cm3/min, P tot = 1 bar) and were found superior to those of an homologous solid containing Pt NPs along its pore channels Pt@{pores}SiO2 and to those of a classical industrial catalysts Pt/Al2O3, (TOF = 2.3 s-1 vs. TOF = 0.90 and 0.92 s-1, respectively, calculated per surface platinum atoms). Pt@{walls}SiO2 also catalyzes fast and selective styrene

  17. Selective and regular localization of accessible Pt nanoparticles inside the walls of an ordered silica: Application as a highly active and well-defined heterogeneous catalyst for propene and styrene hydrogenation reactions

    KAUST Repository

    Boualleg, Malika; Norsic, Sé bastien; Baudouin, David; Sayah, Reine; Quadrelli, Elsje Alessandra; Basset, Jean-Marie; Candy, Jean Pierre; Dé lichè re, Pierre; Pelzer, Katrin; Veyre, Laurent; Thieuleux, Chloé

    2011-01-01

    We describe here an original methodology related to the "build-the-bottle-around-the-ship" approach yielding a highly ordered silica matrix containing regularly distributed Pt nanoparticles (NPs) located inside the silica walls, Pt@{walls}SiO2. The starting colloidal solution of crystalline Pt nanoparticles was obtained from Pt(dba)2 (dba = dibenzylidene acetone) and 3-chloropropylsilane. The resulting nanoparticles (diameter: 2.0 ± 0.4 nm determined by HRTEM) resulted hydrophilic. The NPs present in the THF colloidal solution were incorporated inside the walls of a highly ordered 2D hexagonal mesoporous silica matrix via sol-gel process using a templating route with tetraethylorthosilicate, TEOS, as the silica source, and block copolymer (EthyleneOxide) 20(PropyleneOxide)70(EthyleneOxide)20 (Pluronic P123) as the structure-directing agent. Low-temperature calcination of the crude material at 593 K led to the final solid Pt@{walls}SiO2. Characterization by IR, HRTEM, BF-STEM and HAADF-STEM, SAXS, WAXS, XRD, XPS, H2 chemisorption, etc. of Pt@{walls}SiO2 confirmed the 2D hexagonal structuration and high mesoporosity (870 m2/g) of the material as well as the presence of stable 2-nm-sized crystalline Pt(0) NPs embedded inside the walls of the silica matrix. The material displayed no tendency to NPs sintering or leaching (Pt loading 0.3 wt.%) during its preparation. Pt@{walls}SiO2 was found to be a stable, selective and highly active hydrogenation catalyst. The catalytic performances in propene hydrogenation were tested under chemical regime conditions in a tubular flow reactor (278 K, propene/H2/He = 20/16/1.09 cm3/min, P tot = 1 bar) and were found superior to those of an homologous solid containing Pt NPs along its pore channels Pt@{pores}SiO2 and to those of a classical industrial catalysts Pt/Al2O3, (TOF = 2.3 s-1 vs. TOF = 0.90 and 0.92 s-1, respectively, calculated per surface platinum atoms). Pt@{walls}SiO2 also catalyzes fast and selective styrene

  18. Controlled Synthesis of Pt Nanowires with Ordered Large Mesopores for Methanol Oxidation Reaction

    Science.gov (United States)

    Zhang, Chengwei; Xu, Lianbin; Yan, Yushan; Chen, Jianfeng

    2016-08-01

    Catalysts for methanol oxidation reaction (MOR) are at the heart of key green-energy fuel cell technology. Nanostructured Pt materials are the most popular and effective catalysts for MOR. Controlling the morphology and structure of Pt nanomaterials can provide opportunities to greatly increase their activity and stability. Ordered nanoporous Pt nanowires with controlled large mesopores (15, 30 and 45 nm) are facilely fabricated by chemical reduction deposition from dual templates using porous anodic aluminum oxide (AAO) membranes with silica nanospheres self-assembled in the channels. The prepared mesoporous Pt nanowires are highly active and stable electrocatalysts for MOR. The mesoporous Pt nanowires with 15 nm mesopores exhibit a large electrochemically active surface area (ECSA, 40.5 m2 g-1), a high mass activity (398 mA mg-1) and specific activity (0.98 mA cm-2), and a good If/Ib ratio (1.15), better than the other mesoporous Pt nanowires and the commercial Pt black catalyst.

  19. Self-activated, self-limiting reactions on Si surfaces

    DEFF Research Database (Denmark)

    Morgen, Per; Hvam, Jeanette; Bahari, Ali

    The direct thermally activated reactions of oxygen and ammonia with Si surfaces in furnaces have been used for a very long time in the semiconductor industry for the growth of thick oxides and nitride layers respectively. The oxidation mechanism was described in the Deal-Grove model as a diffusion...... mechanism for the direct growth of ultrathin films (0-3 nm) of oxides and nitrides under ultrahigh vacuum conditions. Neutral oxygen and a microwave excited nitrogen plasma interact directly with Si surfaces kept at different temperatures during the reaction. The gas pressures are around 10-6 Torr...... energy of an oxide system, which happened for an ordered structure, at a thickness of 0.7-0.8 nm. Thus this thin oxide structure has definite crystalline features. We have closely monitored the reaction kinetics with normal x-ray induced photoelectron spectroscopies, and also the structure, composition...

  20. Ordered hierarchically porous carbon codoped with iron and nitrogen as electrocatalyst for the oxygen reduction reaction.

    Science.gov (United States)

    Deng, Chengwei; Zhong, Hexiang; Yao, Lan; Liu, Sisi; Xu, Zhuang; Zhang, Huamin

    2014-12-01

    N-doped carbon catalysts have attracted great attention as potential alternatives to expensive Pt-based catalysts used in fuel cells. Herein, an ordered hierarchically porous carbon codoped with N and Fe (Fe-NOHPC) is prepared by an evaporation-induced self-assembly process followed by carbonization under ammonia. The soft template and Fe species promote the formation of the porous structure and facilitate the oxygen reduction reaction (ORR).The catalyst possesses an ordered hierarchically porous structure with a large surface area (1172.5 m(2) g(-1) ) and pore volume of 1.03 cm(3) g(-1) . Compared to commercial 20% Pt/C, it exhibits better ORR catalytic activity and higher stability as well as higher methanol tolerance in an alkaline electrolyte, which demonstrates its potential use in fuel cells as a nonprecious cathode catalyst. The N configuration, Fe species, and pore structure of the catalysts are believed to correlate with its high catalytic activity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Cognitive analysis of physicians' medication ordering activity.

    Science.gov (United States)

    Pelayo, Sylvia; Leroy, Nicolas; Guerlinger, Sandra; Degoulet, Patrice; Meaux, Jean-Jacques; Beuscart-Zéphir, Marie-Catherine

    2005-01-01

    Computerized Physician Order Entry (CPOE) addresses critical functions in healthcare systems. As the name clearly indicates, these systems focus on order entry. With regard to medication orders, such systems generally force physicians to enter exhaustively documented orders. But a cognitive analysis of the physician's medication ordering task shows that order entry is the last (and least) important step of the entire cognitive therapeutic decision making task. We performed a comparative analysis of these complex cognitive tasks in two working environments, computer-based and paper-based. The results showed that information gathering, selection and interpretation are critical cognitive functions to support the therapeutic decision making. Thus the most important requirement from the physician's perspective would be an efficient display of relevant information provided first in the form of a summarized view of the patient's current treatment, followed by in a more detailed focused display of those items pertinent to the current situation. The CPOE system examined obviously failed to provide the physicians this critical summarized view. Following these results, consistent with users' complaints, the Company decided to engage in a significant re-engineering process of their application.

  2. Polyaniline-Derived Ordered Mesoporous Carbon as an Efficient Electrocatalyst for Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Kai Wan

    2015-06-01

    Full Text Available Nitrogen-doped ordered mesoporous carbon was synthesized by using polyaniline as the carbon source and SBA-15 as the template. The microstructure, composition and electrochemical behavior were extensively investigated by the nitrogen sorption isotherm, X-ray photoelectron spectroscopy, cyclic voltammetry and rotating ring-disk electrode. It is found that the pyrolysis temperature yielded a considerable effect on the pore structure, elemental composition and chemical configuration. The pyrolysis temperature from 800 to 1100 °C yielded a volcano-shape relationship with both the specific surface area and the content of the nitrogen-activated carbon. Electrochemical tests showed that the electrocatalytic activity followed a similar volcano-shape relationship, and the carbon catalyst synthesized at 1000 °C yielded the best performance. The post-treatment in NH3 was found to further increase the specific surface area and to enhance the nitrogen doping, especially the edge-type nitrogen, which favored the oxygen reduction reaction in both acid and alkaline media. The above findings shed light on electrocatalysis and offer more strategies for the controllable synthesis of the doped carbon catalyst.

  3. Enhancing Activity for the Oxygen Evolution Reaction

    DEFF Research Database (Denmark)

    Frydendal, Rasmus; Busch, Michael; Halck, Niels Bendtsen

    2014-01-01

    Electrochemical production of hydrogen, facilitated in electrolyzers, holds great promise for energy storage and solar fuel production. A bottleneck in the process is the catalysis of the oxygen evolution reaction, involving the transfer of four electrons. The challenge is that the binding energies...... of all reaction intermediates cannot be optimized individually. However, experimental investigations have shown that drastic improvements can be realized for manganese and cobalt-based oxides if gold is added to the surface or used as substrate. We propose an explanation for these enhancements based...... that the oxygen evolution reaction overpotential decreases by 100–300 mV for manganese oxides and 100 mV for cobalt oxides....

  4. Critical ignition conditions in exothermically reacting systems: first-order reactions.

    Science.gov (United States)

    Filimonov, Valeriy Yu

    2017-10-01

    In this paper, the comparative analysis of the thermal explosion (TE) critical conditions on the planes temperature-conversion degree and temperature-time was conducted. It was established that the ignition criteria are almost identical only at relatively small values of Todes parameter. Otherwise, the results of critical conditions analysis on the plane temperature-conversion degree may be wrong. The asymptotic method of critical conditions calculation for the first-order reactions was proposed (taking into account the reactant consumption). The degeneration conditions of TE were determined. The calculation of critical conditions for specific first-order reaction was made. The comparison of the analytical results obtained with the results of numerical calculations and experimental data showed that they are in good agreement.

  5. Critical ignition conditions in exothermically reacting systems: first-order reactions

    Science.gov (United States)

    Filimonov, Valeriy Yu.

    2017-10-01

    In this paper, the comparative analysis of the thermal explosion (TE) critical conditions on the planes temperature-conversion degree and temperature-time was conducted. It was established that the ignition criteria are almost identical only at relatively small values of Todes parameter. Otherwise, the results of critical conditions analysis on the plane temperature-conversion degree may be wrong. The asymptotic method of critical conditions calculation for the first-order reactions was proposed (taking into account the reactant consumption). The degeneration conditions of TE were determined. The calculation of critical conditions for specific first-order reaction was made. The comparison of the analytical results obtained with the results of numerical calculations and experimental data showed that they are in good agreement.

  6. Catalytic activity of catalysts for steam reforming reaction. Contract research

    Energy Technology Data Exchange (ETDEWEB)

    Ohashi, Hirofumi; Inagaki, Yoshiyuki [Japan Atomic Energy Research Inst., Oarai, Ibaraki (Japan). Oarai Research Establishment

    2003-05-01

    Japan Atomic Energy Research Institute has been developing a hydrogen production system by means of steam reforming of methane (chemical reation: CH{sub 4} + H{sub 2}O = CO + 3H{sub 2}) coupling with High Temperature Engineering Test Reactor (HTTR) to demonstrate effectiveness of high-temperature nuclear heat utilization. Prior to construction of HTTR hydrogen production system, a mock-up test facility with a full-scale reaction tube was constructed to investigate transient behavior of the hydrogen production system an establish system controllability. In order to predict transient behavior and hydrogen productivity of the hydrogen production system, it is important to estimate the reaction characteristics under the same temperature and pressure conditions as those of HTTR hydrogen production system. For the purpose of investigate an apparent activation energy of catalysts, catalytic activity test using small apparatus was carried out under the condition of methane flow rate from 1.18 x 10{sup -3} to 3.19 x 10{sup -3} mol/s, temperature from 500 to 900degC, pressure from 1.1 to 4.1MPa, and mol ratio of steam to methane from 2.5 to 3.5. It was confirmed that apparent activation energies of two kinds of Ni catalysts which are to be used in the mock-up test were 51.7 and 57.4kJ/mol, respectively, and reaction rate constants were propositional to the value from P{sup -0.15} to P{sup -0.33}. (author)

  7. "JCE" Classroom Activity #111: Redox Reactions in Three Representations

    Science.gov (United States)

    Nieves, Edgardo L. Ortiz; Barreto, Reizelie; Medina, Zuleika

    2012-01-01

    This activity introduces students to the concept of reduction-oxidation (redox) reactions. To help students obtain a thorough understanding of redox reactions, the concept is explored at three levels: macroscopic, submicroscopic, and symbolic. In this activity, students perform hands-on investigations of the three levels as they work at different…

  8. Kinetics of two simultaneous second-order reactions occurring in different zones

    International Nuclear Information System (INIS)

    Dole, M.; Hsu, C.S.; Patel, V.M.; Patel, G.N.

    1975-01-01

    Equations have been derived for the case of free radicals recombining according to the second-order kinetics with or without diffusion control under the conditions that there are two simultaneous spatially separated recombination reactions but that only the overall free-radical concentration can be observed. The properties of these equations are discussed and methods for determining the three independent parameters in the first case and five in the second developed. The resulting equations have been applied to the interpretation of data obtained in studying the decay of allyl chain free radicals in irradiated extended chain crystalline polyethylene

  9. Activation barriers for series of exothermic homologous reactions. VI. Reactions of lanthanide and transition metal atoms.

    Science.gov (United States)

    Blue, Alan S.; Fontijn, Arthur

    2001-09-01

    Semiempirical configuration interaction (SECI) theory to predict activation barriers, E, as given by k(T)=ATn exp(-E(RT), has been applied to homologous series of lanthanide (LN) and transition metal (TM) atom oxidation reactions. This was achieved by considering as homologous series reactions of elements differing only by the number of electrons in one subshell. Comparison between SECI and experimental results leads to an average deviation for the LN+N2O reactions of 0.66 kJ mol-1, and up to 5.5 kJ mol-1 for other series. Thirty-one activation barriers are reported.

  10. Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Dawei [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA; Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory Physical Chemistry Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen Fujian 361005 China; Kou, Ronghui [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Ren, Yang [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Sun, Cheng-Jun [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Zhao, Hu [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA; Zhang, Ming-Jian [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA; School of Advanced Materials, Peking University Shenzhen Graduate School, Shenzhen Guangdong 518055 P. R. China; Li, Yan [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Huq, Ashifia [Chemical and Engineering Materials Division, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Ko, J. Y. Peter [The Cornell High Energy Synchrotron Source, Cornell University, Ithaca NY 14853 USA; Pan, Feng [School of Advanced Materials, Peking University Shenzhen Graduate School, Shenzhen Guangdong 518055 P. R. China; Sun, Yang-Kook [Department of Energy Engineering, Hanyang University, Seoul 133-791 South Korea; Yang, Yong [Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory Physical Chemistry Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen Fujian 361005 China; Amine, Khalil [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Bai, Jianming [National Synchrotron Light Source II, Brookhaven National Laboratory, Upton NY 11973 USA; Chen, Zonghai [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Wang, Feng [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA

    2017-08-25

    Nickel-rich layered transition metal oxides, LiNi1-x(MnCo)(x)O-2 (1-x >= 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi0.7Mn0.15Co0.15O2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs.

  11. Radiation-reaction force on a small charged body to second order

    Science.gov (United States)

    Moxon, Jordan; Flanagan, Éanna

    2018-05-01

    In classical electrodynamics, an accelerating charged body emits radiation and experiences a corresponding radiation-reaction force, or self-force. We extend to higher order in the total charge a previous rigorous derivation of the electromagnetic self-force in flat spacetime by Gralla, Harte, and Wald. The method introduced by Gralla, Harte, and Wald computes the self-force from the Maxwell field equations and conservation of stress-energy in a limit where the charge, size, and mass of the body go to zero, and it does not require regularization of a singular self-field. For our higher-order computation, an adjustment of the definition of the mass of the body is necessary to avoid including self-energy from the electromagnetic field sourced by the body in the distant past. We derive the evolution equations for the mass, spin, and center-of-mass position of the body through second order. We derive, for the first time, the second-order acceleration dependence of the evolution of the spin (self-torque), as well as a mixing between the extended body effects and the acceleration-dependent effects on the overall body motion.

  12. Surface-Activated Coupling Reactions Confined on a Surface.

    Science.gov (United States)

    Dong, Lei; Liu, Pei Nian; Lin, Nian

    2015-10-20

    Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density

  13. Analysis by nuclear reactions and activations. A current bibliography

    International Nuclear Information System (INIS)

    Bujdoso, E.

    2001-01-01

    A current bibliography based on INIS Atomindex with 78 references on Analysis by nuclear reactions and activations has been prepared for year 1998. References are arranged by first authors' name. (N.T.)

  14. Higher-order force moments of active particles

    Science.gov (United States)

    Nasouri, Babak; Elfring, Gwynn J.

    2018-04-01

    Active particles moving through fluids generate disturbance flows due to their activity. For simplicity, the induced flow field is often modeled by the leading terms in a far-field approximation of the Stokes equations, whose coefficients are the force, torque, and stresslet (zeroth- and first-order force moments) of the active particle. This level of approximation is quite useful, but may also fail to predict more complex behaviors that are observed experimentally. In this study, to provide a better approximation, we evaluate the contribution of the second-order force moments to the flow field and, by reciprocal theorem, present explicit formulas for the stresslet dipole, rotlet dipole, and potential dipole for an arbitrarily shaped active particle. As examples of this method, we derive modified Faxén laws for active spherical particles and resolve higher-order moments for active rod-like particles.

  15. Higher-order chaotic oscillator using active bessel filter

    DEFF Research Database (Denmark)

    Lindberg, Erik; Mykolaitis, Gytis; Bumelien, Skaidra

    2010-01-01

    A higher-order oscillator, including a nonlinear unit and an 8th-order low-pass active Bessel filter is described. The Bessel unit plays the role of "three-in-one": a delay line, an amplifier and a filter. Results of hardware experiments and numerical simulation are presented. Depending...

  16. Stereo and regioselectivity in ''Activated'' tritium reactions

    International Nuclear Information System (INIS)

    Ehrenkaufer, R.L.E.; Hembree, W.C.; Wolf, A.P.

    1988-01-01

    To investigate the stereo and positional selectivity of the microwave discharge activation (MDA) method, the tritium labeling of several amino acids was undertaken. The labeling of L-valine and the diastereomeric pair L-isoleucine and L-alloisoleucine showed less than statistical labeling at the α-amino C-H position mostly with retention of configuration. Labeling predominated at the single β C-H tertiary (methyne) position. The labeling of L-valine and L-proline with and without positive charge on the α-amino group resulted in large increases in specific activity (greater than 10-fold) when positive charge was removed by labeling them as their sodium carboxylate salts. Tritium NMR of L-proline labeled both as its zwitterion and sodium salt showed also large differences in the tritium distribution within the molecule. The distribution preferences in each of the charge states are suggestive of labeling by an electrophilic like tritium species(s). 16 refs., 5 tabs

  17. Using a CBL Unit, a Temperature Sensor, and a Graphing Calculator to Model the Kinetics of Consecutive First-Order Reactions as Safe In-Class Demonstrations

    Science.gov (United States)

    Moore-Russo, Deborah A.; Cortes-Figueroa, Jose E.; Schuman, Michael J.

    2006-01-01

    The use of Calculator-Based Laboratory (CBL) technology, the graphing calculator, and the cooling and heating of water to model the behavior of consecutive first-order reactions is presented, where B is the reactant, I is the intermediate, and P is the product for an in-class demonstration. The activity demonstrates the spontaneous and consecutive…

  18. SIMULTANEOUS ABSORPTION AND DESORPTION WITH REVERSIBLE 1ST-ORDER CHEMICAL-REACTION - ANALYTICAL SOLUTION AND NEGATIVE ENHANCEMENT FACTORS

    NARCIS (Netherlands)

    WINKELMAN, JGM; BEENACKERS, AACM

    The problem of ps absorption accompanied by a first-order reversible reaction, producing a volatile reaction product, is considered. A general analytical solution is developed for the film model, resulting in explicit relations for the concentration profiles in the film and for the mass transfer

  19. Ordered mesoporous silica prepared by quiescent interfacial growth method - effects of reaction chemistry

    Science.gov (United States)

    2013-01-01

    Acidic interfacial growth can provide a number of industrially important mesoporous silica morphologies including fibers, spheres, and other rich shapes. Studying the reaction chemistry under quiescent (no mixing) conditions is important for understanding and for the production of the desired shapes. The focus of this work is to understand the effect of a number of previously untested conditions: acid type (HCl, HNO3, and H2SO4), acid content, silica precursor type (TBOS and TEOS), and surfactant type (CTAB, Tween 20, and Tween 80) on the shape and structure of products formed under quiescent two-phase interfacial configuration. Results show that the quiescent growth is typically slow due to the absence of mixing. The whole process of product formation and pore structuring becomes limited by the slow interfacial diffusion of silica source. TBOS-CTAB-HCl was the typical combination to produce fibers with high order in the interfacial region. The use of other acids (HNO3 and H2SO4), a less hydrophobic silica source (TEOS), and/or a neutral surfactant (Tweens) facilitate diffusion and homogenous supply of silica source into the bulk phase and give spheres and gyroids with low mesoporous order. The results suggest two distinct regions for silica growth (interfacial region and bulk region) in which the rate of solvent evaporation and local concentration affect the speed and dimension of growth. A combined mechanism for the interfacial bulk growth of mesoporous silica under quiescent conditions is proposed. PMID:24237719

  20. Direct activation of allylic alcohols in palladium catalyzed coupling reactions

    NARCIS (Netherlands)

    Gümrükçü, Y.

    2014-01-01

    The direct use of allylic alcohols in substitution reactions without pre-activation of the hydroxyl-group into a better leaving group or the use of additional stoichiometric in situ activators remains challenging due to the poor leaving group ability of the hydroxyl-group. Hence, it is important to

  1. Exact criteria for uniqueness and multiplicity of an nth order chemical reaction via catastrophe theory approach. [Determines boundaries between unique and multiple steady state conditions

    Energy Technology Data Exchange (ETDEWEB)

    Chang, H C; Calo, J M

    1979-01-01

    A simple, generalized technique for the exact determination of the boundaries between regions of unique and of multiple solutions to certain nonlinear equations was developed by applying catastrophe theory to the mapping of implicit and explicit functions. Its application to an nth order reaction in continuous stirred tank reactor (CSTR) yields exact, explicit expressions for the boundaries between regions of single and multiple steady states, expressed in terms of the dimensionless heat transfer coefficient and activation energy. An exact implicit expression for the boundaries between regions of uniqueness and multiplicity was also derived for an nth order reaction in a catalyst particle with an intraparticle concentration gradient and uniform temperature and is fully demonstrated for the first-order reaction. In addition, explicit criteria were developed by assuming the limits on d ln g/d ln q, where g is the effectiveness factor and q the Thiele modulus, proposed by van den Bosch and Luss.

  2. Mesoporous Ruthenium/Ruthenium Oxide Thin Films: Active Electrocatalysts for the Oxygen Evolution Reaction

    DEFF Research Database (Denmark)

    Kibsgaard, Jakob; Hellstern, Thomas R.; Choi, Shin-Jung

    2017-01-01

    We report the first synthesis of a fully contiguous large area supported thin film of highly ordered mesoporous Ru and RuO2 and investigate the electrocatalytic properties towards the oxygen evolution reaction (OER). We find that the nanoscale porous network of these catalysts provides significant...... enhancements in geometric OER activity without any loss in specific activity. This work demonstrates a strategy for engineering materials at the nanoscale that can simultaneously decrease precious metal loading and increase electrode activity....

  3. Activation barriers for series of exothermic homologous reactions. V. Boron group diatomic species reactions

    Science.gov (United States)

    Blue, Alan S.; Belyung, David P.; Fontijn, Arthur

    1997-09-01

    Semiempirical configuration interaction (SECI) theory is used to predict activation barriers E, as defined by k(T)=ATn exp(-E/RT). Previously SECI has been applied to homologous series of oxidation reactions of s1, s2, and s2p1 metal atoms. Here it is extended to oxidation reactions of diatomic molecules containing one s2p1 atom. E values are calculated for the reactions of BH, BF, BCl, AlF, AlCl, AlBr, GaF, GaI, InCl, InBr, InI, TlF, TlCl, TlBr, and TlI with O2, CO2, SO2, or N2O. These values correlate with the sums of the ionization potentials and Σ-Π promotion energies of the former minus the electron affinities of the latter. In the earlier work n was chosen somewhat arbitrarily, which affected the absolute values of E. Here it is shown that examination of available experimental and theoretical results allows determination of the best values of n. Using this approach yields n=1.9 for the present series. For the seven reactions which have been studied experimentally, the average deviation of the SECI activation barrier prediction from experiment is 4.0 kJ mol-1. Energy barriers are calculated for another 52 reactions.

  4. Highly Stable and Active Catalyst for Sabatier Reactions

    Science.gov (United States)

    Hu, Jianli; Brooks, Kriston P.

    2012-01-01

    Highly active Ru/TiO2 catalysts for Sabatier reaction have been developed. The catalysts have shown to be stable under repeated shutting down/startup conditions. When the Ru/TiO2 catalyst is coated on the engineered substrate Fe-CrAlY felt, activity enhancement is more than doubled when compared with an identically prepared engineered catalyst made from commercial Degussa catalyst. Also, bimetallic Ru-Rh/TiO2 catalysts show high activity at high throughput.

  5. Activated by Combined Magnrtic Field Gravitropic Reaction Reply on Nanodose of Biologicaly Active Compounds

    Science.gov (United States)

    Sheykina, Nadezhda; Bogatina, Nina

    The new science direction nanotechnologies initiated a big jump in the pharmacology and medicine. This leads to the big development of homeopathy. The most interest appeared while investigating of the reaction of biological object on the nano dose of iologically substances. The changing of concentration (in nmol/l) of biologically active material is also possible during weak energy action. For instance, weak combined magnetic field may change a little the concentration of ions that are oriented parallel to the external magnetic field and, by the analogy with said above, lead to the similar effects. Simple estimations give the value for the threshold to the magnetic field by two orders smaller than the geomagnetic field. By this investigation we wanted to understand whether the analogy in the action of nano dose of biologically active substances and weak combined magnetic field presents and whether the action of one of these factors may be replaced by other one. The effect of one of biologically active substances NPA (Naphtyl-Phtalame Acid) solution with the concentration 0.01 mol/l on the gravitropic reaction of cress roots was investigated. It was shown that its effect was the inhibition of cress roots gravitropic reaction. The same inhibition was achieved by the combined magnetic field action on the cress roots, germinated in water. The alternative component of the combined magnetic field coincided formally with the cyclotron frequency of NPA ions. So the analogy in the action of nano dose of biologically active substances and weak combined magnetic field was shown. The combined magnetic field using allows to decrease sufficiently the dose of biologically active substances. This fact can be of great importance in pharmacy and medicine.

  6. Comparing temporal order judgments and choice reaction time tasks as indices of exogenous spatial cuing.

    Science.gov (United States)

    Eskes, Gail A; Klein, Raymond M; Dove, Mary Beth; Coolican, Jamesie; Shore, David I

    2007-11-30

    Attentional disorders are common in individuals with neurological or psychiatric conditions and impact on recovery and outcome. Thus, it is critical to develop theory-based measures of attentional function to understand potential mechanisms underlying the disorder and to evaluate the effect of intervention. The present study compared two alternative methods to measure the effects of attentional cuing that could be used in populations of individuals who may not be able to make manual responses normally or may show overall slowing in responses. Spatial attention was measured with speeded and unspeeded methods using either manual or voice responses in two standard attention paradigms: the cued target discrimination reaction time (RT) paradigm and the unspeeded temporal order judgment (TOJ) task. The comparison of speeded and unspeeded tasks specifically addresses the concern about interpreting RT differences between cued and uncued trials (taken as a proxy for attention) in the context of drastically different baseline RTs. We found significant cuing effects for both tasks (speeded RT and untimed TOJ) and both response types (vocal and manual) giving clinicians and researchers alternative methods with which to measure the effects of attention in different populations who may not be able to perform the standard speeded RT task.

  7. Photocatalysis reaction on ordered arrays of Au nanorads with controlled orientations

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Min Jung; Han, Sang Woo [Dept. of Chemistry and KI for the NanoCentury, KAIST, Daejeon (Korea, Republic of)

    2015-03-15

    Surface photocatalysis reactions of aromatic compounds self-assembled on metal surfaces have been extensively explored for the past decades. Despite the numerous studies on the surface photocatalysis reactions of aromatic compounds, that on Au surface has rarely been reported due to the inefficiency of Au toward these reactions compared to Ag. The detailed experimental and theoretical studies on the mechanism of the enhanced photocatalytic function of the AuNR arrays are currently underway.

  8. Charting an Alternate Pathway to Reaction Orders and Rate Laws in Introductory Chemistry Courses

    Science.gov (United States)

    Rushton, Gregory T.; Criswell, Brett A.; McAllister, Nicole D.; Polizzi, Samuel J.; Moore, Lamesha A.; Pierre, Michelle S.

    2014-01-01

    Reaction kinetics is an axiomatic topic in chemistry that is often addressed as early as the high school course and serves as the foundation for more sophisticated conversations in college-level organic, physical, and biological chemistry courses. Despite the fundamental nature of reaction kinetics, students can struggle with transforming their…

  9. Question order in the assessment of misperception of physical activity

    Directory of Open Access Journals (Sweden)

    van Dijke Marius

    2007-09-01

    Full Text Available Abstract Background People often have misperceptions (overestimation or underestimation about the health-related behaviours they engage in, which may have adverse consequences for their susceptibility to behavioural change. Misperception is usually measured by combining and comparing quantified behavioural self-reports with subjective classification of the behaviour. Researchers assume that such assessments of misperception are not influenced by the order of the two types of measurement, but this has never been studied. Based on the precaution adoption model and the information processing theory, it might be expected that taking the subjective measurement after a detailed quantified behavioural self-report would improve the accuracy of the subjective measurement because the quantified report urges a person to think more in detail about their own behaviour. Methods In an experiment (n = 521, quantified self-report and subjective assessment were manipulated in a questionnaire. In one version, the quantified self-report was presented before the subjective assessment, whereas in the other version, the subjective assessment came first. Results Neither subjective assessment nor overestimation of physical activity were biased by the order of the questions. Underestimation was more prevalent among subgroups of the group which answered the subjective assessment after the quantified self-report. Conclusion Question order in questionnaires does not seem to influence misperceptions concerning physical activity in groups relevant for health education (overestimators: those who do not meet the guidelines for physical activity while rating their physical activity as sufficient or high. The small order effect found in underestimators is less relevant for health education because this subgroup already meets the guideline and therefore does not need to change behaviour.

  10. Study of reactions induced by the halo nucleus 11Li with the active target MAYA

    International Nuclear Information System (INIS)

    Roger, Th.

    2009-09-01

    Active targets are perfect tools for the study of nuclear reactions induced by very low intensity radioactive ion beams. They also enable the simultaneous study of direct and compound nuclear reactions. The active target MAYA, built at GANIL, has been used to study the reactions induced by a 4.3*A MeV 11 Li beam at the ISAC2 accelerator TRIUMF (Canada). The angular distributions for the elastic scattering and the one and two neutron transfer reaction have been reconstructed. The elastic scattering angular distribution indicates a strong enhancement of the flux absorption with respect to the neighbouring nuclei. From a coupled channel analysis of the two neutron transfer reaction for different three body models, the information on the structure of the halo of the Borromean nucleus 11 Li have been extracted. Meanwhile, the energy dependence of the elastic scattering reaction has been studied, using the active target MAYA as a thick target. The resulting spectrum shows a resonance around 3 MeV centre of mass. This resonance could be an isobaric analog state of 12 Li, observed in 12 Be. R matrix calculations have been performed in order to extract the parameters (spin and parity) of this state. (author)

  11. Fourth order Douglas implicit scheme for solving three dimension reaction diffusion equation with non-linear source term

    Directory of Open Access Journals (Sweden)

    Shahid Hasnain

    2017-07-01

    Full Text Available This research paper represents a numerical approximation to non-linear three dimension reaction diffusion equation with non-linear source term from population genetics. Since various initial and boundary value problems exist in three dimension reaction diffusion phenomena, which are studied numerically by different numerical methods, here we use finite difference schemes (Alternating Direction Implicit and Fourth Order Douglas Implicit to approximate the solution. Accuracy is studied in term of L2, L∞ and relative error norms by random selected grids along time levels for comparison with analytical results. The test example demonstrates the accuracy, efficiency and versatility of the proposed schemes. Numerical results showed that Fourth Order Douglas Implicit scheme is very efficient and reliable for solving 3-D non-linear reaction diffusion equation.

  12. Fourth order Douglas implicit scheme for solving three dimension reaction diffusion equation with non-linear source term

    Science.gov (United States)

    Hasnain, Shahid; Saqib, Muhammad; Mashat, Daoud Suleiman

    2017-07-01

    This research paper represents a numerical approximation to non-linear three dimension reaction diffusion equation with non-linear source term from population genetics. Since various initial and boundary value problems exist in three dimension reaction diffusion phenomena, which are studied numerically by different numerical methods, here we use finite difference schemes (Alternating Direction Implicit and Fourth Order Douglas Implicit) to approximate the solution. Accuracy is studied in term of L2, L∞ and relative error norms by random selected grids along time levels for comparison with analytical results. The test example demonstrates the accuracy, efficiency and versatility of the proposed schemes. Numerical results showed that Fourth Order Douglas Implicit scheme is very efficient and reliable for solving 3-D non-linear reaction diffusion equation.

  13. Audience reaction movie trailers and the Paranormal Activity franchise

    OpenAIRE

    Alexander Swanson

    2015-01-01

    This article addresses the concept and growing practice of audience reaction movie trailers, specifically for films in the horror genre. Popularized by the Paranormal Activity series of films, these trailers primarily utilize green night-vision video footage of a movie theater audience reacting to the film being advertised, yet also consist of webcam recordings of screaming fans, documentary-style B-roll footage of audiences filing into preview screenings with high levels of anticipation, and...

  14. 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

  15. Serial killers: ordering caspase activation events in apoptosis.

    Science.gov (United States)

    Slee, E A; Adrain, C; Martin, S J

    1999-11-01

    Caspases participate in the molecular control of apoptosis in several guises; as triggers of the death machinery, as regulatory elements within it, and ultimately as a subset of the effector elements of the machinery itself. The mammalian caspase family is steadily growing and currently contains 14 members. At present, it is unclear whether all of these proteases participate in apoptosis. Thus, current research in this area is focused upon establishing the repertoire and order of caspase activation events that occur during the signalling and demolition phases of cell death. Evidence is accumulating to suggest that proximal caspase activation events are typically initiated by molecules that promote caspase aggregation. As expected, distal caspase activation events are likely to be controlled by caspases activated earlier in the cascade. However, recent data has cast doubt upon the functional demarcation of caspases into signalling (upstream) and effector (downstream) roles based upon their prodomain lengths. In particular, caspase-3 may perform an important role in propagating the caspase cascade, in addition to its role as an effector caspase within the death programme. Here, we discuss the apoptosis-associated caspase cascade and the hierarchy of caspase activation events within it.

  16. Biological activities of secondary metabolites of the order Zoanthids

    Directory of Open Access Journals (Sweden)

    Zahra Aminikhoei

    2015-11-01

    Full Text Available The phylum Cnidaria is a large, diverse and ecologically important group of marine invertebrates, which produce powerful toxins and venoms. The number of marine natural product from cnidarians isolated from class Anthozoa. Among the Anthozoa, the order of zoanthids are sessile, clonal and mostly brightly colored invertebrate which produce high biodiversity of cytolitic, neurotoxic and cardiotoxic compounds. Zoanthids containing palytoxins are reportedly among the most toxic marine organisms known. In addition, a high concentration of zoanthamine alkaloids extracted from this group.The zoanthamine alkaloids were isolated over 20 years ago, exhibit a broad range of biological activities.The best studied and most well-known biological activity of zoanthamine derivative significantly suppressed bone resorption and enhanced bone formation.

  17. Analysis of gas absorption to a thin liquid film in the presence of a zero-order chemical reaction

    Science.gov (United States)

    Rajagopalan, S.; Rahman, M. M.

    1995-01-01

    The paper presents a detailed theoretical analysis of the process of gas absorption to a thin liquid film adjacent to a horizontal rotating disk. The film is formed by the impingement of a controlled liquid jet at the center of the disk and subsequent radial spreading of liquid along the disk. The chemical reaction between the gas and the liquid film can be expressed as a zero-order homogeneous reaction. The process was modeled by establishing equations for the conservation of mass, momentum, and species concentration and solving them analytically. A scaling analysis was used to determine dominant transport processes. Appropriate boundary conditions were used to solve these equations to develop expressions for the local concentration of gas across the thickness of the film and distributions of film height, bulk concentration, and Sherwood number along the radius of the disk. The partial differential equation for species concentration was solved using the separation of variables technique along with the Duhamel's theorem and the final analytical solution was expressed using confluent hypergeometric functions. Tables for eigenvalues and eigenfunctions are presented for a number of reaction rate constants. A parametric study was performed using Reynolds number, Ekman number, and dimensionless reaction rate as parameters. At all radial locations, Sherwood number increased with Reynolds number (flow rate) as well as Ekman number (rate of rotation). The enhancement of mass transfer due to chemical reaction was found to be small when compared to the case of no reaction (pure absorption), but the enhancement factor was very significant when compared to pure absorption in a stagnant liquid film. The zero-order reaction processes considered in the present investigation included the absorption of oxygen in aqueous alkaline solutions of sodiumdithionite and rhodium complex catalyzed carbonylation of methanol. Present analytical results were compared to previous theoretical

  18. Anisotropic swim stress in active matter with nematic order

    Science.gov (United States)

    Yan, Wen; Brady, John F.

    2018-05-01

    Active Brownian particles (ABPs) transmit a swim pressure {{{\\Pi }}}{{swim}}=n\\zeta {D}{{swim}} to the container boundaries, where ζ is the drag coefficient, D swim is the swim diffusivity and n is the uniform bulk number density far from the container walls. In this work we extend the notion of the isotropic swim pressure to the anisotropic tensorial swim stress {{\\boldsymbol{σ }}}{{swim}}=-n\\zeta {{\\boldsymbol{D}}}{{swim}}, which is related to the anisotropic swim diffusivity {{\\boldsymbol{D}}}{{swim}}. We demonstrate this relationship with ABPs that achieve nematic orientational order via a bulk external field. The anisotropic swim stress is obtained analytically for dilute ABPs in both 2D and 3D systems. The anisotropy, defined as the ratio of the maximum to the minimum of the three principal stresses, is shown to grow exponentially with the strength of the external field. We verify that the normal component of the anisotropic swim stress applies a pressure {{{\\Pi }}}{{swim}}=-({{\\boldsymbol{σ }}}{{swim}}\\cdot {\\boldsymbol{n}})\\cdot {\\boldsymbol{n}} on a wall with normal vector {\\boldsymbol{n}}, and, through Brownian dynamics simulations, this pressure is shown to be the force per unit area transmitted by the active particles. Since ABPs have no friction with a wall, the difference between the normal and tangential stress components—the normal stress difference—generates a net flow of ABPs along the wall, which is a generic property of active matter systems.

  19. Simultaneous measurements of reactive scalar and velocity in a planar liquid jet with a second-order chemical reaction

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Tomoaki; Sakai, Yasuhiko; Nagata, Kouji; Terashima, Osamu [Nagoya University, Department of Mechanical Science and Engineering, Nagoya (Japan); Kubo, Takashi [Meijo University, Faculty of Science and Technology, Nagoya (Japan)

    2012-11-15

    This paper presents a new experimental approach for simultaneous measurements of velocity and concentration in a turbulent liquid flow with a chemical reaction. For the simultaneous measurements, we developed a combined probe consisting of an I-type hot-film probe and an optical fiber probe based on the light absorption spectrometric method. In a turbulent planar liquid jet with a second-order chemical reaction (A+B{yields}R), streamwise velocity and concentrations of all reactive species are measured by the combined probe. The turbulent mass fluxes of the reactive species are estimated from the simultaneous measurements. The results show that the influence of the chemical reaction on the turbulent mass flux of the reactant species near the jet exit is different from its influence in other regions, and the turbulent mass flux of the product species has a negative value near the jet exit and a positive value in other regions. (orig.)

  20. Radiative corrections to e+e- reactions to all orders in α using the renormalization group

    International Nuclear Information System (INIS)

    Tsai, Y.S.

    1983-01-01

    Renormalization group technique is used to improve the accuracy of the lowest order radiative corrections in QED. The exponentiation of infrared terms comes automatically. It also leads to exponentiation of the vertex functions. It predicts the existence of conversion of photons into pairs and the result agrees with the Kroll-Wada relation. Kinoshita-Lee-Nauenberg cancellation of mass singularities occurs to all order in α in leading log approximation in the final state if we sum over all the final states. Higher order corrections to the order α 3 asymmetry is shown to be small. The results are used to derive useful formulas for the radiative corrections to processes such as e + e - → μ + μ - , e + e - → μ + μ - γ, e + e - → hadron continuum, e + e - → very narrow resonance such as phi, and e + e - → not very narrow resonance such as Z 0

  1. Preparation, Characterization, and Catalytic Activity of MoCo/USY Catalyst on Hydrodeoxygenation Reaction of Anisole

    Science.gov (United States)

    Nugrahaningtyas, K. D.; Suharbiansah, R. S. R.; Rahmawati, F.

    2018-03-01

    This research aims to prepare, characterize, and study the catalytic activity of Molybdenum (Mo) and Cobalt (Co) metal with supporting material Ultra Stable Y-Zeolite (USY), to produce catalysts with activity in hydrotreatment reaction and in order to eliminate impurities compounds that containing unwanted groups heteroatoms. The bimetallic catalysts MoCo/USY were prepared by wet impregnation method with weight variation of Co metal 0%, 2%, 4%, 6%, 8%, and Mo metal 8% (w/w), respectively. Activation method of the catalyst included calcination, oxidation, reduction and the crystallinity was characterized using X-ray diffraction (XRD), the acidity of the catalyst was analyzed using Fourier Transform Infrared Spectroscopy (FT-IR) and gravimetry method, minerals present in the catalyst was analyzed using X-Ray Fluorescence (XRF), and surface of the catalyst was analyzed using Surface Area Analyzer (SAA). Catalytic activity test (benzene yield product) of MoCo/USY on hydrodeoxigenation reaction of anisole aimed to determine the effect of Mo-Co/USY for catalytic activity in the reaction hydrodeoxigenation (HDO) anisole. Based on characterization and test of catalytic activity, it is known that catalytic of MoCo/USY 2% (catalyst B) shows best activities with acidity of 10.209 mmol/g, specific area of catalyst of 426.295 m2/g, pore average of 14.135 Å, total pore volume 0.318 cc/g, and total yield of HDO products 6.06%.

  2. Joint of activities related to the territorial ordering

    International Nuclear Information System (INIS)

    Perez Vilca, Wilmer

    2005-01-01

    The process of territorial ordering in Peru has little experiences; one of them is the one that comes carrying out in the department from san martin, with the conduction of its respective regional government. This department is in the Amazonian natural region and comes being affected by a series from problems social (like the existence of an uncontrolled migration, deficiency of basic services), economic (unemployment, unmannerliness), legal (territorial invasions to the property, conflicts) and environmental (deforestation, gradual loss of the biodiversity, environmental contamination), in addition to the loss of leadership of the organizations responsible for the departmental development. As opposed to it, the local institutional organizations decided to give priority as of year 2004 to the project of territorial ordering as a measurement to obtain the use and suitable occupation of the territory. This project has between its characteristics the one to gather and to group the experiences in demarcation and territorial organization, economic ecological zonification, road management of the use of the territory, plans and conformation of regions. This set of activities arisen without a national technical-legal frame that unifies them is being articulated by means of the execution of a project of public investment denominated 'territorial ordering of the department of san cultural, institutional, economic and environmental martin whose indicators of management are being constructed with the purpose of evaluating their social impact. Like all developing process, it has his discharges and losses, whose lessons will be with the purpose of taking advantage of the obtained knowledge and that it has in the geomatic to one of his tools of technological support

  3. Joint of activities related to the territorial ordering

    International Nuclear Information System (INIS)

    Perez Vilca, Wilmer

    2006-01-01

    The process of territorial ordering in Peru has little experiences; one of them is the one that comes carrying out in the department from san martin, with the conduction of its respective regional government. This department is in the Amazonian natural region and comes being affected by a series from problems social (like the existent of an uncontrolled migration, deficiency of basic services), economic (unemployment, un mannerliness), legal (territorial invasions to the property, conflicts) and environmental (deforestation, gradual loss of the biodiversity, environmental contamination), in addition to the loss of leadership of the organizations responsible for the departmental development. As opposed to it, the local institutional organizations decided to give priority as of year 2004 to the project of territorial ordering as a measurement to obtain the use and suitable occupation of the territory. This project has between its characteristics the one to gather and to group the experiences in demarcation and territorial organization, economic ecological zincification, road management of the use of the territory, plans and conformation of regions. This set of activities arisen without a national technical-legal frame that unifies them is being articulated by means of the execution of a project of public investment denominated territorial ordering of the department of san cultural, institutional, economic and environmental martin, whose indicators of management are being constructed with the purpose of evaluating their social impact. Like all developing process, it has his discharges and losses, whose lessons will be with the purpose of taking advantage of the obtained knowledge and that it has in the geomatic to one of his tools of technological support

  4. Chalcogenide metal centers for oxygen reduction reaction: Activity and tolerance

    International Nuclear Information System (INIS)

    Feng Yongjun; Gago, Aldo; Timperman, Laure; Alonso-Vante, Nicolas

    2011-01-01

    This mini-review summarizes materials design methods, oxygen reduction kinetics, tolerance to small organic molecules and fuel cell performance of chalcogenide metal catalysts, particularly, ruthenium (Ru x Se y ) and non-precious transition metals (M x X y : M = Co, Fe and Ni; X = Se and S). These non-platinum catalysts are potential alternatives to Pt-based catalysts because of their comparable catalytic activity (Ru x Se y ), low cost, high abundance and, in particular, a high tolerance to small organic molecules. Developing trends of synthesis methods, mechanism of oxygen reduction reaction and applications in direct alcohol fuel cells as well as the substrate effect are highlighted.

  5. A higher-order numerical framework for stochastic simulation of chemical reaction systems.

    KAUST Repository

    Székely, Tamás

    2012-07-15

    BACKGROUND: In this paper, we present a framework for improving the accuracy of fixed-step methods for Monte Carlo simulation of discrete stochastic chemical kinetics. Stochasticity is ubiquitous in many areas of cell biology, for example in gene regulation, biochemical cascades and cell-cell interaction. However most discrete stochastic simulation techniques are slow. We apply Richardson extrapolation to the moments of three fixed-step methods, the Euler, midpoint and θ-trapezoidal τ-leap methods, to demonstrate the power of stochastic extrapolation. The extrapolation framework can increase the order of convergence of any fixed-step discrete stochastic solver and is very easy to implement; the only condition for its use is knowledge of the appropriate terms of the global error expansion of the solver in terms of its stepsize. In practical terms, a higher-order method with a larger stepsize can achieve the same level of accuracy as a lower-order method with a smaller one, potentially reducing the computational time of the system. RESULTS: By obtaining a global error expansion for a general weak first-order method, we prove that extrapolation can increase the weak order of convergence for the moments of the Euler and the midpoint τ-leap methods, from one to two. This is supported by numerical simulations of several chemical systems of biological importance using the Euler, midpoint and θ-trapezoidal τ-leap methods. In almost all cases, extrapolation results in an improvement of accuracy. As in the case of ordinary and stochastic differential equations, extrapolation can be repeated to obtain even higher-order approximations. CONCLUSIONS: Extrapolation is a general framework for increasing the order of accuracy of any fixed-step stochastic solver. This enables the simulation of complicated systems in less time, allowing for more realistic biochemical problems to be solved.

  6. A higher-order numerical framework for stochastic simulation of chemical reaction systems.

    KAUST Repository

    Szé kely, Tamá s; Burrage, Kevin; Erban, Radek; Zygalakis, Konstantinos C

    2012-01-01

    , to demonstrate the power of stochastic extrapolation. The extrapolation framework can increase the order of convergence of any fixed-step discrete stochastic solver and is very easy to implement; the only condition for its use is knowledge of the appropriate

  7. Consumer Activities and Reactions to Social Network Marketing

    Directory of Open Access Journals (Sweden)

    Bistra Vassileva

    2017-06-01

    Full Text Available The purpose of this paper is to understand consumer behavioural models with respect to their reactions to social network marketing. Theoretical background is focused on online and social network usage, motivations and behaviour. The research goal is to explore consumer reactions to the exposure of social network marketing based on the following criteria: level of brand engagement, word-of-mouth (WOM referral behaviour, and purchase intentions. Consumers are investigated based on their attitudes toward social network marketing and basic socio-demographic covariates using data from a sample size of 700 Bulgarian respondents (age group 21–54 years, Internet users, urban inhabitants. Factor and cluster analyses are applied. It is found that consumers are willing to receive information about brands and companies through social networks. They like to talk in social networks about these brands and companies and to share information as well (factor 2, brand engagement. Internet users are willing to share information received through social network advertising (factor 1, wom referral behaviour but they would not buy a certain brand as a result of brand communication activities in social networks (factor 3, purchase intention. Several practical implications regarding marketing activities through social networks are drawn.

  8. From bare to renormalized order parameter in gauge space: Structure and reactions

    Science.gov (United States)

    Potel, G.; Idini, A.; Barranco, F.; Vigezzi, E.; Broglia, R. A.

    2017-09-01

    It is not physically obvious why one can calculate with similar accuracy, as compared to the experimental data, the absolute cross section associated with two-nucleon transfer processes between members of pairing rotational bands, making use of simple BCS (constant matrix elements) or of many-body [Nambu-Gorkov (NG), nuclear field theory (NFT)] spectroscopic amplitudes. Restoration of spontaneous symmetry breaking and associated emergent generalized rigidity in gauge space provides the answer and points to a new emergence: A physical sum rule resulting from the intertwining of structure and reaction processes, closely connected with the central role induced pairing interaction plays in structure, together with the fact that successive transfer dominates Cooper pair tunneling.

  9. THERMOKINETIC STUDY OF THE ZERO, FIRST AND SECOND ORDER REACTIONS IN A PSEUDO-ADIABATIC CALORIMETER: Numerical approach and experimental dat

    Directory of Open Access Journals (Sweden)

    Johanna Mendoza

    2012-11-01

    Full Text Available The signal produced by a pseudo-adiabaticcalorimeter is simulated by numericalsolution of the differential equations thatmodel the chemical kinetics [1], the thermalproperties of the calorimetric cell[2], and the response of the thermistorused as a thermometric sensor [3]. These equations show that the calorimetricsignal is related with concentrationin a complex way. Therefore, a comparisonbetween the signals of the threebasic kinetics reactions (zero, first andsecond order was made, as a first stepto obtain a standard procedure to followchemical kinetics using a calorimeter. Inorder to help understanding this relationship,the initial rate method was applied to the simulated data to assess the relationshipbetween the order and the kineticconstants calculated with those usedfor the simulations. As it was expected,the initial rate method for the calorimetricdata, do not give a slope directly relatedwith the order of the reaction, as itwould be produced, for example, in datafrom a spectrophotometer. However, alinear relationship was found betweenwhat we call the “calorimetric order”and the kinetic order. Finally, the developedprocedure was applied to the studyof the H2O2 decomposition catalyzedwith Fe3+ in homogeneous phase andwith activated carbon in heterogeneousphase, finding the order and the kineticsconstants of the global processes, whichwere in close agreement with those inthe literature.

  10. Transient modeling of non-Fickian transport and first-order reaction using continuous time random walk

    Science.gov (United States)

    Burnell, Daniel K.; Hansen, Scott K.; Xu, Jie

    2017-09-01

    Contaminants in groundwater may experience a broad spectrum of velocities and multiple rates of mass transfer between mobile and immobile zones during transport. These conditions may lead to non-Fickian plume evolution which is not well described by the advection-dispersion equation (ADE). Simultaneously, many groundwater contaminants are degraded by processes that may be modeled as first-order decay. It is now known that non-Fickian transport and reaction are intimately coupled, with reaction affecting the transport operator. However, closed-form solutions for these important scenarios have not been published for use in applications. In this paper, we present four new Green's function analytic solutions in the uncoupled, uncorrelated continuous time random walk (CTRW) framework for reactive non-Fickian transport, corresponding to the quartet of conservative tracer solutions presented by Kreft and Zuber (1978) for Fickian transport. These consider pulse injection for both resident and flux concentration combined with detection in both resident and flux concentration. A pair of solutions for resident concentration temporal pulses with detection in both flux and resident concentration is also presented. We also derive the relationship between flux and resident concentration for non-Fickian transport with first-order reaction for this CTRW formulation. An explicit discussion of employment of the new solutions to model transport with arbitrary upgradient boundary conditions as well as mobile-immobile mass transfer is then presented. Using the new solutions, we show that first-order reaction has no effect on the anomalous spatial spreading rate of concentration profiles, but produces breakthrough curves at fixed locations that appear to have been generated by Fickian transport. Under the assumption of a Pareto CTRW transition distribution, we present a variety of numerical simulations including results showing coherence of our analytic solutions and CTRW particle

  11. Higher-order human telomeric G-quadruplex DNA metalloenzymes enhance enantioselectivity in the Diels-Alder reaction.

    Science.gov (United States)

    Li, Yinghao; Jia, Guoqing; Wang, Changhao; Cheng, Mingpan; Li, Can

    2015-03-02

    Short human telomeric (HT) DNA sequences form single G-quadruplex (G4 ) units and exhibit structure-based stereocontrol for a series of reactions. However, for more biologically relevant higher-order HT G4 -DNAs (beyond a single G4 unit), the catalytic performances are unknown. Here, we found that higher-order HT G4 -DNA copper metalloenzymes (two or three G4 units) afford remarkably higher enantioselectivity (>90 % ee) and a five- to sixfold rate increase, compared to a single G4 unit, for the Diels-Alder reaction. Electron paramagnetic resonance (EPR) and enzymatic kinetic studies revealed that the distinct catalytic function between single and higher-order G4 -DNA copper metalloenzymes can be attributed to different Cu(II) coordination environments and substrate specificity. Our finding suggests that, like protein enzymes and ribozymes, higher-order structural organization is crucial for G4 -DNA-based catalysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ju, Hua [School of Urban Rail Transportation, Soochow University, Suzhou 215006 (China); Li, Zhihu [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China); Xu, Yanhui, E-mail: xuyanhui@suda.edu.cn [College of Physics, Optoelectronics and Energy, Soochow University, Moye Rd. 688, Suzhou 215006 (China)

    2015-04-15

    Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.

  13. Porous platinum mesoflowers with enhanced activity for methanol oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang Lina; Wang Wenjin; Hong Feng [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China); Yang Shengchun, E-mail: ysch1209@mail.xjtu.edu.cn [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China); You Hongjun, E-mail: hjyou@mail.xjtu.edu.cn [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China); Fang Jixiang; Ding Bingjun [School of Science, MOE Key Laboratory for Non-equilibrium Synthesis and Modulation of Condensed Matter, Xi' an Jiaotong University, Xi' an 710049 (China)

    2012-07-15

    Porous Pt and Pt-Ag alloy mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesized using Ag mesoflowers as sacrificial template by galvanic reaction. The silver content in Pt-Ag alloys can be facilely controlled by nitric acid treatment. And the pure Pt MFs can be obtained by selective removal of silver element from Pt{sub 72}Ag{sub 28} MFs electrochemically. Both Pt{sub 45}Ag{sub 55}, Pt{sub 72}Ag{sub 28} and pure Pt show a high catalytic performance in methanol oxidation reaction (MOR). Especially, pure Pt MFs exhibited a 2 to 3 times current density enhancement in MOR compared with the commercial used Pt black, which can be attributed to their porous nanostructure with 3-dimentional nature and small crystal sizes. - Graphical Abstract: The CVs of MOR on Pt (red) and Pt black (green) catalysts in 0.1 M HClO{sub 4} and 0.5 M CH{sub 3}OH for specific mass current. The insert shows the SEM images of two porous Pt MFs. Platinum mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesised with Ag mesoflowers as sacrificial template by galvanic replacement. The porous Pt MFs exhibited a more than 3 times enhancement in electrocatalytic performance for methanol oxidation reaction compared the commercial used Pt black. Highlights: Black-Right-Pointing-Pointer Porous Pt and Pt-Ag mesoflowers (MFs) were synthesized using Ag MFs sacrifical template. Black-Right-Pointing-Pointer Pt MFs presents an improved catalytic activity in MOR compared with Pt black. Black-Right-Pointing-Pointer We provided a facile approach for the development of high performance Pt electrocatalysts for fuel cells.

  14. Audience reaction movie trailers and the Paranormal Activity franchise

    Directory of Open Access Journals (Sweden)

    Alexander Swanson

    2015-03-01

    Full Text Available This article addresses the concept and growing practice of audience reaction movie trailers, specifically for films in the horror genre. Popularized by the Paranormal Activity series of films, these trailers primarily utilize green night-vision video footage of a movie theater audience reacting to the film being advertised, yet also consist of webcam recordings of screaming fans, documentary-style B-roll footage of audiences filing into preview screenings with high levels of anticipation, and close-up shots of spectator facial expressions, accompanied by no footage whatsoever from the film being advertised. In analyzing these audience-centric promotional paratexts, my aim is to reveal them as attempting to sell and legitimize the experiential, communal, and social qualities of the theatrical movie viewing experience while at the same time calling for increased fan investment in both physical and online spaces. Through the analysis of audience reaction trailers, this article hopes to both join and engender conversations about horror fan participation, the nature of anticipatory texts as manipulative, and the current state of horror gimmickry in the form of the promotional paratext.

  15. Quantum infinite order sudden approximation for ion-molecule reactions: treatment of the He + H2+ system

    International Nuclear Information System (INIS)

    Baer, M.; Nakamura, H.; Kouri, D.J.

    1986-01-01

    In this work the ion-molecule reaction He + H 2 + (v/sub i/) → HeH + (v/sub f/) + H(v/sub i/ = 0-7, v/sub f/ = 0-2) was studied quantum mechanically in the energy range 1.3 eV ≤ E/sub tot/ ≤ 1.8 eV. The calculations were carried out employing the Reactive Infinite Order Sudden Approximation (RIOSA). The two features characteristic of this system in the above energy range, namely the strong enhancement of the reaction rate with the initial vibrational energy (at a fixed total energy) and the relatively weak dependence of the cross sections on translational energy, were found to be well reproduced in the numerical treatment. The results also revealed the existence of two mechanisms of the exchange process: one is the ordinary mechanism and the other is probably related to the spectator stripping model

  16. Infinite-order-sudden method for light--heavy--light reactions: Application to D+HCl→DCl+H

    International Nuclear Information System (INIS)

    Clary, D.C.; Drolshagen, G.

    1982-01-01

    An infinite-order-sudden (IOS) theory for light-heavy-light reactions is applied to the D+HCl(v = 0, j)→DCl(v'< or =1, j')+H reaction. The results are compared with those obtained using a more accurate quantum-dynamical technique, the ESA--CSA method, in which the energy sudden approximation is used for the entrance channel, while the centrifugal sudden approximation is employed for the exit channel. The computations have been performed using LEPS and DIM potential energy surfaces. We obtain good agreement between the IOS and ESA--CSA results, not only for averaged quantities such as rate coefficients, but also for detailed vibrational-rotational reactive cross sections

  17. Recent development of active nanoparticle catalysts for fuel cell reactions

    Energy Technology Data Exchange (ETDEWEB)

    Mazumder, Vismadeb; Lee, Youngmin; Sun, Shouheng [Department of Chemistry Brown University Providence, RI (United States)

    2010-04-23

    This review focuses on the recent advances in the synthesis of nanoparticle (NP) catalysts of Pt-, Pd- and Au-based NPs as well as composite NPs. First, new developments in the synthesis of single-component Pt, Pd and Au NPs are summarized. Then the chemistry used to make alloy and composite NP catalysts aiming to enhance their activity and durability for fuel cell reactions is outlined. The review next introduces the exciting new research push in developing CoN/C and FeN/C as non-Pt catalysts. Examples of size-, shape- and composition-dependent catalyses for oxygen reduction at cathode and formic acid oxidation at anode are highlighted to illustrate the potentials of the newly developed NP catalysts for fuel cell applications. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  18. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  19. syk kinase activation by a src kinase-initiated activation loop phosphorylation chain reaction

    Science.gov (United States)

    El-Hillal, O.; Kurosaki, T.; Yamamura, H.; Kinet, J.-P.; Scharenberg, A. M.

    1997-01-01

    Activation of the syk tyrosine kinase occurs almost immediately following engagement of many types of antigen receptors, including Fc receptors, but the mechanism through which syk is activated is currently unclear. Here we demonstrate that Fc receptor-induced syk activation occurs as the result of phosphorylation of the syk activation loop by both src family kinases and other molecules of activated syk, suggesting that syk activation occurs as the result of a src kinase-initiated activation loop phosphorylation chain reaction. This type of activation mechanism predicts that syk activation would exhibit exponential kinetics, providing a potential explanation for its rapid and robust activation by even weak antigen receptor stimuli. We propose that a similar mechanism may be responsible for generating rapid activation of other cytoplasmic tyrosine kinases, such as those of the Bruton tyrosine kinase/tec family, as well. PMID:9050880

  20. Some Investigations of the Reaction of Activated Charcoal with Fluorine and Uranium Hexafluoride

    Energy Technology Data Exchange (ETDEWEB)

    Del Cul, G.D.; Fiedor, J.N.; Simmons, D.W.; Toth, L.M.; Trowbridge, L.D.; Williams

    1998-09-01

    The Molten Salt Reactor Experiment (MSRE) at Oak Ridge National Laboratory has been shut down since 1969, when the fuel salt was drained from the core into two Hastelloy N drain tanks at the reactor site. Over time, fluorine (F{sub 2}) and uranium hexafluoride (UF{sub 6}) moved from the salt through the gas piping to a charcoal bed, where they reacted with the activated charcoal. Some of the immediate concerns related to the migration of F{sub 2} and UF{sub 6} to the charcoal bed were the possibility of explosive reactions between the charcoal and F{sub 2}, the existence of conditions that could induce a criticality accident, and the removal and recovery of the fissile uranium from the charcoal. This report addresses the reactions and reactivity of species produced by the reaction of fluorine and activated charcoal and between charcoal and F{sub 2}-UF{sub 6} gas mixtures in order to support remediation of the MSRE auxiliary charcoal bed (ACB) and the recovery of the fissile uranium. The chemical identity, stoichiometry, thermochemistry, and potential for explosive decomposition of the primary reaction product, fluorinated charcoal, was determined.

  1. Some Investigations of the Reaction of Activated Charcoal with Fluorine and Uranium Hexafluoride

    International Nuclear Information System (INIS)

    Del Cul, G.D.; Fiedor, J.N.; Simmons, D.W.; Toth, L.M.; Trowbridge, L.D.; Williams

    1998-01-01

    The Molten Salt Reactor Experiment (MSRE) at Oak Ridge National Laboratory has been shut down since 1969, when the fuel salt was drained from the core into two Hastelloy N drain tanks at the reactor site. Over time, fluorine (F 2 ) and uranium hexafluoride (UF 6 ) moved from the salt through the gas piping to a charcoal bed, where they reacted with the activated charcoal. Some of the immediate concerns related to the migration of F 2 and UF 6 to the charcoal bed were the possibility of explosive reactions between the charcoal and F 2 , the existence of conditions that could induce a criticality accident, and the removal and recovery of the fissile uranium from the charcoal. This report addresses the reactions and reactivity of species produced by the reaction of fluorine and activated charcoal and between charcoal and F 2 -UF 6 gas mixtures in order to support remediation of the MSRE auxiliary charcoal bed (ACB) and the recovery of the fissile uranium. The chemical identity, stoichiometry, thermochemistry, and potential for explosive decomposition of the primary reaction product, fluorinated charcoal, was determined

  2. SENSMG: First-Order Sensitivities of Neutron Reaction Rates, Reaction-Rate Ratios, Leakage, keff, and α Using PARTISN

    Energy Technology Data Exchange (ETDEWEB)

    Favorite, Jeffrey A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-11-21

    SENSMG is a tool for computing first-order sensitivities of neutron reaction rates, reaction-rate ratios, leakage, keff, and α using the PARTISN multigroup discrete-ordinates code. SENSMG computes sensitivities to all of the transport cross sections and data (total, fission, nu, chi, and all scattering moments), two edit cross sections (absorption and capture), and the density for every isotope and energy group. It also computes sensitivities to the mass density for every material and derivatives with respect to all interface locations. The tool can be used for one-dimensional spherical (r) and two-dimensional cylindrical (r-z) geometries. The tool can be used for fixed-source and eigenvalue problems. The tool implements Generalized Perturbation Theory (GPT) as discussed by Williams and Stacey. Section II of this report describes the theory behind adjoint-based sensitivities, gives the equations that SENSMG solves, and defines the sensitivities that are output. Section III describes the user interface, including the input file and command line options. Section IV describes the output. Section V gives some notes about the coding that may be of interest. Section VI discusses verification, which is ongoing. Section VII lists needs and ideas for future work. Appendix A lists all of the input files whose results are presented in Sec. VI.

  3. The Active Fractional Order Control for Maglev Suspension System

    Directory of Open Access Journals (Sweden)

    Peichang Yu

    2015-01-01

    Full Text Available Maglev suspension system is the core part of maglev train. In the practical application, the load uncertainties, inherent nonlinearity, and misalignment between sensors and actuators are the main issues that should be solved carefully. In order to design a suitable controller, the attention is paid to the fractional order controller. Firstly, the mathematical model of a single electromagnetic suspension unit is derived. Then, considering the limitation of the traditional PD controller adaptation, the fractional order controller is developed to obtain more excellent suspension specifications and robust performance. In reality, the nonlinearity affects the structure and the precision of the model after linearization, which will degrade the dynamic performance. So, a fractional order controller is addressed to eliminate the disturbance by adjusting the parameters which are added by the fractional order controller. Furthermore, the controller based on LQR is employed to compare with the fractional order controller. Finally, the performance of them is discussed by simulation. The results illustrated the validity of the fractional order controller.

  4. Determination of redox reaction rates and orders by in situ liquid cell electron microscopy of Pd and Au solution growth.

    Science.gov (United States)

    Sutter, Eli A; Sutter, Peter W

    2014-12-03

    In-situ liquid cell transmission and scanning transmission electron microscopy (TEM/STEM) experiments are important, as they provide direct insight into processes in liquids, such as solution growth of nanoparticles, among others. In liquid cell TEM/STEM redox reaction experiments, the hydrated electrons e(-)aq created by the electron beam are responsible for the reduction of metal-ion complexes. Here we investigate the rate equation of redox reactions involving reduction by e(-)aq generated by the electron beam during in situ liquid TEM/STEM. Specifically we consider the growth of Pd on Au seeds in aqueous solutions containing Pd-chloro complexes. From the quantification of the rate of Pd deposition at different electron beam currents and as a function of distance from a stationary, nanometer-sized exciting beam, we determine that the reaction is first order with respect to the concentration of hydrated electrons, [e(-)aq]. By comparing Pd- and Au-deposition, we further demonstrate that measurements of the local deposition rate on nanoparticles in the solution via real-time imaging can be used to measure not only [e(-)aq] but also the rate of reduction of a metal-ion complex to zerovalent metal atoms in solution.

  5. Controlling morphology, mesoporosity, crystallinity, and photocatalytic activity of ordered mesoporous TiO{sub 2} films prepared at low temperature

    Energy Technology Data Exchange (ETDEWEB)

    Elgh, Björn; Yuan, Ning; Palmqvist, Anders E. C. [Applied Surface Chemistry, Department of Chemical and Biological Engineering, Chalmers University of Technology, SE 412 96 Göteborg (Sweden); Cho, Hae Sung; Terasaki, Osamu [Graduate School of EEWS (WCU), KAIST, Daejeon 305-701 (Korea, Republic of); Magerl, David; Philipp, Martine; Müller-Buschbaum, Peter [Lehrstuhl für Funktionelle Materialien, Physik-Department, Technische Universität München, 85748 Garching (Germany); Roth, Stephan V. [DESY, Notkestrasse 85, 22603 Hamburg (Germany); Yoon, Kyung Byung [Department of Chemistry, Sogang University, Seoul 121-742 (Korea, Republic of)

    2014-11-01

    Partly ordered mesoporous titania films with anatase crystallites incorporated into the pore walls were prepared at low temperature by spin-coating a microemulsion-based reaction solution. The effect of relative humidity employed during aging of the prepared films was studied using SEM, TEM, and grazing incidence small angle X-ray scattering to evaluate the mesoscopic order, porosity, and crystallinity of the films. The study shows unambiguously that crystal growth occurs mainly during storage of the films and proceeds at room temperature largely depending on relative humidity. Porosity, pore size, mesoscopic order, crystallinity, and photocatalytic activity of the films increased with relative humidity up to an optimum around 75%.

  6. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15-December 31, 1984

    International Nuclear Information System (INIS)

    1985-01-01

    Energetic halogen atoms or ions, activated by various nuclear transformations are studied in gas, high pressure and condensed phase saturated and unsaturated hydrocarbons, halomethanes, and liquid and solid aqueous solutions of biomolecular and organic solutes in order to understand better the mechanisms and dynamics of high energy monovalent species. The experimental program and its goals remain the same, consisting of four interrelated areas: (1) The stereochemistry of energetic 18 F, /sup 34m/Cl, and 38 Cl substitution reactions with chiral molecules in the gas and condensed phase is studied. (2) The gas to condensed state transition in halogen high energy chemistry, involving energetic chlorine, bromine, and iodine reactions in halomethanes, saturated and unsaturated hydrocarbons and aqueous solutions of biomolecules and alkyl halides is being investigated in more detail. Current attention is given to defining the nature of the enhancement yields in the condensed phase. Specifically, energetic halogen reactions in liquid and frozen aqueous solutions or organic and biomolecular solutes are studied. (3) Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular and organic solutes in liquid and frozen aqueous solutions are being studied in an attempt to learn more about the activation events in the condensed phase. (4) The applications of hot chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Current attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as site indicators in liquid and frozen aqueous solutions of halogenated bases and nucleosides are currently being developed. 14 references

  7. Aerobic composting of waste activated sludge: Kinetic analysis for microbiological reaction and oxygen consumption

    International Nuclear Information System (INIS)

    Yamada, Y.; Kawase, Y.

    2006-01-01

    In order to examine the optimal design and operating parameters, kinetics for microbiological reaction and oxygen consumption in composting of waste activated sludge were quantitatively examined. A series of experiments was conducted to discuss the optimal operating parameters for aerobic composting of waste activated sludge obtained from Kawagoe City Wastewater Treatment Plant (Saitama, Japan) using 4 and 20 L laboratory scale bioreactors. Aeration rate, compositions of compost mixture and height of compost pile were investigated as main design and operating parameters. The optimal aerobic composting of waste activated sludge was found at the aeration rate of 2.0 L/min/kg (initial composting mixture dry weight). A compost pile up to 0.5 m could be operated effectively. A simple model for composting of waste activated sludge in a composting reactor was developed by assuming that a solid phase of compost mixture is well mixed and the kinetics for microbiological reaction is represented by a Monod-type equation. The model predictions could fit the experimental data for decomposition of waste activated sludge with an average deviation of 2.14%. Oxygen consumption during composting was also examined using a simplified model in which the oxygen consumption was represented by a Monod-type equation and the axial distribution of oxygen concentration in the composting pile was described by a plug-flow model. The predictions could satisfactorily simulate the experiment results for the average maximum oxygen consumption rate during aerobic composting with an average deviation of 7.4%

  8. Development of various reaction abilities and their relationships with favorite play activities in preschool children.

    Science.gov (United States)

    Miyaguchi, Kazuyoshi; Demura, Shinich; Sugiura, Hiroki; Uchiyama, Masanobu; Noda, Masahiro

    2013-10-01

    This study examines the development of various reaction movements in preschool children and the relationship between reaction times and favorite play activities. The subjects were 167 healthy preschool children aged 4-6 (96 boys and 71 girls). This study focused on the reaction times of the upper limbs (reaction 1: release; reaction 2: press) and the whole body (reaction 3: forward jump). The activities frequently played in preschools are largely divided into dynamic play activities (tag, soccer, gymnastics set, dodge ball, and jump rope) and static play activities (drawing, playing house, reading, playing with sand, and building blocks). The subjects chose 3 of 10 cards picturing their favorite play activities, depicting 10 different activities. All intraclass correlation coefficients of measured reaction times were high (0.73-0.79). In addition, each reaction time shortened with age. Reaction 1 showed a significant and low correlation with reaction 3 (r = 0.37). The effect size of the whole body reaction time was the largest. Whole body reaction movement, which is largely affected by the exercise output function, develops remarkably in childhood. Children who liked "tag" were faster in all reaction times. The children who chose "soccer" were faster in reactions 2 and 3. In contrast, children who liked "playing house" tended to have slower reaction times. Dynamic activities, such as tag and soccer, promote development of reaction speed and agility in movements involving the whole body. Preschool teachers and physical educators should re-examine the effect of tag and use it periodically as one of the exercise programs to avoid unexpected falls and injuries in everyday life.

  9. Biological activities of secondary metabolites of the order Zoanthids

    OpenAIRE

    Zahra Aminikhoei; Zeinab Janahmadi; Iraj Nabipour

    2015-01-01

    The phylum Cnidaria is a large, diverse and ecologically important group of marine invertebrates, which produce powerful toxins and venoms. The number of marine natural product from cnidarians isolated from class Anthozoa. Among the Anthozoa, the order of zoanthids are sessile, clonal and mostly brightly colored invertebrate which produce high biodiversity of cytolitic, neurotoxic and cardiotoxic compounds. Zoanthids containing palytoxins are reportedly among the most toxic marine organisms k...

  10. Catalytic activation of molecular hydrogen in alkyne hydrogenation reactions by lanthanide metal vapor reaction products

    International Nuclear Information System (INIS)

    Evans, W.J.; Bloom, I.; Engerer, S.C.

    1983-01-01

    A rotary metal vapor was used in the synthesis of Lu, Er, Nd, Sm, Yb, and La alkyne, diene, and phosphine complexes. A typical catalytic hydrogenation experiment is described. The lanthanide metal vapor product is dissolved in tetrahydrofuran or toluene and placed in a pressure reaction vessel 3-hexyne (or another substrate) is added, the chamber attached to a high vacuum line, cooled to -196 0 C, evacuated, warmed to ambient temperature and hydrogen is added. The solution is stirred magnetically while the pressure in monitored. The reaction products were analyzed by gas chromatography. Rates and products of various systems are listed. This preliminary survey indicates that catalytic reaction chemistry is available to these metals in a wide range of coordination environments. Attempts to characterize these compounds are hampered by their paramagnetic nature and their tendency to polymerize

  11. Reaction kinetics aspect of U3O8 kernel with gas H2 on the characteristics of activation energy, reaction rate constant and O/U ratio of UO2 kernel

    International Nuclear Information System (INIS)

    Damunir

    2007-01-01

    The reaction kinetics aspect of U 3 O 8 kernel with gas H 2 on the characteristics of activation energy, reaction rate constant and O/U ratio of UO 2 kernel had been studied. U 3 O 8 kernel was reacted with gas H 2 in a reduction furnace at varied reaction time and temperature. The reaction temperature was varied at 600, 700, 750 and 850 °C with a pressure of 50 mmHg for 3 hours in gas N 2 atmosphere. The reation time was varied at 1, 2, 3 and 4 hours at a temperature of 750 °C using similar conditions. The reaction product was UO 2 kernel. The reaction kinetic aspect between U 3 O 8 and gas H 2 comprised the minimum activation energy (ΔE), the reaction rate constant and the O/U ratio of UO 2 kernel. The minimum activation energy was determined from a straight line slope of equation ln [{D b . R o {(1 - (1 - X b ) ⅓ } / (b.t.Cg)] = -3.9406 x 10 3 / T + 4.044. By multiplying with the straight line slope -3.9406 x 10 3 , the ideal gas constant (R) 1.985 cal/mol and the molarity difference of reaction coefficient 2, a minimum activation energy of 15.644 kcal/mol was obtained. The reaction rate constant was determined from first-order chemical reaction control and Arrhenius equation. The O/U ratio of UO 2 kernel was obtained using gravimetric method. The analysis result of reaction rate constant with chemical reaction control equation yielded reaction rate constants of 0.745 - 1.671 s -1 and the Arrhenius equation at temperatures of 650 - 850 °C yielded reaction rate constants of 0.637 - 2.914 s -1 . The O/U ratios of UO 2 kernel at the respective reaction rate constants were 2.013 - 2.014 and the O/U ratios at reaction time 1 - 4 hours were 2.04 - 2.011. The experiment results indicated that the minimum activation energy influenced the rate constant of first-order reaction and the O/U ratio of UO 2 kernel. The optimum condition was obtained at reaction rate constant of 1.43 s -1 , O/U ratio of UO 2 kernel of 2.01 at temperature of 750 °C and reaction time of 3

  12. Consumer Activities and Reactions to Social Network Marketing

    OpenAIRE

    Bistra Vassileva

    2017-01-01

    The purpose of this paper is to understand consumer behavioural models with respect to their reactions to social network marketing. Theoretical background is focused on online and social network usage, motivations and behaviour. The research goal is to explore consumer reactions to the exposure of social network marketing based on the following criteria: level of brand engagement, word-of-mouth (WOM) referral behaviour, and purchase intentions. Consumers are investigated ...

  13. Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model

    NARCIS (Netherlands)

    Bickelhaupt, F. Matthias; Houk, Kendall N.

    2017-01-01

    The activation strain or distortion/interaction model is a tool to analyze activation barriers that determine reaction rates. For bimolecular reactions, the activation energies are the sum of the energies to distort the reactants into geometries they have in transition states plus the interaction

  14. Catalytic Activities of Noble Metal Phosphides for Hydrogenation and Hydrodesulfurization Reactions

    Directory of Open Access Journals (Sweden)

    Yasuharu Kanda

    2018-04-01

    Full Text Available In this work, the development of a highly active noble metal phosphide (NMXPY-based hydrodesulfurization (HDS catalyst with a high hydrogenating ability for heavy oils was studied. NMXPY catalysts were obtained by reduction of P-added noble metals (NM-P, NM: Rh, Pd, Ru supported on SiO2. The order of activities for the hydrogenation of biphenyl was Rh-P > NiMoS > Pd-P > Ru-P. This order was almost the same as that of the catalytic activities for the HDS of dibenzothiophene. In the HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT, the HDS activity of the Rh-P catalyst increased with increasing reaction temperature, but the maximum HDS activity for the NiMoS catalyst was observed at 270 °C. The Rh-P catalyst yielded fully hydrogenated products with high selectivity compared with the NiMoS catalyst. Furthermore, XRD analysis of the spent Rh-P catalysts revealed that the Rh2P phase possessed high sulfur tolerance and resistance to sintering.

  15. A highly efficient electrocatalyst for oxygen reduction reaction: phosphorus and nitrogen co-doped hierarchically ordered porous carbon derived from an iron-functionalized polymer

    Science.gov (United States)

    Deng, Chengwei; Zhong, Hexiang; Li, Xianfeng; Yao, Lan; Zhang, Huamin

    2016-01-01

    Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic electrolytes, thus making the catalyst promising for fuel cells. The correlations between the unique pore structure and the nitrogen and phosphorus configuration of the catalysts with high catalytic activity are thoroughly investigated.Heteroatom-doped carbon materials have shown respectable activity for the oxygen reduction reaction (ORR) in alkaline media. However, the performances of these materials are not satisfactory for energy conversion devices, such as fuel cells. Here, we demonstrate a new type of phosphorus and nitrogen co-doped hierarchically ordered porous carbon (PNHOPC) derived from an iron-functionalized mesoporous polymer through an evaporation-induced self-assembly process that simultaneously combines the carbonization and nitrogen doping processes. The soft template and the nitrogen doping process facilitate the formation of the hierarchically ordered structure for the PNHOPC. The catalyst possesses a large surface area (1118 cm2 g-1) and a pore volume of 1.14 cm3 g-1. Notably, it exhibits excellent ORR catalytic performance, superior stability and methanol tolerance in acidic

  16. Enrichment: CRISLA [chemical reaction by isotope selective activation] aims to reduce costs

    International Nuclear Information System (INIS)

    Eerkens, J.W.

    1989-01-01

    Every year, more than $3 billion is spent on enriching uranium. CRISLA (Chemical Reaction by Isotope Selective Activation) uses a laser-catalyzed chemical reaction which, its proponents claim, could substantially reduce these costs. In CRISLA, an infrared CO laser illuminates the intracavity reaction cell (IC) at a frequency tuned to excite primarily UF 6 . When UF 6 and co-reactant RX are passed through the IC, the tuned laser photons preferentially enhance the reaction of UF 6 with RX ten-thousand-fold over the thermal reaction rate. Thus the laser serves as an activator and the chemical energy for separation is largely chemical. (author)

  17. The Atmospherically Important Reaction of Hydroxyl Radicals with Methyl Nitrate: A Theoretical Study Involving the Calculation of Reaction Mechanisms, Enthalpies, Activation Energies, and Rate Coefficients.

    Science.gov (United States)

    Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

    2017-09-07

    A theoretical study, involving the calculation of reaction enthalpies, activation energies, mechanisms, and rate coefficients, was made of the reaction of hydroxyl radicals with methyl nitrate, an important process for methyl nitrate removal in the earth's atmosphere. Four reaction channels were considered: formation of H 2 O + CH 2 ONO 2 , CH 3 OOH + NO 2 , CH 3 OH + NO 3 , and CH 3 O + HNO 3 . For all channels, geometry optimization and frequency calculations were performed at the M06-2X/6-31+G** level, while relative energies were improved at the UCCSD(T*)-F12/CBS level. The major channel is found to be the H abstraction channel, to give the products H 2 O + CH 2 ONO 2 . The reaction enthalpy (ΔH 298 K RX ) of this channel is computed as -17.90 kcal mol -1 . Although the other reaction channels are also exothermic, their reaction barriers are high (>24 kcal mol -1 ), and therefore these reactions do not contribute to the overall rate coefficient in the temperature range considered (200-400 K). Pathways via three transition states were identified for the H abstraction channel. Rate coefficients were calculated for these pathways at various levels of variational transition state theory including tunneling. The results obtained are used to distinguish between two sets of experimental rate coefficients, measured in the temperature range of 200-400 K, one of which is approximately an order of magnitude greater than the other. This comparison, as well as the temperature dependence of the computed rate coefficients, shows that the lower experimental values are favored. The implications of the results to atmospheric chemistry are discussed.

  18. Activation measurements of α-induced reactions at sub-Coulomb energies

    Energy Technology Data Exchange (ETDEWEB)

    Scholz, Philipp; Dewald, Alfred; Heinze, Stefan; Mayer, Jan; Mueller-Gatermann, Claus; Netterdon, Lars; Zilges, Andreas [Institute for Nuclear Physics, University of Cologne (Germany); Endres, Anne [Institute for Applied Physics, Goethe University Frankfurt am Main (Germany)

    2015-07-01

    Network calculations of the γ process rely almost completely on theoretically predicted reaction rates within the scope of the Hauser-Feshbach Statistical Model. Especially the prediction of cross sections for (γ,α)-reactions at energies within or close to the astrophysically relevant energy window remains a problem due to the uncertainties in the underlying α-optical-model potentials. Although experimental values far above the Coulomb-barrier are well reproduced, commonly used α-optical potentials often fail to describe the trend at energies comparable to those at astrophysical sites of the γ process. Improvements of the adopted optical-model potentials are hampered by the lack of experimental cross sections at sub-Coulomb energies. In order to enlarge the experimental data base, cross sections of the {sup 187}Re(α,n) and {sup 108}Cd(α,n) reactions were investigated using the activation technique with the Cologne Clover Counting Setup. Besides recent experimental results, future plans for more sensitive cross-section studies applying Accelerator Mass Spectrometry using CologneAMS are presented.

  19. Statistical analysis of activation and reaction energies with quasi-variational coupled-cluster theory

    Science.gov (United States)

    Black, Joshua A.; Knowles, Peter J.

    2018-06-01

    The performance of quasi-variational coupled-cluster (QV) theory applied to the calculation of activation and reaction energies has been investigated. A statistical analysis of results obtained for six different sets of reactions has been carried out, and the results have been compared to those from standard single-reference methods. In general, the QV methods lead to increased activation energies and larger absolute reaction energies compared to those obtained with traditional coupled-cluster theory.

  20. Proliferative activity as a prognostic factor of a human tumor radiation reactions

    International Nuclear Information System (INIS)

    Karakulov, R.K.; Pelevina, I.I.

    1986-01-01

    The following questions are considered: 1) whether cell proliferation initial parameters can serve for predicting the tumor radial reaction; 2) whether proliferative activity change can be a criterion for estimating the treatment efficiency; 3) acquisition of data on biological peculiarities of different types of tumors. Connection between proliferative activity drop and clinical reaction under tumor radiotherapy is ascertained

  1. Halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1975--February 14, 1976

    International Nuclear Information System (INIS)

    Rack, E.P.

    1976-02-01

    High energy reactions of halogen atoms or ions, activated by nuclear transformations, are being studied in gaseous, high pressure, and condensed phase saturated and unsaturated hydrocarbons, halomethanes, and other organic systems. Experimental and theoretical data are presented in the following areas: systematics of iodine hot atom reactions in halomethanes, reactions and systematics of iodine reactions with pentene and butene isomers, radiative neutron capture activated reactions of iodine with acetylene, gas to liquid to solid transition in hot atom chemistry, kinetic theory applications of hot atom reactions and the mathematical development of caging reactions, solvent dependence of the stereochemistry of the 38 Cl for Cl substitution following 37 Cl(n,γ) 38 Cl in liquid meso and dl-(CHFCl) 2 . A technique was also developed for the radioassay of Al in urine specimens

  2. Reactions of 3-Formylchromone with Active Methylene and Methyl Compounds and Some Subsequent Reactions of the Resulting Condensation Products

    Directory of Open Access Journals (Sweden)

    M. Lácova

    2005-08-01

    Full Text Available This review presents a survey of the condensations of 3-formylchromone with various active methylene and methyl compounds, e.g. malonic or barbituric acid derivatives, five-membered heterocycles, etc. The utilisation of the condensation products for the synthesis of different heterocyclic systems, which is based on the ability of the γ-pyrone ring to be opened by the nucleophilic attack is also reviewed. Finally, the applications of microwave irradiation as an unconventional method of reaction activation in the synthesis of condensation products is described and the biological activity of some chromone derivatives is noted.

  3. Alkali silica reaction (ASR) in cement free alkali activated sustainable concrete.

    Science.gov (United States)

    2016-12-19

    This report summarizes the findings of an experimental evaluation into alkali silica : reaction (ASR) in cement free alkali-activated slag and fly ash binder concrete. The : susceptibility of alkali-activated fly ash and slag concrete binders to dele...

  4. Health Activities Project (HAP): Action/Reaction Module.

    Science.gov (United States)

    Buller, Dave; And Others

    Contained within this Health Activities Project (HAP) learning packet are activities for children in grades 5-8. Design of the activities centers around the idea that students can control their own health and safety. Within this module are teacher and student folios describing activities in timing, improving, and practicing to improve reaction…

  5. Improvement of ACE inhibitory activity of casein hydrolysate by Maillard reaction with xylose.

    Science.gov (United States)

    Hong, Xu; Meng, Jun; Lu, Rong-Rong

    2015-01-01

    The Maillard reaction is widely used to improve the functional properties or biological activities of food. The purpose of this study was to investigate the effect of the Maillard reaction on angiotensin I converting enzyme (ACE) inhibitory activity in a casein hydrolysate-xylose system. Two-step hydrolysis was used to prepare casein ACE inhibitory peptides. Maillard reaction products (MRPs) were prepared by heating hydrolyzed casein with xylose at pH 8.0, 110 °C for up to 16 h. The results showed that the content of free amino group decreased (P Maillard reaction (P reaction in the MRPs. The study shows that the Maillard reaction under appropriate conditions can improve the ACE inhibitory activity of casein hydrolysate effectively. © 2014 Society of Chemical Industry.

  6. Carbonylation as a key reaction in anaerobic acetone activation by Desulfococcus biacutus.

    Science.gov (United States)

    Gutiérrez Acosta, Olga B; Hardt, Norman; Schink, Bernhard

    2013-10-01

    Acetone is activated by aerobic and nitrate-reducing bacteria via an ATP-dependent carboxylation reaction to form acetoacetate as the first reaction product. In the activation of acetone by sulfate-reducing bacteria, acetoacetate has not been found to be an intermediate. Here, we present evidence of a carbonylation reaction as the initial step in the activation of acetone by the strictly anaerobic sulfate reducer Desulfococcus biacutus. In cell suspension experiments, CO was found to be a far better cosubstrate for acetone activation than CO2. The hypothetical reaction product, acetoacetaldehyde, is extremely reactive and could not be identified as a free intermediate. However, acetoacetaldehyde dinitrophenylhydrazone was detected by mass spectrometry in cell extract experiments as a reaction product of acetone, CO, and dinitrophenylhydrazine. In a similar assay, 2-amino-4-methylpyrimidine was formed as the product of a reaction between acetoacetaldehyde and guanidine. The reaction depended on ATP as a cosubstrate. Moreover, the specific activity of aldehyde dehydrogenase (coenzyme A [CoA] acylating) tested with the putative physiological substrate was found to be 153 ± 36 mU mg(-1) protein, and its activity was specifically induced in extracts of acetone-grown cells. Moreover, acetoacetyl-CoA was detected (by mass spectrometry) after the carbonylation reaction as the subsequent intermediate after acetoacetaldehyde was formed. These results together provide evidence that acetoacetaldehyde is an intermediate in the activation of acetone by sulfate-reducing bacteria.

  7. The dual effects of Maillard reaction and enzymatic hydrolysis on the antioxidant activity of milk proteins.

    Science.gov (United States)

    Oh, N S; Lee, H A; Lee, J Y; Joung, J Y; Lee, K B; Kim, Y; Lee, K W; Kim, S H

    2013-08-01

    The objective of this study was to determine the enhanced effects on the biological characteristics and antioxidant activity of milk proteins by the combination of the Maillard reaction and enzymatic hydrolysis. Maillard reaction products were obtained from milk protein preparations, such as whey protein concentrates and sodium caseinate with lactose, by heating at 55°C for 7 d in sodium phosphate buffer (pH 7.4). The Maillard reaction products, along with untreated milk proteins as controls, were hydrolyzed for 0 to 3h with commercial proteases Alcalase, Neutrase, Protamex, and Flavorzyme (Novozymes, Bagsværd, Denmark). The antioxidant activity of hydrolyzed Maillard reaction products was determined by reaction with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt, their 1,1-diphenyl-2-picrylhydrazyl radical scavenging activity, and the ability to reduce ferric ions. Further characteristics were evaluated by the o-phthaldialdehyde method and sodium dodecyl sulfate-PAGE. The degree of hydrolysis gradually increased in a time-dependent manner, with the Alcalase-treated Maillard reaction products being the most highly hydrolyzed. Radical scavenging activities and reducing ability of hydrolyzed Maillard reaction products increased with increasing hydrolysis time. The combined products of enzymatic hydrolysis and Maillard reaction showed significantly greater antioxidant activity than did hydrolysates or Maillard reaction products alone. The hydrolyzed Maillard reaction products generated by Alcalase showed significantly higher antioxidant activity when compared with the other protease products and the antioxidant activity was higher for the whey protein concentrate groups than for the sodium caseinate groups. These findings indicate that Maillard reaction products, coupled with enzymatic hydrolysis, could act as potential antioxidants in the pharmaceutical, food, and dairy industries. Copyright © 2013 American Dairy Science Association

  8. The Effect of Sports and Physical Activity on Elderly Reaction Time and Response Time

    Directory of Open Access Journals (Sweden)

    Abdolrahman Khezri

    2014-07-01

    Full Text Available Objectives: Physical activities ameliorate elderly motor and cognitive performance. The aim of this research is to study the effect of sport and physical activity on elderly reaction time and response time. Methods & Materials: The research method is causal-comparative and its statistical population consists of 60 active and non-active old males over 60 years residing at Mahabad city. Reaction time was measured by reaction timer apparatus, made in Takei Company (YB1000 model. Response time was measured via Nelson’s Choice- Response Movement Test. At first, reaction time and then response time was measured. For data analysis, descriptive statistic, K-S Test and One Sample T Test were used Results K-S Test show that research data was parametric. According to the results of this research, physical activity affected reaction time and response time. Results: of T test show that reaction time (P=0.000 and response time (P=0.000 of active group was statistically shorter than non- active group. Conclusion: The result of current study demonstrate that sport and physical activity, decrease reaction and response time via psychomotor and physiological positive changes.

  9. Mass transfer with complex chemical reactions in gas–liquid systems : two-step reversible reactions with unit stoichiometric and kinetic orders

    NARCIS (Netherlands)

    Vas Bhat, R.D.; Kuipers, J.A.M.; Versteeg, G.F.

    2000-01-01

    An absorption model to study gas–liquid mass transfer accompanied by reversible two-step reactions in the liquid phase has been presented. This model has been used to determine mass transfer rates, enhancement factors and concentration profiles over a wide range of process conditions. Although

  10. Mass transfer with complex chemical reactions in gas-liquid systems: two-step reversible reactions with unit stoichiometric and kinetic orders

    NARCIS (Netherlands)

    Vas bhat, R.D.; Kuipers, J.A.M.; Versteeg, Geert

    2000-01-01

    An absorption model to study gas¿liquid mass transfer accompanied by reversible two-step reactions in the liquid phase has been presented. This model has been used to determine mass transfer rates, enhancement factors and concentration profiles over a wide range of process conditions. Although

  11. Rate kernel theory for pseudo-first-order kinetics of diffusion-influenced reactions and application to fluorescence quenching kinetics.

    Science.gov (United States)

    Yang, Mino

    2007-06-07

    Theoretical foundation of rate kernel equation approaches for diffusion-influenced chemical reactions is presented and applied to explain the kinetics of fluorescence quenching reactions. A many-body master equation is constructed by introducing stochastic terms, which characterize the rates of chemical reactions, into the many-body Smoluchowski equation. A Langevin-type of memory equation for the density fields of reactants evolving under the influence of time-independent perturbation is derived. This equation should be useful in predicting the time evolution of reactant concentrations approaching the steady state attained by the perturbation as well as the steady-state concentrations. The dynamics of fluctuation occurring in equilibrium state can be predicted by the memory equation by turning the perturbation off and consequently may be useful in obtaining the linear response to a time-dependent perturbation. It is found that unimolecular decay processes including the time-independent perturbation can be incorporated into bimolecular reaction kinetics as a Laplace transform variable. As a result, a theory for bimolecular reactions along with the unimolecular process turned off is sufficient to predict overall reaction kinetics including the effects of unimolecular reactions and perturbation. As the present formulation is applied to steady-state kinetics of fluorescence quenching reactions, the exact relation between fluorophore concentrations and the intensity of excitation light is derived.

  12. Enabling nucleophilic substitution reactions of activated alkyl fluorides through hydrogen bonding.

    Science.gov (United States)

    Champagne, Pier Alexandre; Pomarole, Julien; Thérien, Marie-Ève; Benhassine, Yasmine; Beaulieu, Samuel; Legault, Claude Y; Paquin, Jean-François

    2013-05-03

    It was discovered that the presence of water as a cosolvent enables the reaction of activated alkyl fluorides for bimolecular nucleophilic substitution reactions. DFT calculations show that activation proceeds through stabilization of the transition structure by a stronger F···H2O interaction and diminishing C-F bond elongation, and not simple transition state electrostatic stabilization. Overall, the findings put forward a distinct strategy for C-F bond activation through H-bonding.

  13. Improving the catalytic activity of amorphous molybdenum sulfide for hydrogen evolution reaction using polydihydroxyphenylalanine modified MWCNTs

    Science.gov (United States)

    Li, Maoguo; Yu, Muping; Li, Xiang

    2018-05-01

    Molybdenum sulfides are promising electrocatalysts for hydrogen evolution reaction (HER) in acid medium due to their unique properties. In order to improve their HER activity, different strategies have been developed. In this study, amorphous molybdenum sulfide was prepared by a simple wet chemical method and its HER activity was further improved by using polydihydroxyphenylalanine (PDOPA) modified MWCNTs as supports. It was found that the PDOPA can effectively improve the hydrophilic properties of multiwalled carbon nanotubes (MWCNTs) and amorphous MoSx can uniformly grow on the surface of PDOPA@MWCNTs. Compared with MoSx and MoSx/MWCNTs, MoSx/PDOPA@MWCNTs show obviously enhanced HER activities due to the superior electrical conductivity and more exposed active sites. In addition, the effect of the ratio of MoSx and PDOPA@MWCNTs and the loading amount of catalysts on the electrodes are also investigated in detail. At the optimum conditions, MoSx/PDOPA@MWCNTs display an overpotential of 198 mV at 10 mA/cm2, a Tafel slope of 53 mV/dec and a good long-term stability in 0.5 M H2SO4, which make them promising candidates for HER application.

  14. Exploration of the Role of Heat Activation in Enhancing Serpentine Carbon Sequestration Reactions

    International Nuclear Information System (INIS)

    McKelvy, M.J.; Chizmeshya, A.V.G.; Diefenbacher, J.; Bearat, H.; Wolf, G.

    2005-01-01

    As compared with other candidate carbon sequestration technologies, mineral carbonation offers the unique advantage of permanent disposal via geologically stable and environmentally benign carbonates. The primary challenge is the development of an economically viable process. Enhancing feedstock carbonation reactivity is key. Heat activation dramatically enhances aqueous serpentine carbonation reactivity. Although the present process is too expensive to implement, the materials characteristics and mechanisms that enhance carbonation are of keen interest for further reducing cost. Simultaneous thermogravimetric and differential thermal analysis (TGA/DTA) of the serpentine mineral lizardite was used to isolate a series of heat-activated materials as a function of residual hydroxide content at progressively higher temperatures. Their structure and composition are evaluated via TGA/DTA, X-ray powder diffraction (including phase analysis), and infrared analysis. The meta-serpentine materials that were observed to form ranged from those with longer range ordering, consistent with diffuse stage-2 like interlamellar order, to an amorphous component that preferentially forms at higher temperatures. The aqueous carbonation reaction process was investigated for representative materials via in situ synchrotron X-ray diffraction. Magnesite was observed to form directly at 15 MPa CO 2 and at temperatures ranging from 100 to 125 C. Carbonation reactivity is generally correlated with the extent of meta-serpentine formation and structural disorder.

  15. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1978--February 14, 1979

    International Nuclear Information System (INIS)

    Rack, E.P.

    1979-02-01

    High energy reactions of halogen atoms or ions, activated by nuclear transformations, were studied in gaseous, high pressure and condensed phase saturated and unsaturated hydrocarbons, halomethanes and other organic systems in order to better understand the mechanisms and dynamics of high energy monovalent species. The experimental and theoretical program consists of six interrelated areas: (1) the reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure and liquid systems; (2) the gas to condensed state transition in halogen high chemistry, involving bromine activated by the (n,γ) and (I.T.) processes in ethane was investigated in more detail; (3) systematics of halogen hot atom reactions. The reactions of 80 Br/sup m/, 80 Br, 82 Br/sup m/ + 82 Br, 82 Br, 128 I, 130 I, and 130 I/sup m/ + 130 I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators; (4) kinetic theory applications of high energy reactions and mathematical development of caging mechanisms were developed; (5) the sterochemistry of 38 Cl substitution reactions involving diastereomeric 1,2-dichloro-1,2-difluorethane in liquid mixtures was completed, suggesting that the stereochemical course of the substitution process is controlled by the properties of the solvent molecules; and (6) the applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems was continued, especially involving aluminum and vanadium trace determinations

  16. Morphology and Activity Tuning of Cu 3 Pt/C Ordered Intermetallic Nanoparticles by Selective Electrochemical Dealloying

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Deli; Yu, Yingchao; Zhu, Jing; Liu, Sufen; Muller, David A.; Abruña, Héctor D.

    2015-02-11

    Improving the catalytic activity of Pt-based bimetallic nanoparticles is a key challenge in the application of proton-exchange membrane fuel cells. Electrochemical dealloying represents a powerful approach for tuning the surface structure and morphology of these catalyst nanoparticles. We present a comprehensive study of using electrochemical dealloying methods to control the morphology of ordered Cu3Pt/C intermetallic nanoparticles, which could dramatically affect their electrocatalytic activity for the oxygen reduction reaction (ORR). Depending on the electrochemical dealloying conditions, the nanoparticles with Pt-rich core–shell or porous structures were formed. We further demonstrate that the core–shell and porous morphologies can be combined to achieve the highest ORR activity. This strategy provides new guidelines for optimizing nanoparticles synthesis and improving electrocatalytic activity.

  17. Pneumatic tool torque reaction: reaction forces, displacement, muscle activity and discomfort in the hand-arm system.

    Science.gov (United States)

    Kihlberg, S; Kjellberg, A; Lindbeck, L

    1993-06-01

    Reaction forces, hand-arm displacement, muscle activity and discomfort ratings were studied during the securing of threaded fasteners with three angle nutrunners with different shut-off mechanisms, but with the same spindle torque (72-74 Nm). The three tools were tested according to the method specified in ISO 6544. One of the tools had an almost instantaneous shut-off. Another had a more slowly declining torque curve. For the third tool the maximum torque was maintained for a while before shut-off. Twelve male subjects participated in the study. A force platform measured the reaction force between the subject and the floor. The option of the hand-arm system and the shoulder was measured with an optoelectronic measuring system. The muscle activity (EMG) in six muscles in the arm and shoulder was measured with surface electrodes. Significant differences in the arm movements and ground reaction forces were found between the three tools. The smallest values were found with the fast shut-off tool while the delayed shut-off tool caused the largest values. The EMG measures gave inconsistent response patterns. Discomfort ratings were highly correlated with the time for which the tool torque exceeded 90% of peak preset torque, but the time for which the tool torque exceeded 90% of peak calculated by the method specified in ISO 6544. Nutrunners with a shut-off mechanism that causes a slowly decreasing torque or a torque that is maintained for a while before shut-off should be avoided. If no substitutes are available, then a torque reaction bar should be mounted on the tool.

  18. 75 FR 50847 - Cotton Program Changes for Upland Cotton, Adjusted World Price, and Active Shipping Orders

    Science.gov (United States)

    2010-08-18

    ... Cotton Program Changes for Upland Cotton, Adjusted World Price, and Active Shipping Orders AGENCY... Assistance Program (EAAP) and clarifying the definition of ``active shipping order.'' DATES: Effective Date... address that matter this rule amends in the payment calculation for semi-processed and reginned motes in 7...

  19. Review of activities concerning sodium water reaction in LMFBR

    International Nuclear Information System (INIS)

    Rajput, A.K.

    1984-01-01

    This paper presents a review of activities concerning safety engineering programme for steam generators of FBT reactor in India. Leak rate and its effect and leak detection system are briefly discussed

  20. Incorporation of Pt, Ru and Pt-Ru nanoparticles into ordered mesoporous carbons for efficient oxygen reduction reaction in alkaline media

    International Nuclear Information System (INIS)

    Stojmenović, Marija; Momčilović, Milan; Gavrilov, Nemanja; Pašti, Igor A.; Mentus, Slavko; Jokić, Bojan; Babić, Biljana

    2015-01-01

    Ordered mesoporous carbon, volume-doped up to 3 w.% with Pt, Ru and Pt-Ru nanoparticles was synthesized by evaporation-induced self-assembly method, under acidic conditions. The content of incorporated metal was determined by EDX analysis. The X-ray diffractometry confirmed the existence of highly dispersed metallic phases in doped samples. Specific surface area was determined by N 2 -physisorption measurements to range between 452 and 545 m 2 g −1 . Raman spectroscopy of investigated materials indicated highly disordered carbon structure with crystallite sizes around 1.4 nm. In a form of thin-layer electrode on glassy carbon support, in 0.1 M KOH solution, the prepared materials displayed high activity toward oxygen reduction reaction (ORR) in alkaline media, with onset potentials more positive than −0.10 V vs. SCE. The kinetics of O 2 reduction was found to be affected by both the specific surface area and the concentration of metal dopants. The ethanol tolerance of (Pt, Ru)-doped OMCs was found to be higher than that of common Pt/C ORR catalysts. Presented study provides a new route for the synthesis of active and selective ORR catalysts in alkaline media, being competitive with, or superior to, the existing ones in terms of performance and price

  1. Activity and selectivity regulation of synthesis gas reaction over supported ruthenium catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Fujimoto, K; Nobusawa, T; Fukushima, T; Tominaga, H

    1985-01-01

    The catalytic activities of supported ruthenium for synthesis-gas conversion to hydrocarbons was found to be in the following order: TiOS > Nb2O3 > ZrO2 > SiO2 > Ta2O5 > Al2O3 > V2O5 > MoO3 > WO3 > MnO2 > ZnO. Turnover frequencies of the supported ruthenium increased with decrease in dispersion of the metal particles for every carrier material. Even the activities per unit weight of metals were higher for low-dispersion ruthenium of Al2O3, TiO2, and ZrO2. The chain-growth probability of a hydrocarbon product, which is characterized by the Schulz-Flory distribution, increased markedly with decrease in the metal dispersion irrespective of the carrier material. The catalytic activity of ruthenium particles with a dispersed ruthenium increased almost linearly with an increase in reaction pressure (up to at least 2.0 MPa). 23 references, 10 figures, 3 tables.

  2. Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction.

    Science.gov (United States)

    Yang, Liu; Cheng, Daojian; Xu, Haoxiang; Zeng, Xiaofei; Wan, Xin; Shui, Jianglan; Xiang, Zhonghua; Cao, Dapeng

    2018-06-26

    It is still a grand challenge to develop a highly efficient nonprecious-metal electrocatalyst to replace the Pt-based catalysts for oxygen reduction reaction (ORR). Here, we propose a surfactant-assisted method to synthesize single-atom iron catalysts (SA-Fe/NG). The half-wave potential of SA-Fe/NG is only 30 mV less than 20% Pt/C in acidic medium, while it is 30 mV superior to 20% Pt/C in alkaline medium. Moreover, SA-Fe/NG shows extremely high stability with only 12 mV and 15 mV negative shifts after 5,000 cycles in acidic and alkaline media, respectively. Impressively, the SA-Fe/NG-based acidic proton exchange membrane fuel cell (PEMFC) exhibits a high power density of 823 mW cm -2 Combining experimental results and density-functional theory (DFT) calculations, we further reveal that the origin of high-ORR activity of SA-Fe/NG is from the Fe-pyrrolic-N species, because such molecular incorporation is the key, leading to the active site increase in an order of magnitude which successfully clarifies the bottleneck puzzle of why a small amount of iron in the SA-Fe catalysts can exhibit extremely superior ORR activity.

  3. Generalization of the Activated Complex Theory of Reaction Rates. I. Quantum Mechanical Treatment

    Science.gov (United States)

    Marcus, R. A.

    1964-01-01

    In its usual form activated complex theory assumes a quasi-equilibrium between reactants and activated complex, a separable reaction coordinate, a Cartesian reaction coordinate, and an absence of interaction of rotation with internal motion in the complex. In the present paper a rate expression is derived without introducing the Cartesian assumption. The expression bears a formal resemblance to the usual one and reduces to it when the added assumptions of the latter are introduced.

  4. High energy halogen atom reactions activated by nuclear transformations

    International Nuclear Information System (INIS)

    Rack, E.P.

    1990-05-01

    This program, which has been supported for twenty-four years by the Us Atomic Energy Commission and its successor agencies, has produced significant advances in the understanding of the mechanisms of chemical activation by nuclear processes; the stereochemistry of radioactivity for solution of specific problems. This program was contributed to the training of approximately seventy scientists at various levels. This final report includes a review of the areas of research and chronological tabulation of the publications

  5. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  6. Activation of generalised inflammatory reaction following electrical cardioversion.

    Science.gov (United States)

    Gajek, Jacek; Zyśko, Dorota; Mysiak, Andrzej; Mazurek, Walentyna

    2004-09-01

    Restoration of sinus rhythm in patients with atrial fibrillation (AF) is associated with an increased risk of thrombo-embolic complications due to delayed return of the left atrial and left atrial appendage systolic function. Direct current cardioversion (DC), used for AF termination, may cause myocardial injury and subsequent activation of inflammatory response. A C-reactive protein (CRP) is a non-specific marker of inflammation. To examine the effects of external DC of AF or atrial flutter (AFlut) on inflammatory processes. The study group consisted of 35 patients (20 females and 15 males, mean age 67.9+/-9.7 years, range 46-83 years) with paroxysmal or persistent AF/AFlut who underwent elective DC. CRP plasma concentration was measured before and 24 hours after DC. The mean total DC energy was 431.2 J. CRP plasma concentration increased significantly following DC - from 3.9+/-3.4 ng/ml before DC to 7.2+/-6.7 ng/ml after DC (p<0.0001). CRP level correlated with body mass index (r=0.34, p<0.05), however, this correlation became non-significant after inclusion of the presence of diabetes into the statistical model. There was also a positive correlation between CRP values before and after DC (r=0.72, p<0.0001). No correlation between CRP and gender, total power of DC nor the number of DC shocks was detected. External DC of AF/Aflut causes activation of inflammatory processes measured as a significant increase in the CRP plasma concentration.

  7. New Method to Synthesize Highly Active and Durable Chemically Ordered fct-PtCo Cathode Catalyst for PEMFCs.

    Science.gov (United States)

    Jung, Won Suk; Popov, Branko N

    2017-07-19

    In the bottom-up synthesis strategy performed in this study, the Co-catalyzed pyrolysis of chelate-complex and activated carbon black at high temperatures triggers the graphitization reaction which introduces Co particles in the N-doped graphitic carbon matrix and immobilizes N-modified active sites for the oxygen reduction reaction (ORR) on the carbon surface. In this study, the Co particles encapsulated within the N-doped graphitic carbon shell diffuse up to the Pt surface under the polymer protective layer and forms a chemically ordered face-centered tetragonal (fct) Pt-Co catalyst PtCo/CCCS catalyst as evidenced by structural and compositional studies. The fct-structured PtCo/CCCS at low-Pt loading (0.1 mg Pt cm -2 ) shows 6% higher power density than that of the state-of-the-art commercial Pt/C catalyst. After the MEA durability test of 30 000 potential cycles, the performance loss of the catalyst is negligible. The electrochemical surface area loss is less than 40%, while that of commercial Pt/C is nearly 80%. After the accelerated stress test, the uniform catalyst distribution is retained and the mean particle size increases approximate 1 nm. The results obtained in this study indicated that highly stable compositional and structural properties of chemically ordered PtCo/CCCS catalyst contribute to its exceptional catalyst durability.

  8. Taste-Active Maillard Reaction Products in Roasted Garlic (Allium sativum).

    Science.gov (United States)

    Wakamatsu, Junichiro; Stark, Timo D; Hofmann, Thomas

    2016-07-27

    In order to gain first insight into candidate Maillard reaction products formed upon thermal processing of garlic, mixtures of glucose and S-allyl-l-cysteine, the major sulfur-containing amino acid in garlic, were low-moisture heated, and nine major reaction products were isolated. LC-TOF-MS, 1D/2D NMR, and CD spectroscopy led to their identification as acortatarin A (1), pollenopyrroside A (2), epi-acortatarin A (3), xylapyrroside A (4), 5-hydroxymethyl-1-[(5-hydroxymethyl-2-furanyl)methyl]-1H-pyrrole-2-carbalde-hyde (5), 3-(allylthio)-2-(2-formyl-5-hydroxymethyl-1H-pyrrol-1-yl)propanoic acid (6), (4S)-4-(allylthiomethyl)-3,4-dihydro-3-oxo-1H-pyrrolo[2,1-c][1,4]oxazine-6-carbaldehyde (7), (2R)-3-(allylthio)-2-[(4R)-4-(allylthiomethyl)-6-formyl-3-oxo-3,4-dihydropyrrolo-[1,2-a]pyrazin-2(1H)-yl]propanoic acid (8), and (2R)-3-(allylthio)-2-((4S)-4-(allylthiomethyl)-6-formyl-3-oxo-3,4-dihydropyrrolo-[1,2-a]pyrazin-2(1H)-yl)propanoic acid (9). Among the Maillard reaction products identified, compounds 5-9 have not previously been published. The thermal generation of the literature known spiroalkaloids 1-4 is reported for the first time. Sensory analysis revealed a bitter taste with thresholds between 0.5 and 785 μmol/kg for 1-5 and 7-9. Compound 6 did not show any intrinsic taste (water) but exhibited a strong mouthfullness (kokumi) enhancing activity above 186 μmol/kg. LC-MS/MS analysis showed 1-9 to be generated upon pan-frying of garlic with the highest concentration of 793.7 μmol/kg found for 6, thus exceeding its kokumi threshold by a factor of 4 and giving evidence for its potential taste modulation activity in processed garlic preparations.

  9. Synchronization of Different Fractional Order Time-Delay Chaotic Systems Using Active Control

    Directory of Open Access Journals (Sweden)

    Jianeng Tang

    2014-01-01

    Full Text Available Chaos synchronization of different fractional order time-delay chaotic systems is considered. Based on the Laplace transform theory, the conditions for achieving synchronization of different fractional order time-delay chaotic systems are analyzed by use of active control technique. Then numerical simulations are provided to verify the effectiveness and feasibility of the developed method. At last, effects of the fraction order and the time delay on synchronization are further researched.

  10. Complement activation in leprosy: a retrospective study shows elevated circulating terminal complement complex in reactional leprosy.

    Science.gov (United States)

    Bahia El Idrissi, N; Hakobyan, S; Ramaglia, V; Geluk, A; Morgan, B Paul; Das, P Kumar; Baas, F

    2016-06-01

    Mycobacterium leprae infection gives rise to the immunologically and histopathologically classified spectrum of leprosy. At present, several tools for the stratification of patients are based on acquired immunity markers. However, the role of innate immunity, particularly the complement system, is largely unexplored. The present retrospective study was undertaken to explore whether the systemic levels of complement activation components and regulators can stratify leprosy patients, particularly in reference to the reactional state of the disease. Serum samples from two cohorts were analysed. The cohort from Bangladesh included multi-bacillary (MB) patients with (n = 12) or without (n = 46) reaction (R) at intake and endemic controls (n = 20). The cohort from Ethiopia included pauci-bacillary (PB) (n = 7) and MB (n = 23) patients without reaction and MB (n = 15) patients with reaction. The results showed that the activation products terminal complement complex (TCC) (P ≤ 0·01), C4d (P ≤ 0·05) and iC3b (P ≤ 0·05) were specifically elevated in Bangladeshi patients with reaction at intake compared to endemic controls. In addition, levels of the regulator clusterin (P ≤ 0·001 without R; P < 0·05 with R) were also elevated in MB patients, irrespective of a reaction. Similar analysis of the Ethiopian cohort confirmed that, irrespective of a reaction, serum TCC levels were increased significantly in patients with reactions compared to patients without reactions (P ≤ 0·05). Our findings suggests that serum TCC levels may prove to be a valuable tool in diagnosing patients at risk of developing reactions. © 2016 British Society for Immunology.

  11. Fast and calibration free determination of first order reaction kinetics in API synthesis using in-situ ATR-FTIR.

    Science.gov (United States)

    Rehbein, Moritz C; Husmann, Sascha; Lechner, Christian; Kunick, Conrad; Scholl, Stephan

    2018-05-01

    In early stages of drug development only sparse amounts of the key substances are available, which is problematic for the determination of important process data like reaction kinetics. Therefore, it is important to perform experiments as economically as possible, especially in regards to limiting compounds. Here we demonstrate the use of a temperature step experiment enabling the determination of complete reaction kinetics in a single non-isothermal experiment. In contrast to the traditionally used HPLC, the method takes advantage of the high measuring rate and the low amount of labor involved in using in-situ ATR-FTIR to determine time-dependent concentration-equivalent data. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Halogenating reaction activity of aromatic organic compounds during disinfection of drinking water

    International Nuclear Information System (INIS)

    Guo Gaimei; Chen Xiaodong

    2009-01-01

    The halogenating reactions of five aromatic organic compounds (AOCs) with aqueous chlorine (HOCl/OCl - ) and aqueous bromine (HOBr/OBr - ) were studied with an aim to compare the formation properties of haloacetic acids (HAAs) for the corresponding chlorination or bromination reactions of AOCs, respectively. The experiment results indicated that the HAAs substitution efficiency for the bromination reactions of AOCs was greater than that for the chlorination reactions, and the formation of HAAs had a strong dependence on the chemical structure of AOCs. The chlorination or bromination reaction activities for the AOCs with electron donating functional groups were higher than that for them with electron withdrawing functional groups. The kinetic experiments indicated that the reactions of aqueous bromine with phenol were faster than those of aqueous chlorine with phenol and the halogen consumption exhibited rapid initial and slower consumption stages for the reactions of phenol with aqueous chlorine and bromine, respectively. In addition, the HAAs production for the chlorination reaction of phenol decreased with the increase of pH. These conclusions could provide the valuable information for the effective control of the disinfection by-products during drinking water treatment operation

  13. Microwave activation of palladium nanoparticles for enhanced ethanol electrocatalytic oxidation reaction in alkaline medium

    CSIR Research Space (South Africa)

    Rohwer, MB

    2015-02-01

    Full Text Available in alkaline medium (in terms of high mass activity stability and fast reaction kinetics). The remarkable microwave-induced properties on the Pd catalyst promise to revolutionize the use of microwave for catalyst activation for enhanced heterogeneous catalysis...

  14. Organocatalytic Michael and Friedel–Crafts reactions in enantioselective synthesis of biologically active compounds

    International Nuclear Information System (INIS)

    Maltsev, O V; Beletskaya, Irina P; Zlotin, Sergei G

    2011-01-01

    Recent applications of organocatalytic Michael and Friedel–Crafts reactions in enantioselective synthesis of biologically active compounds: natural products, pharmaceutical agents and plant protection agents are reviewed. The key mechanisms of stereoinduction, types of organocatalysts and reagents used in these reactions are considered. The material is classified according to the type of newly formed bonds incorporating the asymmetric carbon atom, and the information for the most numerous C–C coupling reactions is systematized according to the natures of the electrophile and the nucleophile. The bibliography includes 433 references.

  15. Evaluation of reactor induced (n,p) reactions for activation analysis of titanium in geological materials

    Energy Technology Data Exchange (ETDEWEB)

    Espinosa Garcia, R; Cohen, I M [Comision Nacional de Energia Atomica, Buenos Aires (Argentina)

    1984-05-01

    The possibilities of reactor induced (n,p) reactions as a tool for neutron activation analysis of titanium in geological samples are discussed. The interference of calcium and scandium is experimentally evaluated. Results for Ti, Ca and Sc in GSP-1 and PCC-1 standard rocks are presented. Based on the experimental values, it is concluded that the /sup 47/Ti(n,p)/sup 47/Sc reaction is the most favourable for titanium determination. 11 refs.

  16. Synthesis and electrocatalytic activity towards oxygen reduction reaction of gold-nanostars

    OpenAIRE

    Oyunbileg G; Batnyagt G; Enkhsaruul B; T Takeguchi

    2018-01-01

    The oxygen reduction reaction (ORR) is a characteristic reaction which determines the performance of fuel cells which convert a chemical energy into an electrical energy. Aims of this study are to synthesize Au-based nanostars (AuNSs) and determine their preliminary electro-catalytic activities towards ORR by a rotating-disk electrode method in alkaline electrolyte. The images obtained from a scanning electron microscope (SEM) and a transmission electron microscope (TEM) analyses confirm the ...

  17. Synthesis of three-dimensionally ordered macro-/mesoporous Pt with high electrocatalytic activity by a dual-templating approach

    Science.gov (United States)

    Zhang, Chengwei; Yang, Hui; Sun, Tingting; Shan, Nannan; Chen, Jianfeng; Xu, Lianbin; Yan, Yushan

    2014-01-01

    Three dimensionally ordered macro-/mesoporous (3DOM/m) Pt catalysts are fabricated by chemical reduction employing a dual-templating synthesis approach combining both colloidal crystal (opal) templating (hard-templating) and lyotropic liquid crystal templating (soft-templating) techniques. The macropore walls of the prepared 3DOM/m Pt exhibit a uniform mesoporous structure composed of polycrystalline Pt nanoparticles. Both the size of the mesopores and Pt nanocrystallites are in the range of 3-5 nm. The 3DOM/m Pt catalyst shows a larger electrochemically active surface area (ECSA), and higher catalytic activity as well as better poisoning tolerance for methanol oxidation reaction (MOR) than the commercial Pt black catalyst.

  18. HEAT AND MASS TRANSFER EFFECTS ON FLOW PAST PARABOLIC STARTING MOTION OF ISOTHERMAL VERTICAL PLATE IN THE PRESENCE OF FIRST ORDER CHEMICAL REACTION

    Directory of Open Access Journals (Sweden)

    R. Muthucumaraswamy

    2013-06-01

    Full Text Available An exact solution of unsteady flow past a parabolic starting motion of the infinite isothermal vertical plate with uniform mass diffusion, in the presence of a homogeneous chemical reaction of the first order, has been studied. The plate temperature and the concentration level near the plate are raised uniformly. The dimensionless governing equations are solved using the Laplace transform technique. The effect of velocity profiles are studied for different physical parameters, such as chemical reaction parameter, thermal Grashof number, mass Grashof number, Schmidt number, and time. It is observed that velocity increases with increasing values of thermal Grashof number or mass Grashof number. The trend is reversed with respect to the chemical reaction parameter.

  19. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1979-February 14, 1980

    International Nuclear Information System (INIS)

    Rack, E.P.

    1980-02-01

    The program consists of six interrelated areas: (1) Reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure, and liquid systems. Special attention was given to the reactivity of excited complex formation and structural effects of electrophilic iodine attack on various pi-bond systems. (2) The gas-to-condensed phase transition in halogen high energy chemistry. Current interest involves the study of caging effects of an ice lattice on recombination reactions involving neutron-irradiated frozen aqueous solutions of halogenated organic and biochemical solutes in order to learn more about kinetic energy effects, halogen size, solute molecule size, steric effects and hydrogen bonding within an ice lattice cage. (3) Systematics of halogen hot atom reactions. The reactions of /sup 80m/Br, 80 Br, /sup 82m/Br + 82 Br, 82 Br, 82 Br, 128 I, 130 I, and /sup 130m/I + 130 I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators are currently being studied. (4) Mathematical and computer simulation studies of caging events within an ice lattice are being investigated. (5) At Brookhaven National Laboratory, cyclotron-produced chlorine and fluorine hot atoms substitution reactions with molecules possessing a single chiral center are under investigation. (6) The applications of high energy techniques and concepts to neutron activation analysis for trace elements and trace molecule determinations in biological systems was continued

  20. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1979-February 14, 1980

    Energy Technology Data Exchange (ETDEWEB)

    Rack, E.P.

    1980-02-01

    The program consists of six interrelated areas: (1) Reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure, and liquid systems. Special attention was given to the reactivity of excited complex formation and structural effects of electrophilic iodine attack on various pi-bond systems. (2) The gas-to-condensed phase transition in halogen high energy chemistry. Current interest involves the study of caging effects of an ice lattice on recombination reactions involving neutron-irradiated frozen aqueous solutions of halogenated organic and biochemical solutes in order to learn more about kinetic energy effects, halogen size, solute molecule size, steric effects and hydrogen bonding within an ice lattice cage. (3) Systematics of halogen hot atom reactions. The reactions of /sup 80m/Br, /sup 80/Br, /sup 82m/Br + /sup 82/Br, /sup 82/Br, /sup 82/Br, /sup 128/I, /sup 130/I, and /sup 130m/I + /sup 130/I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators are currently being studied. (4) Mathematical and computer simulation studies of caging events within an ice lattice are being investigated. (5) At Brookhaven National Laboratory, cyclotron-produced chlorine and fluorine hot atoms substitution reactions with molecules possessing a single chiral center are under investigation to determine the role of hot atom kinetic energy, halogen atom, enantioner structure, steric effects and phase on the extent of substitution by retention of configuration or by Walden inversion. (6) The applications of high energy techniques and concepts to neutron activation analysis for trace element determinations in biological systems was continued.

  1. Kinetic Study of the Aroxyl-Radical-Scavenging Activity of Five Fatty Acid Esters and Six Carotenoids in Toluene Solution: Structure-Activity Relationship for the Hydrogen Abstraction Reaction.

    Science.gov (United States)

    Mukai, Kazuo; Yoshimoto, Maya; Ishikura, Masaharu; Nagaoka, Shin-Ichi

    2017-08-17

    A kinetic study of the reaction between an aroxyl radical (ArO • ) and fatty acid esters (LHs 1-5, ethyl stearate 1, ethyl oleate 2, ethyl linoleate 3, ethyl linolenate 4, and ethyl arachidonate 5) has been undertaken. The second-order rate constants (k s ) for the reaction of ArO • with LHs 1-5 in toluene at 25.0 °C have been determined spectrophotometrically. The k s values obtained increased in the order of LH 1 LHs 1-5. The k s value for LH 5 was 2.93 × 10 -3 M -1 s -1 . From the result, it has been clarified that the reaction of ArO • with LHs 1-5 was explained by an allylic hydrogen abstraction reaction. A similar kinetic study was performed for the reaction of ArO • with six carotenoids (Car-Hs 1-6, astaxanthin 1, β-carotene 2, lycopene 3, capsanthin 4, zeaxanthin 5, and lutein 6). The k s values obtained increased in the order of Car-H 1 LHs 1-5. The results of detailed analyses of the k s values for the above reaction indicated that the reaction was also explained by an allylic hydrogen abstraction reaction. Furthermore, the structure-activity relationship for the reaction was discussed by taking the result of density functional theory calculation reported by Martinez and Barbosa into account.

  2. Recurrent activity in higher order, modality non-specific brain regions

    DEFF Research Database (Denmark)

    Lou, Hans Olav Christensen; Joensson, Morten; Biermann-Ruben, Katja

    2011-01-01

    It has been proposed that the workings of the brain are mainly intrinsically generated recurrent neuronal activity, with sensory inputs as modifiers of such activity in both sensory and higher order modality non-specific regions. This is supported by the demonstration of recurrent neuronal activity...... in the visual system as a response to visual stimulation. In contrast recurrent activity has never been demonstrated before in higher order modality non-specific regions. Using magneto-encephalography and Granger causality analysis, we tested in a paralimbic network the hypothesis that stimulation may enhance...... causal recurrent interaction between higher-order, modality non-specific regions. The network includes anterior cingulate/medial prefrontal and posterior cingulate/medial parietal cortices together with pulvinar thalami, a network known to be effective in autobiographic memory retrieval and self...

  3. Oxygen Reduction Reaction Activity of Platinum Thin Films with Different Densities

    Energy Technology Data Exchange (ETDEWEB)

    Ergul, Busra; Begum, Mahbuba; Kariuki, Nancy; Myers, Deborah J.; Karabacak, Tansel

    2017-08-24

    Platinum thin films with different densities were grown on glassy carbon electrodes by high pressure sputtering deposition and evaluated as oxygen reduction reaction catalysts for polymer electrolyte fuel cells using cyclic voltammetry and rotating disk electrode techniques in aqueous perchloric acid electrolyte. The electrochemically active surface area, ORR mass activity (MA) and specific activity (SA) of the thin film electrodes were obtained. MA and SA were found to be higher for low-density films than for high-density film.

  4. Thermally activated reaction–diffusion-controlled chemical bulk reactions of gases and solids

    Directory of Open Access Journals (Sweden)

    S. Möller

    2015-01-01

    Full Text Available The chemical kinetics of the reaction of thin films with reactive gases is investigated. The removal of thin films using thermally activated solid–gas to gas reactions is a method to in-situ control deposition inventory in vacuum and plasma vessels. Significant scatter of experimental deposit removal rates at apparently similar conditions was observed in the past, highlighting the need for understanding the underlying processes. A model based on the presence of reactive gas in the films bulk and chemical kinetics is presented. The model describes the diffusion of reactive gas into the film and its chemical interaction with film constituents in the bulk using a stationary reaction–diffusion equation. This yields the reactive gas concentration and reaction rates. Diffusion and reaction rate limitations are depicted in parameter studies. Comparison with literature data on tokamak co-deposit removal results in good agreement of removal rates as a function of pressure, film thickness and temperature.

  5. Rate Constants and Activation Energies for Gas-Phase Reactions of Three Cyclic Volatile Methyl Siloxanes with the Hydroxyl Radical.

    Science.gov (United States)

    Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie; Macleod, Matthew

    2015-07-01

    Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second-order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ), and dodecamethylcyclohexasiloxane (D 6 ) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140-mL gas-phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D 4 and D 5 with the OH radical are 1.9 × 10 -12 (95% confidence interval (CI): (1.7-2.2) × 10 -12 ) and 2.6 × 10 -12 (CI: (2.3-2.9) × 10 -12 ) cm 3 molecule -1 s -1 , respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D 6 is 2.8 × 10 -12 (CI: (2.5-3.2) × 10 -12 ) cm 3 molecule -1 s -1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D 5 were 33% higher than for D 4 (CI: 30-37%), whereas the rates for D 6 were only 8% higher than for D 5 (CI: 5-10%). The activation energies of the reactions of D 4 , D 5 , and D 6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol.

  6. Rate Constants and Activation Energies for Gas‐Phase Reactions of Three Cyclic Volatile Methyl Siloxanes with the Hydroxyl Radical

    Science.gov (United States)

    Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie

    2015-01-01

    ABSTRACT Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second‐order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140‐mL gas‐phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D4 and D5 with the OH radical are 1.9 × 10−12 (95% confidence interval (CI): (1.7–2.2) × 10−12) and 2.6 × 10−12 (CI: (2.3–2.9) × 10−12) cm3 molecule−1 s−1, respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D6 is 2.8 × 10−12 (CI: (2.5–3.2) × 10−12) cm3 molecule−1 s−1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D5 were 33% higher than for D4 (CI: 30–37%), whereas the rates for D6 were only 8% higher than for D5 (CI: 5–10%). The activation energies of the reactions of D4, D5, and D6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol. PMID:27708500

  7. I. Activation energies for the gas phase reactions of hydrogen atom with carbon monoxide and with ethylene. II. Rate constants for the reactions of benzyl cation with triethylphosphine and with triethylarsine in 1,2-dichloroethane

    International Nuclear Information System (INIS)

    Wang, H.Y.

    1976-01-01

    Two H-atom reactions H + CO + H 2 → HCO + H 2 and H + C 2 H 4 → C 2 H 5 * were separately studied from room temperature to about 100 0 C, and the activation energies for these two reactions were determined in this temperature range. For H + C 2 H 4 system, a small activation energy of 0.2 kcal/mole was obtained in the present narrow temperature range. The low activation energy indicates that the pre-exponential factor has a predominant contribution to the rate constant of this reaction and has about the same magnitude as that of the rate constant. For H + CO system, a fairly large activation energy of more than 7 kcal/mole was speculated in the potential energy surfaces of the system. The activation energy obtained in the present work, however, has a low value of about 2 kcal/mole. This low value reveals the low level of crossing of this reaction in the potential energy surface and thus indicates considerable complexity involved in the surface. Carbonium ions can be formed from chosen solutes in pulse-irradiated 1,2-dichloroethane (RCl) solutions. Upon irradiation, the electrons generated from the ionization of the solvent become localized on chloride ions as a result of their reaction with the neutral solvent molecules. The solvent counterion, RCl + , on the other hand, is free to exchange charge with the solute molecule. By choosing appropriate solutes, carbonium ion can be formed through a dissociative ionization process in the exchange. The benzyl cation was formed from its precursor compound dibenzylmercury and its reactions with two nucleophiles, triethylphosphine and triethylarsine, were separately studied. The formation and decay of benzyl cation were observed at 363 nm, the position of the maximum of its absorption band, and the second-order rate constants for the two reactions were determined at room temperature

  8. Potential Effect of Physical Activity Calorie Equivalent (PACE) Labeling on Adult Fast Food Ordering and Exercise

    OpenAIRE

    Antonelli, Ray; Viera, Anthony J.

    2015-01-01

    Introduction Numeric calorie content labels show limited efficacy in reducing the number of calories ordered from fast food meals. Physical activity calorie equivalent (PACE) labels are an alternative that may reduce the number of calories ordered in fast food meals while encouraging patrons to exercise. Methods A total of 1000 adults from 47 US states were randomly assigned via internet survey to one of four generic fast food menus: no label, calories only, calories + minutes, or calories + ...

  9. Demonstration of physical phenomenas and scavenging activity from d-psicose and methionine maillard reaction products

    Directory of Open Access Journals (Sweden)

    Arum Tiyas Suminar

    2017-01-01

    Full Text Available Maillard reaction has been well understood as a non-enzymatic reaction between reducing sugars and amino acids to generate the Maillard reaction products (MRPs. This study is aimed to demonstrate the browning intensity, color development, spectra measurements, scavenging activity, and the correlation between browning intensity and scavenging activity of the MRPs generated from D-Psicose and Methionine (Psi-Met at 50℃. The browning intensity of MRPs was investigated based on the absorbance using spectrophotometer at 420 nm, the color development was observed using digital colorimeter to gained L*a*b* value then calculated as browning index, the spectra development was analyzed using spectrophotometer at 190 - 750 nm, and the scavenging activity was determined with ABTS method using spectrophotometer at 734 nm. The browning intensity, color development, and scavenging activity were improved along with the increase in heating process. Based on spectra analysis, MRPs from Psi-Met was initially detected at 21 h and Psi at 24 h of heating treatment, which indicating that Psi-Met have faster and better reaction than Psi during heating process. Positive non-linear and significant correlation between browning intensity and scavenging activity were assigned. This finding may provide beneficial information of D-psicose and MRPs to the next scientific research and to the food industries which applies MRPs in their products.

  10. Ground reaction forces, kinematics, and muscle activations during the windmill softball pitch.

    Science.gov (United States)

    Oliver, Gretchen D; Plummer, Hillary

    2011-07-01

    The aims of the present study were to examine quantitatively ground reaction forces, kinematics, and muscle activations during the windmill softball pitch, and to determine relationships between knee valgus and muscle activations, ball velocity and muscle activation as well as ball velocity and ground reaction forces. It was hypothesized that there would be an inverse relationship between degree of knee valgus and muscle activation, a direct relationship between ground reaction forces and ball velocity, and non-stride leg muscle activations and ball velocity. Ten female windmill softball pitchers (age 17.6 ± 3.47 years, stature 1.67 ± 0.07 m, weight 67.4 ± 12.2 kg) participated. Dependent variables were ball velocity, surface electromyographic (sEMG), kinematic, and kinetic data while the participant was the independent variable. Stride foot contact reported peak vertical forces of 179% body weight. There were positive relationships between ball velocity and ground reaction force (r = 0.758, n = 10, P = 0.029) as well as ball velocity and non-stride leg gluteus maximus (r = 0.851, n = 10, P = 0.007) and medius (r = 0.760, n = 10, P = 0.029) muscle activity, while there was no notable relationship between knee valgus and muscle activation. As the windmill softball pitcher increased ball velocity, her vertical ground reaction forces also increased. Proper conditioning of the lumbopelvic-hip complex, including the gluteals, is essential for injury prevention. From the data presented, it is evident that bilateral strength and conditioning of the gluteal muscle group is salient in the windmill softball pitch as an attempt to decrease incidence of injury.

  11. Control and switching synchronization of fractional order chaotic systems using active control technique

    KAUST Repository

    Radwan, A.G.; Moaddy, K.; Salama, Khaled N.; Momani, S.; Hashim, I.

    2013-01-01

    This paper discusses the continuous effect of the fractional order parameter of the Lü system where the system response starts stable, passing by chaotic behavior then reaching periodic response as the fractional-order increases. In addition, this paper presents the concept of synchronization of different fractional order chaotic systems using active control technique. Four different synchronization cases are introduced based on the switching parameters. Also, the static and dynamic synchronizations can be obtained when the switching parameters are functions of time. The nonstandard finite difference method is used for the numerical solution of the fractional order master and slave systems. Many numeric simulations are presented to validate the concept for different fractional order parameters.

  12. Control and switching synchronization of fractional order chaotic systems using active control technique

    KAUST Repository

    Radwan, A.G.

    2013-03-13

    This paper discusses the continuous effect of the fractional order parameter of the Lü system where the system response starts stable, passing by chaotic behavior then reaching periodic response as the fractional-order increases. In addition, this paper presents the concept of synchronization of different fractional order chaotic systems using active control technique. Four different synchronization cases are introduced based on the switching parameters. Also, the static and dynamic synchronizations can be obtained when the switching parameters are functions of time. The nonstandard finite difference method is used for the numerical solution of the fractional order master and slave systems. Many numeric simulations are presented to validate the concept for different fractional order parameters.

  13. A novel reaction catalysed by active carbons production of dichloromethane from phosgene and formaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, T A; Stacey, M H

    1984-08-01

    A variety of Activated charcoals have been found to catalyse a reaction between phosgene and formaldehyde. In a continuous flow fluidized bed reactor, the reaction rate reaches a broad maximum near 170/sup 0/C where the selectivity is consistent with the stoichiometry. The reaction proceeds via a strongly adsorbed intermediate which has been identified as chloromethyl chloroformate. This ester is an adduct of formaldehyde and phosgen and forms rapidly above 100/sup 0/C in co-adsorption/desorption experiments. It decomposes rapidly 170/sup 0/C without significant desorption of the intact molecule to give the observed products dichloromethane and carbon dioxide. Under steady-state conditions the rate-determining step is the formation of this ester so that it is normally only present on the surface at low coverages; hence it is not observable in the gas phase. The catalysis is probably due to the presence of polar acid or base sites on the surface of the activated charcoals.

  14. Electronic interactions decreasing the activation barrier for the hydrogen electro-oxidation reaction

    International Nuclear Information System (INIS)

    Santos, Elizabeth; Schmickler, Wolfgang

    2008-01-01

    A unified model for electrochemical electron transfer reactions which explicitly accounts for the electronic structure of the electrode recently proposed by us is applied to the hydrogen oxidation reaction at different metal electrocatalysts. We focus on the changes produced in the transition state (saddle point) as a consequence of the interactions with d-bands. We discuss different empirical correlations between properties of the metal and catalytic activity proposed in the past. We show which role is played by the band structure of the different metals and its interaction with the molecule for decreasing the activation barrier. Finally, we demonstrate why some metals are better electrocatalysts for the hydrogen electro-oxidation reaction than others

  15. Chaotic incommensurate fractional order Rössler system: active control and synchronization

    Directory of Open Access Journals (Sweden)

    Baleanu Dumitru

    2011-01-01

    Full Text Available Abstract In this article, we present an active control methodology for controlling the chaotic behavior of a fractional order version of Rössler system. The main feature of the designed controller is its simplicity for practical implementation. Although in controlling such complex system several inputs are used in general to actuate the states, in the proposed design, all states of the system are controlled via one input. Active synchronization of two chaotic fractional order Rössler systems is also investigated via a feedback linearization method. In both control and synchronization, numerical simulations show the efficiency of the proposed methods.

  16. Second-Order Perturbation Theory for Generalized Active Space Self-Consistent-Field Wave Functions.

    Science.gov (United States)

    Ma, Dongxia; Li Manni, Giovanni; Olsen, Jeppe; Gagliardi, Laura

    2016-07-12

    A multireference second-order perturbation theory approach based on the generalized active space self-consistent-field (GASSCF) wave function is presented. Compared with the complete active space (CAS) and restricted active space (RAS) wave functions, GAS wave functions are more flexible and can employ larger active spaces and/or different truncations of the configuration interaction expansion. With GASSCF, one can explore chemical systems that are not affordable with either CASSCF or RASSCF. Perturbation theory to second order on top of GAS wave functions (GASPT2) has been implemented to recover the remaining electron correlation. The method has been benchmarked by computing the chromium dimer ground-state potential energy curve. These calculations show that GASPT2 gives results similar to CASPT2 even with a configuration interaction expansion much smaller than the corresponding CAS expansion.

  17. Highly stable and active Ni-doped ordered mesoporous carbon catalyst on the steam reforming of ethanol application

    Directory of Open Access Journals (Sweden)

    Josh Y.Z. Chiou

    2017-02-01

    Full Text Available A novel one-step direct synthesis of nickel embedded in an ordered mesoporous carbon catalyst (NiOMC is done in a basic medium of nonaqueous solution by a solvent evaporation-induced self-assembly process. The NiOMC sample is characterized by a variety of analytical and spectroscopy techniques, e.g., N2 adsorption/desorption isotherm measurement, X-ray diffraction (XRD, transmission electron microscopy (TEM and temperature-programed reduction (TPR. In this study, the NiOMC catalyst is found to exhibit superior catalytic activity for the steam reforming of ethanol (SRE, showing high hydrogen selectivity and durability. Ethanol can be completely converted at 350 °C over the NiOMC catalyst. Also, the durability of the NiOMC catalyst on the SRE reaction exceeds 100 h at 450 °C, with SH2 approaching 65% and SCO of less than 1%.

  18. Bisindeno-annulated pentacenes with exceptionally high photo-stability and ordered molecular packing: Simple synthesis by a regio-selective Scholl reaction

    KAUST Repository

    Naibi Lakshminarayana, Arun; Chang, Jingjing; Luo, Jie; Zheng, Bin; Huang, Kuo-Wei; Chi, Chunyan

    2015-01-01

    Bisindeno-annulated pentacenes 3a and 3b were synthesized by a simple regio-selective, FeCl3-mediated Scholl reaction from the corresponding 6,13-diaryl pentacene precursors. The fusion of two indeno-units dramatically changes the electronic properties and chemical reactivity of pentacene and the obtained compounds exhibited exceptionally high photo-stability in the solution, with a half-life time of 11.2 (3a) and 32.0 (3b) days under ambient light and air conditions. Ordered molecular packing with a small π-π stacking distance was observed in the single crystals of 3a and 3b. Our research provides a promising strategy to access stable higher order acenes with controlled molecular order. This journal is

  19. The hydration of slag, part 1: reaction models for alkali-activated slag

    NARCIS (Netherlands)

    Chen, Wei; Brouwers, H.J.H.

    2007-01-01

    Reaction models are proposed to quantify the hydration products and to determine the composition of C–S–H from alkali-activated slags (AAS). Products of the slag hydration are first summarized from observations in literature. The main hydration products include C–S–H, hydrotalcite, hydrogarnet, AFm

  20. Deeper Insight into the Diels-Alder Reaction through the Activation Strain Model

    NARCIS (Netherlands)

    Fernandez, Israel; Bickelhaupt, F. Matthias

    2016-01-01

    In this Focus Review, we present the application of the so-called Activation Strain Model of chemical reactivity to the Diels–Alder cycloaddition reaction. To this end, representative recent examples have been selected to illustrate the power of this new computational approach to gain a deeper

  1. Deeper Insight into the Diels-Alder Reaction through the Activation Strain Model

    NARCIS (Netherlands)

    Fernandez, I.; Bickelhaupt, F.M.

    2016-01-01

    The Diels–Alder (DA) cycloaddition reaction has the ability to significantly increase molecular complexity regioselectively and stereospecifically in a single synthetic step. In this review it is discussed how the activation strain model of chemical reactivity reveals the physical factors that

  2. Synthesis of E-Diiodoalkenes: 1,2-diaminobenzene Activated Reaction of Alkvnes With iodine

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Article history:ReceivedReceived in revised formAcceptedAvailable online 1,2-diaminobenzene was found to active the reaction of iodine with terminal alkynes and E-diiodoalkenes were obtained in good to excellent yields.2009 Elsevier Ltd. All rights reserved.

  3. Pi-activated alcohols: an emerging class of alkylating agents for catalytic Friedel-Crafts reactions.

    Science.gov (United States)

    Bandini, Marco; Tragni, Michele

    2009-04-21

    The direct functionalization of aromatic compounds, via Friedel-Crafts alkylation reactions with alcohols, is one of the cornerstones in organic chemistry. The present emerging area deals with the recent advances in the use of pi-activated alcohols in the catalytic and stereoselective construction of benzylic stereocenters.

  4. MSU SINP CDFE nuclear data activities in the nuclear reaction data centres network

    International Nuclear Information System (INIS)

    Boboshin, I.N.; Varlamov, V.V.; Komarov, S.Yu.; Peskov, N.N.; Semin, S.B.; Stepanov, M.E.; Chesnokov, V.V.

    2002-01-01

    This paper is the progress report of the Centre for Photonuclear Experiments Data, Moscow. It is a short review of the works carried out by the CDFE concerning the IAEA nuclear reaction data centers network activities from May 2001 until May 2002. and the description of the main results obtained. (a.n.)

  5. Generalization of the Activated Complex Theory of Reaction Rates. II. Classical Mechanical Treatment

    Science.gov (United States)

    Marcus, R. A.

    1964-01-01

    In its usual classical form activated complex theory assumes a particular expression for the kinetic energy of the reacting system -- one associated with a rectilinear motion along the reaction coordinate. The derivation of the rate expression given in the present paper is based on the general kinetic energy expression.

  6. Activation pathways taking place at molecular copper precatalysts for the oxygen evolution reaction

    NARCIS (Netherlands)

    van der Ham, C.J.M.; Işık, F.; Verhoeven, T.W.G.M.; Niemantsverdriet, J.W.; Hetterscheid, D.G.H.

    2017-01-01

    The activation processes of [CuII(bdmpza)2] in the water oxidation reaction were investigated using cyclic voltammetry and chronoamperometry. Two different paths wherein CuO is formed were distinguished. [CuII(bdmpza)2] can be oxidized at high potentials to form CuO, which was observed by a slight

  7. Cerebral activation related to implicit sequence learning in a Double Serial Reaction Time task

    NARCIS (Netherlands)

    van der Graaf, FHCE; Maguire, RP; Leenders, KL; de Jong, BM

    2006-01-01

    Using functional magnetic resonance imaging (fMRI), we examined the distribution of cerebral activations related to implicitly learning a series of fixed stimulus-response combinations. In a novel - bimanual - variant of the Serial Reaction Time task (SRT), simultaneous finger movements of the two

  8. Measurement of activation cross sections for quasi-monoenergetic neutron induced reactions of {sup 89}Y

    Energy Technology Data Exchange (ETDEWEB)

    Zaman, Muhammad; Kim, Guinyun; Kim, Kwangsoo; Nadeem, Muhammad [Kyungpook National University, Department of Physics and Center for High Energy Physics, Daegu (Korea, Republic of); Naik, Haladhara [Kyungpook National University, Department of Physics and Center for High Energy Physics, Daegu (Korea, Republic of); Bhabha Atomic Research Centre, Radiochemistry Division, Mumbai (India); Lee, Manwoo [Dongnam Inst. of Radiological and Medical Sciences, Research Center, Busan (Korea, Republic of)

    2017-09-15

    The neutron induced cross sections of the {sup 89}Y(n, 2n){sup 88}Y, {sup 89}Y(n, 3n){sup 87}Y and {sup 89}Y(n, 4n){sup 86}Y reactions were measured in the neutron energy range of 15.2 to 37.2 MeV by using an activation and off-line γ-ray spectrometric technique. The quasi-monoenergetic neutrons used for the above reactions are based on a {sup 9}Be(p, n) reaction. Simulations of the neutron spectra from the Be target were done using the MCNPX 2.6.0 program. Theoretical calculations were performed for the {sup 89}Y(n, 2n){sup 88}Y, {sup 89}Y(n, 3n){sup 87}Y and {sup 89}Y(n, 4n){sup 86}Y reaction cross sections using nuclear model code Talys 1.8. The measured and calculated cross sections were compared with the literature data given in EXFOR and the TENDL-2015 data libraries. The present data of the {sup 89}Y(n, xn) reaction were also compared with the similar data of the {sup 89}Y(γ, xn) reaction to examine the effect of the entrance channel parameters as well as the role of projectiles and ejectiles. (orig.)

  9. Antibacterial Characteristics and Activity of Water-Soluble Chitosan Derivatives Prepared by the Maillard Reaction

    Directory of Open Access Journals (Sweden)

    Ying-Chien Chung

    2011-10-01

    Full Text Available The antibacterial activity of water-soluble chitosan derivatives prepared by Maillard reactions against Staphylococcus aureus, Listeria monocytogenes, Bacillus cereus, Escherichia coli, Shigella dysenteriae, and Salmonella typhimurium was examined. Relatively high antibacterial activity against various microorganisms was noted for the chitosan-glucosamine derivative as compared to the acid-soluble chitosan. In addition, it was found that the susceptibility of the test organisms to the water-soluble chitosan derivative was higher in deionized water than in saline solution. Metal ions were also found to reduce the antibacterial activity of the water-soluble chitosan derivative on S. aureus. The marked increase in glucose level, protein content and lactate dehydrogenase (LDH activity was observed in the cell supernatant of S. aureus exposed to the water-soluble chitosan derivative in deionized water. The results suggest that the water-soluble chitosan produced by Maillard reaction may be a promising commercial substitute for acid-soluble chitosan.

  10. Temperature dependent investigation on optically active process of higher-order bands in irradiated silicon

    International Nuclear Information System (INIS)

    Shi Yi; Nanjing Univ., JS; Wu Fengmei; Nanjing Univ., JS; Zheng Youdou; Nanjing Univ., JS; Suezawa, M.; Imai, M.; Sumino, K.

    1996-01-01

    Optically active processes of the higher-order bands (HOB) are investigated at different temperatures in fast neutron irradiated silicon using Fourier transform infrared absorption measurement. It is shown that the optically active process is nearly temperature independent below 80 K, the slow decay process remains up to a heating temperature of 180 K. The observations are analyzed in terms of the relaxation behavior of photoexcited carriers governed by fast neutron radiation induced defect clusters. (orig.)

  11. Incidence of transfusion reactions: a multi-center study utilizing systematic active surveillance and expert adjudication

    Science.gov (United States)

    Hendrickson, Jeanne E.; Roubinian, Nareg H.; Chowdhury, Dhuly; Brambilla, Don; Murphy, Edward L.; Wu, Yanyun; Ness, Paul M.; Gehrie, Eric A.; Snyder, Edward L.; Hauser, R. George; Gottschall, Jerome L.; Kleinman, Steve; Kakaiya, Ram; Strauss, Ronald G.

    2017-01-01

    Background Prevalence estimates of serious hazards of transfusion vary widely. We hypothesized that the current reporting infrastructure in the United States fails to capture many transfusion reactions, and undertook a multi-center study utilizing active surveillance, data review, and adjudication to test this hypothesis. Study Design and Methods A retrospective record review was completed for a random sample of 17% of all inpatient transfusion episodes over 6 months at 4 academic tertiary care hospitals, with an episode defined as all blood products released to a patient in 6 hours. Data were recorded by trained clinical research nurses, and serious reactions were adjudicated by a panel of transfusion medicine experts. Results Of 4857 transfusion episodes investigated, 1.1% were associated with a serious reaction. Transfusion associated circulatory overload (TACO) was the most frequent serious reaction noted, being identified in 1% of transfusion episodes. Despite clinical notes describing a potential transfusion association in 59% of these cases, only 5.1% were reported to the transfusion service. Suspected transfusion related acute lung injury (TRALI/possible TRALI), anaphylactic, and hypotensive reactions were noted in 0.08%, 0.02%, and 0.02% of transfusion episodes. Minor reactions, including febrile non-hemolytic and allergic, were noted in 0.62% and 0.29% of transfusion episodes, with 30–50% reported to the transfusion service. Conclusion Underreporting of cardiopulmonary transfusion reactions is striking among academic, tertiary care hospitals. Complete and accurate reporting is essential to identify, define, establish pathogenesis, and mitigate/treat transfusion reactions. A better understanding of the failure to report may improve the accuracy of passive reporting systems. PMID:27460200

  12. Study of the influence of decay data in activation reaction cross section

    International Nuclear Information System (INIS)

    Huang Xiaolong; Lu Hanlin

    2002-01-01

    The effect of the decay data on the measured activation cross section is investigated carefully and testified by several examples. These decay data include the half-life of the product, γ branching ratio of the product and decay scheme. Present work shows that these effects must be considered carefully when evaluating the activation reaction cross section. Sometimes they are main reason for causing the discrepancies among the experimental data

  13. Laboratory Activity Worksheet to Train High Order Thinking Skill of Student on Surface Chemistry Lecture

    Science.gov (United States)

    Yonata, B.; Nasrudin, H.

    2018-01-01

    A worksheet has to be a set with activity which is help students to arrange their own experiments. For this reason, this research is focused on how to train students’ higher order thinking skills in laboratory activity by developing laboratory activity worksheet on surface chemistry lecture. To ensure that the laboratory activity worksheet already contains aspects of the higher order thinking skill, it requires theoretical and empirical validation. From the data analysis results, it shows that the developed worksheet worth to use. The worksheet is worthy of theoretical and empirical feasibility. This conclusion is based on the findings: 1) Assessment from the validators about the theoretical feasibility aspects in the category is very feasible with an assessment range of 95.24% to 97.92%. 2) students’ higher thinking skill from N Gain values ranges from 0.50 (enough) to 1.00 (high) so it can be concluded that the laboratory activity worksheet on surface chemistry lecture is empirical in terms of worth. The empirical feasibility is supported by the responses of the students in very reasonable categories. It is expected that the laboratory activity worksheet on surface chemistry lecture can train students’ high order thinking skills for students who program surface chemistry lecture.

  14. Activity of molybdenum-containing oxide catalysts in the reaction of ethane oxidation

    International Nuclear Information System (INIS)

    Konovalov, V.I.; Ehpova, T.I.; Shchukin, V.P.; Averbukh, A.Ya.

    1977-01-01

    Investigation results concerning the catalytic activity of molybdenum-containing catalysts in ethane oxidation reaction are presented. It has been found that the greatest activity in the temperature range from 450 to 600 deg C is exhibited by cobalt-molybdenum catalyst; at 600 deg C bismuth-molybdenum catalyst is the most active. Nickel-molybdenum catalyst is selective and active with respect to ethylene. Iron- and manganese-molybdenum catalysts do not show high ethane oxidation rates and their selectivity is insignificant

  15. Effect of Heterogeneous Chemical Reactions on the Köhler Activation of Aqueous Organic Aerosols.

    Science.gov (United States)

    Djikaev, Yuri S; Ruckenstein, Eli

    2018-05-03

    We study some thermodynamic aspects of the activation of aqueous organic aerosols into cloud droplets considering the aerosols to consist of liquid solution of water and hydrophilic and hydrophobic organic compounds, taking into account the presence of reactive species in the air. The hydrophobic (surfactant) organic molecules on the surface of such an aerosol can be processed by chemical reactions with some atmospheric species; this affects the hygroscopicity of the aerosol and hence its ability to become a cloud droplet either via nucleation or via Köhler activation. The most probable pathway of such processing involves atmospheric hydroxyl radicals that abstract hydrogen atoms from hydrophobic organic molecules located on the aerosol surface (first step), the resulting radicals being quickly oxidized by ubiquitous atmospheric oxygen molecules to produce surface-bound peroxyl radicals (second step). These two reactions play a crucial role in the enhancement of the Köhler activation of the aerosol and its evolution into a cloud droplet. Taking them and a third reaction (next in the multistep chain of relevant heterogeneous reactions) into account, one can derive an explicit expression for the free energy of formation of a four-component aqueous droplet on a ternary aqueous organic aerosol as a function of four independent variables of state of a droplet. The results of numerical calculations suggest that the formation of cloud droplets on such (aqueous hydrophilic/hydrophobic organic) aerosols is most likely to occur as a Köhler activation-like process rather than via nucleation. The model allows one to determine the threshold parameters of the system necessary for the Köhler activation of such aerosols, which are predicted to be very sensitive to the equilibrium constant of the chain of three heterogeneous reactions involved in the chemical aging of aerosols.

  16. Motor unit activation order during electrically evoked contractions of paralyzed or partially paralyzed muscles

    NARCIS (Netherlands)

    Thomas, CK; Nelson, G; Than, L; Zijdewind, Inge

    The activation order of motor units during electrically evoked contractions of paralyzed or partially paralyzed thenar muscles was determined in seven subjects with chronic cervical spinal cord injury. The median nerve was stimulated percutaneously with pulses of graded intensity to produce

  17. Thermal annealing and recoil reactions of 128I atoms in thermal neutron activated iodate-nitrate mixed crystals

    International Nuclear Information System (INIS)

    Mishra, S.P.; Sharma, R.B.

    1983-01-01

    Recoil reaction of 128 I atoms in neutron irradiated mixed crystals (iodate-nitrate) have been studied by thermal annealing methods. The retention of 128 I (i.e. radioactivity of 128 I retained in the parent chemi cal form) decreases sharply in the beginning and then attains saturation value with the increase in concentration of nitrate. The annealing followed the usual characteristic pattern, viz., a steep rise in retention within the first few minutes and then a saturation value thereafter but these saturation values in case of mixed crystals are lower in comparison to those of pure iodate targets. The process obeys simple first order kinetics and the activation energy obtained are of lower order than those obtained in case of pure targets. The results are discussed in the light of present ideas and the role of nitrate ion and its radiolytic products have also been invoked. (author)

  18. Fractional-order positive position feedback compensator for active vibration control of a smart composite plate

    Science.gov (United States)

    Marinangeli, L.; Alijani, F.; HosseinNia, S. Hassan

    2018-01-01

    In this paper, Active Vibration Control (AVC) of a rectangular carbon fibre composite plate with free edges is presented. The plate is subjected to out-of-plane excitation by a modal vibration exciter and controlled by Macro Fibre Composite (MFC) transducers. Vibration measurements are performed by using a Laser Doppler Vibrometer (LDV) system. A fractional-order Positive Position Feedback (PPF) compensator is proposed, implemented and compared to the standard integer-order PPF. MFC actuator and sensor are positioned on the plate based on maximal modal strain criterion, so as to control the second natural mode of the plate. Both integer and fractional-order PPF allowed for the effective control of the second mode of vibration. However, the newly proposed fractional-order controller is found to be more efficient in achieving the same performance with less actuation voltage. Moreover, it shows promising performance in reducing spillover effect due to uncontrolled modes.

  19. Deeper Insight into the Diels-Alder Reaction through the Activation Strain Model.

    Science.gov (United States)

    Fernández, Israel; Bickelhaupt, F Matthias

    2016-12-06

    In this Focus Review, we present the application of the so-called Activation Strain Model of chemical reactivity to the Diels-Alder cycloaddition reaction. To this end, representative recent examples have been selected to illustrate the power of this new computational approach to gain a deeper quantitative understanding of this fundamental process in chemistry. We cover a wide range of issues, such as, the "endo-rule", reactivity trends emerging from systematic variation in the reactants' strain, and cycloaddition reactions involving relevant species in material science, that is, fullerenes, polycyclic aromatic hydrocarbons and nanotubes. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Velocity and thermal slip effects on MHD third order blood flow in an irregular channel though a porous medium with homogeneous/ heterogeneous reactions

    Science.gov (United States)

    Gnaneswara Reddy, M.

    2017-09-01

    This communication presents the transportation of third order hydromagnetic fluid with thermal radiation by peristalsis through an irregular channel configuration filled a porous medium under the low Reynolds number and large wavelength approximations. Joule heating, Hall current and homogeneous-heterogeneous reactions effects are considered in the energy and species equations. The Second-order velocity and energy slip restrictions are invoked. Final dimensionless governing transport equations along the boundary restrictions are resolved numerically with the help of NDsolve in Mathematica package. Impact of involved sundry parameters on the non-dimensional axial velocity, fluid temperature and concentration characteristics have been analyzed via plots and tables. It is manifest that an increasing porosity parameter leads to maximum velocity in the core part of the channel. Fluid velocity boosts near the walls of the channel where as the reverse effect in the central part of the channel for higher values of first order slip. Larger values of thermal radiation parameter R reduce the fluid temperature field. Also, an increase in heterogeneous reaction parameter Ks magnifies the concentration profile. The present study has the crucial application of thermal therapy in biomedical engineering.

  1. Activation cross section of 63Cu(n,α)60Co reaction

    International Nuclear Information System (INIS)

    Lu Hanlin; Zhao Wenrong; Yu Weixiang; Yuan Xialin

    1990-01-01

    The mechanical properties of copper during the irradiation with intensive neutron fluence rate are significant for the safe operation of D-T fusion power reactors. The cross sections measured by activation method show a large discrepancy from 36 to 54 mb in 14 MeV region. The cross sections of 69 Cu(n, α) 60 Co reaction were measured by activation method. Two irradiations were carried out at the Cockcroft-wallon and Van de Graaff accelerators of CIAE using T(d, n) 4 He reaction to produce neutrons. The activities of 24 Na and 60 Co γ-rays for monitor and sample foils were determined absolutely by a calibrated Ge(Li) detector system with an accuracy better than 1%. The present results are compared with the others

  2. Influence of Exercise Order on Electromyographic Activity During Upper Body Resistance Training

    Directory of Open Access Journals (Sweden)

    Soncin Rafael

    2014-12-01

    Full Text Available The purpose of this study was to investigate the effects of exercise order on electromyographic activity in different muscle groups among youth men with experience in strength training. Three sets of 8 RM were performed of each exercise in two sequences order: (a sequence A: bench press, chest fly, shoulder press, shoulder abduction, close grip bench press and lying triceps extension; (b sequence B: the opposite order. The electromyographic activity was analyzed in the sternocostal head of the pectoralis major, anterior deltoid, and long head triceps brachii, normalized for maximal voluntary isometric contraction. The muscles activity of the sternocostal head of the pectoralis major, anterior deltoid, and long head triceps brachii showed significant interaction between sequence and exercise. The sternocostal head of the pectoralis major showed considerably higher activity in sequence A (100.13 ± 13.56% than sequence B (81.47 ± 13.09% for the chest fly. The anterior deltoid showed significantly higher electromyographic activity in sequence B (86.81 ± 40.43% than sequence A (66.15 ± 22.02% for the chest fly, whereas for the lying triceps extension, the electromyographic activity was significantly higher in sequence A (53.89 ± 27.09% than sequence B (34.32 ± 23.70%. For the long head triceps brachii, only the shoulder press showed differences between sequences (A = 52.43 ± 14.64 vs. B = 38.53 ± 16.26. The present study showed that the exercise order could modify the training results even though there was no alteration in volume and intensity of the exercise. These changes may result in different training adaptations.

  3. Determination of the absolute second-order rate constant for the reaction Na + O3 → NaO + O2

    International Nuclear Information System (INIS)

    Husain, David; Marshall, Paul; Plane, J.M.C.

    1985-01-01

    The absolute second-order rate constant for the reaction Na + O 3 -> NaO + O 2 (k 1 ) has been determined by time-resolved atomic resonance absorption spectroscopy at lambda = 589 nm [Na(3 2 Psub(j)) 2 Ssub(1/2))] following pulsed irradiation, coupled with monitoring of O 3 by light absorption in the ultra-violet; this yields k 1 (500 K) = 4(+4,-2) x 10 -10 cm 3 molecule -1 s -1 , resolving large differences for various estimates of this important quantity used in modelling the sodium layer in the mesosphere. (author)

  4. Directing reaction pathways by catalyst active-site selection using self-assembled monolayers.

    Science.gov (United States)

    Pang, Simon H; Schoenbaum, Carolyn A; Schwartz, Daniel K; Medlin, J Will

    2013-01-01

    One key route for controlling reaction selectivity in heterogeneous catalysis is to prepare catalysts that exhibit only specific types of sites required for desired product formation. Here we show that alkanethiolate self-assembled monolayers with varying surface densities can be used to tune selectivity to desired hydrogenation and hydrodeoxygenation products during the reaction of furfural on supported palladium catalysts. Vibrational spectroscopic studies demonstrate that the selectivity improvement is achieved by controlling the availability of specific sites for the hydrogenation of furfural on supported palladium catalysts through the selection of an appropriate alkanethiolate. Increasing self-assembled monolayer density by controlling the steric bulk of the organic tail ligand restricts adsorption on terrace sites and dramatically increases selectivity to desired products furfuryl alcohol and methylfuran. This technique of active-site selection simultaneously serves both to enhance selectivity and provide insight into the reaction mechanism.

  5. Potential Effect of Physical Activity Calorie Equivalent (PACE) Labeling on Adult Fast Food Ordering and Exercise.

    Science.gov (United States)

    Antonelli, Ray; Viera, Anthony J

    2015-01-01

    Numeric calorie content labels show limited efficacy in reducing the number of calories ordered from fast food meals. Physical activity calorie equivalent (PACE) labels are an alternative that may reduce the number of calories ordered in fast food meals while encouraging patrons to exercise. A total of 1000 adults from 47 US states were randomly assigned via internet survey to one of four generic fast food menus: no label, calories only, calories + minutes, or calories + miles necessary to walk to burn off the calories. After completing hypothetical orders participants were asked to rate the likelihood of calorie-only and PACE labels to influence (1) food choice and (2) physical activity. Respondents (n = 823) ordered a median of 1580 calories from the no-label menu, 1200 from the calories-only menu, 1140 from the calories + minutes menu, and 1210 from the calories + miles menu (p = 0.0001). 40% of respondents reported that PACE labels were "very likely" to influence food item choice vs. 28% for calorie-only labels (pcalorie-only labels (pcalories ordered in fast food meals and may have the added benefit of encouraging exercise.

  6. Hydrogen desorption reactions of Li-N-H hydrogen storage system: Estimation of activation free energy

    International Nuclear Information System (INIS)

    Matsumoto, Mitsuru; Haga, Tetsuya; Kawai, Yasuaki; Kojima, Yoshitsugu

    2007-01-01

    The dehydrogenation reactions of the mixtures of lithium amide (LiNH 2 ) and lithium hydride (LiH) were studied under an Ar atmosphere by means of temperature programmed desorption (TPD) technique. The dehydrogenation reaction of the LiNH 2 /LiH mixture was accelerated by addition of 1 mol% Ti(III) species (k = 3.1 x 10 -4 s -1 at 493 K), and prolonged ball-milling time (16 h) further enhanced reaction rate (k = 1.1 x 10 -3 s -1 at 493 K). For the hydrogen desorption reaction of Ti(III) doped samples, the activation energies estimated by Kissinger plot (95 kJ mol -1 ) and Arrhenius plot (110 kJ mol -1 ) were in reasonable agreement. The LiNH 2 /LiH mixture without Ti(III) species, exhibited slower hydrogen desorption process and the kinetic traces deviated from single exponential behavior. The results indicated the Ti(III) additives change the hydrogen desorption reaction mechanism of the LiNH 2 /LiH mixture

  7. Active specific immunotherapy using the immune reaction of a low-dose irradiated tumor tissue

    International Nuclear Information System (INIS)

    Ogawa, Y.; Imanaka, K.; Ashida, C.; Takashima, H.; Imajo, Y.; Kimura, S.

    1983-01-01

    Active specific immunotherapy using the immune reaction of a low-dose irradiated tumor tissue was studied on the transplanted MM46 tumor of female C3H/He mice after radiotherapy. MM46 tumor cells were inoculated into the right hind paws of mice. On the 5th day, irradiation with the dose irradiated tumor tissue (2000 rad on the fifth day), were injected into the left hind paws of the tumor-bearing mice. Effectiveness of this active specific immunotherapy against tumor was evaluated by the regression of tumor and survival rate of mice. Tumor was markedly regressed and survival rate was significantly increased by the active specific immunitherapy

  8. Factors responsible for activity of catalysts of different chemical types in the reaction of hydrogen oxidation

    International Nuclear Information System (INIS)

    Il'chenko, N.I.; Dolgikh, L.Yu.

    1985-01-01

    Reasons of differences in the kinetics and mechanism of the H 2 oxidation on optimum metallic (Pt), carbide (WC) and oxide (Co 3 O 4 ) catalysts are discussed. These differences lead to unequal specific activity. It is shown that the catalytic activity of the catalysts in question increases with respect to reactions of isotopic exchange and hydrogen oxidation with an increasing electron-donating ability of anat of the transition metal M on which H 2 is adsorbed. The possibility is considered of increasing the transition metal activity by introduction of additions to increase the electron-donating ability of M

  9. Efficient numerical simulation of non-integer-order space-fractional reaction-diffusion equation via the Riemann-Liouville operator

    Science.gov (United States)

    Owolabi, Kolade M.

    2018-03-01

    In this work, we are concerned with the solution of non-integer space-fractional reaction-diffusion equations with the Riemann-Liouville space-fractional derivative in high dimensions. We approximate the Riemann-Liouville derivative with the Fourier transform method and advance the resulting system in time with any time-stepping solver. In the numerical experiments, we expect the travelling wave to arise from the given initial condition on the computational domain (-∞, ∞), which we terminate in the numerical experiments with a large but truncated value of L. It is necessary to choose L large enough to allow the waves to have enough space to distribute. Experimental results in high dimensions on the space-fractional reaction-diffusion models with applications to biological models (Fisher and Allen-Cahn equations) are considered. Simulation results reveal that fractional reaction-diffusion equations can give rise to a range of physical phenomena when compared to non-integer-order cases. As a result, most meaningful and practical situations are found to be modelled with the concept of fractional calculus.

  10. Formation of Reactive Intermediates, Color, and Antioxidant Activity in the Maillard Reaction of Maltose in Comparison to d-Glucose.

    Science.gov (United States)

    Kanzler, Clemens; Schestkowa, Helena; Haase, Paul T; Kroh, Lothar W

    2017-10-11

    In this study, the Maillard reaction of maltose and d-glucose in the presence of l-alanine was investigated in aqueous solution at 130 °C and pH 5. The reactivity of both carbohydrates was compared in regards of their degradation, browning, and antioxidant activity. In order to identify relevant differences in the reaction pathways, the concentrations of selected intermediates such as 1,2-dicarbonyl compounds, furans, furanones, and pyranones were determined. It was found, that the degradation of maltose predominantly yields 1,2-dicarbonyls that still carry a glucosyl moiety and thus subsequent reactions to HMF, furfural, and 2-acetylfuran are favored due to the elimination of d-glucose, which is an excellent leaving group in aqueous solution. Consequently, higher amounts of these heterocycles are formed from maltose. 3-deoxyglucosone and 3-deoxygalactosone represent the only relevant C 6 -1,2-dicarbonyls in maltose incubations and are produced in nearly equimolar amounts during the first 60 min of heating as byproducts of the HMF formation.

  11. Person-based differences in pay reactions: A compensation-activation theory and integrative conceptual review.

    Science.gov (United States)

    Fulmer, Ingrid Smithey; Shaw, Jason D

    2018-06-07

    Compensation research has focused traditionally on how pay design characteristics (e.g., pay level, individual or group incentives) relate to average employee outcomes and, in toto, on how these outcomes affect organizational performance. Recently, scholars have begun to pay more attention to how individuals vary in the strength of their reactions to pay. Empirical research in several disciplines examines how the interplay of pay systems and person-based characteristics (psychological individual differences, demographics, and relative performance or position in a group) relate to important work-related outcomes. We develop a compensation-activation theory that frames compensation design characteristics as workplace "situations" providing cues that activate individuals' corresponding fundamental social motives made salient due to chronic or transient person-based characteristics. Where activation occurs, stronger-than-average responses to the compensation "situation" are expected. Using the theory as a lens, we synthesize and reinterpret existing research on person-based reactions to pay characteristics, including sorting, incentive/motivational effects, and effects on collective pay system reactions and unit/organizational outcomes. We conclude with a research agenda aimed at refining compensation-activation theory and advancing the study of compensation as it affects individual and organizational outcomes. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

  12. Analytical basis for neutron-activation analysis measuring nuclides with a half-life of second order

    International Nuclear Information System (INIS)

    Yonezawa, Chushiro; Ichimura, Shigeju; Matsue, Hideaki; Kurosawa, Tatsuya

    1998-01-01

    An analytical basis for a neutron-activation analysis (NAA) for measuring nuclides of second-order half-lives produced by the (n, γ) reaction has been studied using a neutron-activation analysis facility (PN-3) of JRR-3M. The NAA facility, comprising a fast pneumatic irradiation system and a high count-rate gamma-ray spectrometer, is able to automatically conduct NAA with short-lived nuclides. Basic experimental conditions, such as a high count-rate gamma-ray measurement, the effects of irradiation-capsule material and the stability of the neutron flux, were examined. The analytical sensitivities and detection limits for 20 elements of which activated radionuclide having half-lives from 0.7 to 100 s were obtained. Scandium, In, Dy and Hf were elements having the highest analytical sensitivity, with detection limits down to 4.2 to 14 ng. Fluorine, which is difficult to determine by other methods, can be detected at above 530 ng. Analytical applications of NAA with short-lived nuclides have been carried out for F, Se, Sc, Hf, In and Dy in various materials, including reference materials. The accuracy, precision and detection limits of NAA with short-lived nuclides have been evaluated. (author)

  13. Structure, activity, and stability of platinum alloys as catalysts for the oxygen reduction reaction

    DEFF Research Database (Denmark)

    Vej-Hansen, Ulrik Grønbjerg

    In this thesis I present our work on theoretical modelling of platinum alloys as catalysts for the Oxygen Reduction Reaction (ORR). The losses associated with the kinetics of the ORR is the main bottleneck in low-temperature fuel cells for transport applications, and more active catalysts...... are essential for wide-spread use of this technology. platinum alloys have shown great promise as more active catalysts, which are still stable under reaction conditions. We have investigated these systems on multiple scales, using either Density Functional Theory (DFT) or Effective Medium Theory (EMT......), depending on the length and time scales involved. Using DFT, we show how diffusion barriers in transition metal alloys in the L12 structure depend on the alloying energy, supporting the assumption that an intrinsically more stable alloy is also more stable towards diffusion-related degradation...

  14. Reaction of active uranium and thorium with aromatic carbonyls and pinacols in hydrocarbon solvents

    International Nuclear Information System (INIS)

    Kahn, B.E.; Rieke, R.D.

    1988-01-01

    Highly reactive uranium and thorium metal powders have been prepared by reduction of the anhydrous metal(IV) chlorides in hydrocarbon solvents. The reduction employs the crystalline hydrocarbon-soluble reducing agent [(TMEDA)Li] 2 [Nap] (TMEDA = N,N,N',N'-tetramethylethylenediamine, Nap = naphthalene). The resulting active metal powders have been shown to be extremely reactive with oxygen-containing compounds and have been used in the reductive coupling of aromatic ketones giving tetra-arylethylenes. Reactions with pinacols have given some mechanistic insight into the ketone coupling reaction. These finely divided metal powders activate very weakly acidic C-H bonds forming metal hydrides, which can be transferred to organic substrates

  15. Experimental studies on excitation functions of the proton-induced activation reactions on silver

    International Nuclear Information System (INIS)

    Uddin, M.S.; Hagiwara, M.; Baba, M.; Tarkanyi, F.; Ditroi, F.

    2005-01-01

    Excitation functions were measured for the production of 106m,105 Ag, 103,101,100 Pd, 105,102,101m,100,99 Rh and 97 Ru via proton-induced activation reactions on natural silver using a stacked foil technique in the energy range 11-80 MeV. The residual activity measurements were carried out nondestructively by the high-resolution HPGe γ-ray spectroscopy. Thick target integral yields were deduced using the measured cross-sections from the respective threshold energies of the investigated reactions up to 80 MeV. The present work gives new results for the investigated radionuclides. The data in MENDL-2P deduced with the theoretical model code ALICE-IPPE are consistent in shape with the measured values, but show disagreement in magnitude

  16. Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Liu, Baocang [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Gong, Xia [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Zheng, Dafang [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Zhang, Jun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Wang, Qin, E-mail: qinwang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China)

    2016-12-15

    Graphical abstract: Ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities (NDs) catalysts, are successfully synthesized by using a facile method. The as-obtained ternary catalysts manifest superior catalytic activity and stability both in terms of surface and mass specific activities toward the methanol oxidation and oxygen reduction reactions, as compared to the binary catalysts and the commercial Pt/C catalysts. - Highlights: • Ternary RuMPt catalysts are synthesized by using a facile method. • The catalysts manifest superior catalytic activity towards the MOR and ORR. • High activities are attributed to enhanced electron density and synergistic effects. - Abstract: The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg{sup −1}) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

  17. Synthesis and electrocatalytic activity towards oxygen reduction reaction of gold-nanostars

    Directory of Open Access Journals (Sweden)

    Oyunbileg G

    2018-02-01

    Full Text Available The oxygen reduction reaction (ORR is a characteristic reaction which determines the performance of fuel cells which convert a chemical energy into an electrical energy. Aims of this study are to synthesize Au-based nanostars (AuNSs and determine their preliminary electro-catalytic activities towards ORR by a rotating-disk electrode method in alkaline electrolyte. The images obtained from a scanning electron microscope (SEM and a transmission electron microscope (TEM analyses confirm the formation of the star-shaped nanoparticles. Among the investigated nanostar catalysts, an AuNS5 with smaller size and a few branches showed the higher electrocatalytic activity towards ORR than other catalysts with a bigger size. In addition, the electron numbers transferred for all the catalysts are approximately two. The present study results infer that the size of the Au-based nanostars may influence greatly on their catalytic activity. The present study results show that the further improvement is needed for Au-based nanostar catalysts towards the ORR reaction.

  18. Simultaneous demonstration of gelatinolytic activity, morphology, and immunohistochemical reaction using zymography film.

    Science.gov (United States)

    Kanomata, Naoki; Hasebe, Takahiro; Moriya, Takuya; Ochiai, Atsushi

    2013-12-01

    In situ zymography has been used to assess gelatinolytic activity, which is mainly due to matrix metalloproteinases (MMPs) in cancer tissues. MMPs play an important role in cancer invasion and metastasis. Film in situ zymography (FIZ) enables the in situ evaluation of gelatinolytic activity with high reproducibility. In this article, we report a study of FIZ, in a case of breast cancer with an invasive carcinoma component showing clear gelatinolytic activity, and in a non-invasive carcinoma component showing little gelatinolytic activity. Immunohistochemistry on FIZ was also performed. The simultaneous detection of gelatinolytic activity and immunohistochemical reaction was established in a single film. Immunohistochemistry on FIZ may have good potential for the investigation of cancer microenvironment.

  19. Selective C–C Coupling Reaction of Dimethylphenol to Tetramethyldiphenoquinone Using Molecular Oxygen Catalyzed by Cu Complexes Immobilized in Nanospaces of Structurally-Ordered Materials

    Directory of Open Access Journals (Sweden)

    Zen Maeno

    2015-02-01

    Full Text Available Two high-performance Cu catalysts were successfully developed by immobilization of Cu ions in the nanospaces of poly(propylene imine (PPI dendrimer and magadiite for the selective C–C coupling of 2,6-dimethylphenol (DMP to 3,3',5,5'-tetramethyldiphenoquinone (DPQ with O2 as a green oxidant. The PPI dendrimer encapsulated Cu ions in the internal nanovoids to form adjacent Cu species, which exhibited significantly high catalytic activity for the regioselective coupling reaction of DMP compared to previously reported enzyme and metal complex catalysts. The magadiite-immobilized Cu complex acted as a selective heterogeneous catalyst for the oxidative C–C coupling of DMP to DPQ. This heterogeneous catalyst was recoverable from the reaction mixture by simple filtration, reusable without loss of efficiency, and applicable to a continuous flow reactor system. Detailed characterization using ultraviolet-visible (UV-vis, Fourier transform infrared (FTIR, electronic spin resonance (ESR, and X-ray absorption fine structure (XAFS spectroscopies and the reaction mechanism investigation revealed that the high catalytic performances of these Cu catalysts were ascribed to the adjacent Cu species generated within the nanospaces of the PPI dendrimer and magadiite.

  20. Trans-methylation reactions in plants: focus on the activated methyl cycle.

    Science.gov (United States)

    Rahikainen, Moona; Alegre, Sara; Trotta, Andrea; Pascual, Jesús; Kangasjärvi, Saijaliisa

    2018-02-01

    Trans-methylation reactions are vital in basic metabolism, epigenetic regulation, RNA metabolism, and posttranslational control of protein function and therefore fundamental in determining the physiological processes in all living organisms. The plant kingdom is additionally characterized by the production of secondary metabolites that undergo specific hydroxylation, oxidation and methylation reactions to obtain a wide array of different chemical structures. Increasing research efforts have started to reveal the enzymatic pathways underlying the biosynthesis of complex metabolites in plants. Further engineering of these enzymatic machineries offers significant possibilities in the development of bio-based technologies, but necessitates deep understanding of their potential metabolic and regulatory interactions. Trans-methylation reactions are tightly coupled with the so-called activated methyl cycle (AMC), an essential metabolic circuit that maintains the trans-methylation capacity in all living cells. Tight regulation of the AMC is crucial in ensuring accurate trans-methylation reactions in different subcellular compartments, cell types, developmental stages and environmental conditions. This review addresses the organization and posttranslational regulation of the AMC and elaborates its critical role in determining metabolic regulation through modulation of methyl utilization in stress-exposed plants. © 2017 Scandinavian Plant Physiology Society.

  1. Negativization rates of IgE radioimmunoassay and basophil activation test in immediate reactions to penicillins.

    Science.gov (United States)

    Fernández, T D; Torres, M J; Blanca-López, N; Rodríguez-Bada, J L; Gomez, E; Canto, G; Mayorga, C; Blanca, M

    2009-02-01

    Skin test sensitivity in patients with immediate allergy to penicillins tends to decrease over time, but no information is available concerning in vitro tests. We analysed the negativization rates of two in vitro methods that determine specific immunoglobulin E (IgE) antibodies, the basophil activation test using flow cytometry (BAT) and the radioallergosorbent test (RAST), in immediate allergic reactions to penicillins. Forty-one patients with immediate allergic reactions to amoxicillin were followed up over a 4-year period. BAT and RAST were performed at 6-month intervals. Patients were randomized into groups: Group I, skin tests carried out at regular intervals; Group II, skin tests made only at the beginning of the study. Differences were observed between RAST and BAT (P testing influenced the rate of negativization of the RAST assay, contributing to maintenance of in vitro sensitivity. Because of the loss of sensitivity over time, the determination of specific IgE antibodies to penicillins in patients with immediate allergic reactions must be done as soon as possible after the reaction.

  2. KOH-activated multi-walled carbon nanotubes as platinum supports for oxygen reduction reaction

    Science.gov (United States)

    He, Chaoxiong; Song, Shuqin; Liu, Jinchao; Maragou, Vasiliki; Tsiakaras, Panagiotis

    In the present investigation, multi-walled carbon nanotubes (MWCNTs) thermally treated by KOH were adopted as the platinum supporting material for the oxygen reduction reaction electrocatalysts. FTIR and Raman spectra were used to investigate the surface state of MWCNTs treated by KOH at different temperatures (700, 800, and 900 °C) and showed MWCNTs can be successfully functionalized. The structural properties of KOH-activated MWCNTs supported Pt were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their electrochemical performance was evaluated by the aid of cyclic voltammetry (CV) and rotating disk electrode (RDE) voltammetry. According to the experimental findings of the present work, the surrface of MWCNTs can be successfully functionalized with oxygen-containing groups after activation by KOH, favoring the good dispersion of Pt nanoparticles with narrow size distribution. The as-prepared Pt catalysts supported on KOH treated MWCNTs at higher temperature, possess higher electrochemical surface area and exhibit desirable activity towards oxygen reduction reaction (ORR). More precisely, it has been found that the electrochemical active area of Pt/MWCNTs-900 is approximately two times higher than that of Pt/MWCNTs. It can be concluded that KOH activation is an effective way to decorate MWCNTs' surface with oxygen-containing groups and bigger surface area, which makes them more suitable as electrocatalyst support materials.

  3. Increase of rutin antioxidant activity by generating Maillard reaction products with lysine.

    Science.gov (United States)

    Zhang, Ru; Zhang, Bian-Ling; He, Ting; Yi, Ting; Yang, Ji-Ping; He, Bin

    2016-06-01

    Rutin exists in medicinal herbs, fruits, vegetables, and a number of plant-derived sources. Dietary sources containing rutin are considered beneficial because of their potential protective roles in multiple diseases related to oxidative stresses. In the present study, the change and antioxidation activity of rutin in Maillard reaction with lysine through a heating process were investigated. There is release of glucose and rhamnose that interact with lysine to give Maillard reaction products (MRPs), while rutin is converted to less-polar quercetin and a small quantity of isoquercitrin. Because of their high cell-membrane permeability, the rutin-lysine MRPs increase the free radical-scavenging activity in HepG2 cells, showing cellular antioxidant activity against Cu(2+)-induced oxidative stress higher than that of rutin. Furthermore, the MRPs significantly increased the Cu/Zn SOD (superoxide dismutase) activity and Cu/Zn SOD gene expression of HepG2 cells, consequently enhancing antioxidation activity. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Enzyme Stability and Activity in Non-Aqueous Reaction Systems: A Mini Review

    Directory of Open Access Journals (Sweden)

    Shihui Wang

    2016-02-01

    Full Text Available Enormous interest in biocatalysis in non-aqueous phase has recently been triggered due to the merits of good enantioselectivity, reverse thermodynamic equilibrium, and no water-dependent side reactions. It has been demonstrated that enzyme has high activity and stability in non-aqueous media, and the variation of enzyme activity is attributed to its conformational modifications. This review comprehensively addresses the stability and activity of the intact enzymes in various non-aqueous systems, such as organic solvents, ionic liquids, sub-/super-critical fluids and their combined mixtures. It has been revealed that critical factors such as Log P, functional groups and the molecular structures of the solvents define the microenvironment surrounding the enzyme molecule and affect enzyme tertiary and secondary structure, influencing enzyme catalytic properties. Therefore, it is of high importance for biocatalysis in non-aqueous media to elucidate the links between the microenvironment surrounding enzyme surface and its stability and activity. In fact, a better understanding of the correlation between different non-aqueous environments and enzyme structure, stability and activity can contribute to identifying the most suitable reaction medium for a given biotransformation.

  5. The effect of changes to question order on the prevalence of 'sufficient' physical activity in an Australian population survey.

    Science.gov (United States)

    Hanley, Christine; Duncan, Mitch J; Mummery, W Kerry

    2013-03-01

    Population surveys are frequently used to assess prevalence, correlates and health benefits of physical activity. However, nonsampling errors, such as question order effects, in surveys may lead to imprecision in self reported physical activity. This study examined the impact of modified question order in a commonly used physical activity questionnaire on the prevalence of sufficient physical activity. Data were obtained from a telephone survey of adults living in Queensland, Australia. A total of 1243 adults participated in the computer-assisted telephone interview (CATI) survey conducted in July 2008 which included the Active Australia Questionnaire (AAQ) presented in traditional or modified order. Binary logistic regression analyses was used to examine relationships between question order and physical activity outcomes. Significant relationships were found between question order and sufficient activity, recreational walking, moderate activity, vigorous activity, and total activity. Respondents who received the AAQ in modified order were more likely to be categorized as sufficiently active (OR = 1.28, 95% CI 1.01-1.60). This study highlights the importance of question order on estimates of self reported physical activity. This study has shown that changes in question order can lead to an increase in the proportion of participants classified as sufficiently active.

  6. Activity and selectivity of three molybdenum catalysts for coal liquefaction reactions

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W.; Pellegrino, J.L.

    The activity and selectivity of three different molybdenum catalysts for reactions occurring in coal liquefaction, specifically for hydrogenation (HYD), hydrodeoxygenation (HDO), hydrodenitrogenation (HDN), hydrodesulfurization (HDS), and hydrocracking (HYC), have been examined. The three molybdenum catalysts used were molybdenum napthenate, molybdenum on ..gamma..-alumina, and a precipitated, disordered MoS/sub 2/. Molybdenum naphthenate was most selective for HYD and HDN. All three catalysts exhibited approximately equal activity for HDS and HDO and little selectivity for HYC of alkyl bridge structures. The activity and selectivity of the three molybdenum catalysts for producing hydrocarbons and removing heteroatoms from coal during liquefaction were determined and compared. Molybdenum naphthenate was the most active catalyst for hydrocarbon production and removal of nitrogen- and oxygen-containing species during coal liquefaction. 31 refs., 4 figs., 7 tabs.

  7. Origins of the Unfavorable Activation and Reaction Energies of 1-Azadiene Heterocycles Compared to 2-Azadiene Heterocycles in Diels-Alder Reactions.

    Science.gov (United States)

    Fell, Jason S; Martin, Blanton N; Houk, K N

    2017-02-17

    The reactivities of butadiene, cyclopentadiene, furan, thiophene, pyrrole, and their 1-aza- and 2-aza-derivatives in Diels-Alder reactions with ethylene and fumaronitrile were investigated with density functional theory (M06-2X/6-311G(d,p)). The activation free energies for the Diels-Alder reactions of cyclic 1-azadienes are 10-14 kcal mol -1 higher than those of cyclic 2-azadienes, and the reaction free energies are 17-20 kcal mol -1 more endergonic. The distortion/interaction model shows that the increased activation energies of cyclic 1-azadienes originate from increased transition state distortion energies and unfavorable interaction energies, arising from addition to the nitrogen terminus of the C═N bond.

  8. Structural and surface changes of cobalt modified manganese oxide during activation and ethanol steam reforming reaction

    Science.gov (United States)

    Gac, Wojciech; Greluk, Magdalena; Słowik, Grzegorz; Turczyniak-Surdacka, Sylwia

    2018-05-01

    Surface and structural changes of unmodified manganese and cobalt-manganese oxide during activation and ethanol steam reforming reaction conditions (ESR) were studied by means of X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed reduction/oxidation (TPR/TPO) and transmission electron microscopy. It was shown that synthesis of cobalt manganese oxide by the redox precipitation method led to the formation of strongly dispersed cobalt ionic species within cryptomelane-based manganese oxide structure. Development of large cube-like MnO nanoparticles with spherical cobalt metallic crystallites decorated by manganese oxide on the high oxidation state and potassium species was observed during reduction. Cobalt manganese catalyst showed high initial activity and selectivity to H2 and CO2 in ethanol stem reforming reaction in the range of 390-480 °C. The drop of ethanol conversion and changes of selectivity with the time-on-stream were observed. An increase of reaction temperature led to intensification of deactivation phenomena. TEM studies evidenced coexistence of Co and CoOx nanoparticles formed under ethanol steam reforming conditions, partially covered by filamentous and encapsulating carbonaceous deposits.

  9. Method for Determining the Activation Energy Distribution Function of Complex Reactions by Sieving and Thermogravimetric Measurements.

    Science.gov (United States)

    Bufalo, Gennaro; Ambrosone, Luigi

    2016-01-14

    A method for studying the kinetics of thermal degradation of complex compounds is suggested. Although the method is applicable to any matrix whose grain size can be measured, herein we focus our investigation on thermogravimetric analysis, under a nitrogen atmosphere, of ground soft wheat and ground maize. The thermogravimetric curves reveal that there are two well-distinct jumps of mass loss. They correspond to volatilization, which is in the temperature range 298-433 K, and decomposition regions go from 450 to 1073 K. Thermal degradation is schematized as a reaction in the solid state whose kinetics is analyzed separately in each of the two regions. By means of a sieving analysis different size fractions of the material are separated and studied. A quasi-Newton fitting algorithm is used to obtain the grain size distribution as best fit to experimental data. The individual fractions are thermogravimetrically analyzed for deriving the functional relationship between activation energy of the degradation reactions and the particle size. Such functional relationship turns out to be crucial to evaluate the moments of the activation energy distribution, which is unknown in terms of the distribution calculated by sieve analysis. From the knowledge of moments one can reconstruct the reaction conversion. The method is applied first to the volatilization region, then to the decomposition region. The comparison with the experimental data reveals that the method reproduces the experimental conversion with an accuracy of 5-10% in the volatilization region and of 3-5% in the decomposition region.

  10. Chemically activated formation of organic acids in reactions of the Criegee intermediate with aldehydes and ketones.

    Science.gov (United States)

    Jalan, Amrit; Allen, Joshua W; Green, William H

    2013-10-21

    Reactions of the Criegee intermediate (CI, ˙CH2OO˙) are important in atmospheric ozonolysis models. In this work, we compute the rates for reactions between ˙CH2OO˙ and HCHO, CH3CHO and CH3COCH3 leading to the formation of secondary ozonides (SOZ) and organic acids. Relative to infinitely separated reactants, the SOZ in all three cases is found to be 48-51 kcal mol(-1) lower in energy, formed via 1,3-cycloaddition of ˙CH2OO˙ across the C=O bond. The lowest energy pathway found for SOZ decomposition is intramolecular disproportionation of the singlet biradical intermediate formed from cleavage of the O-O bond to form hydroxyalkyl esters. These hydroxyalkyl esters undergo concerted decomposition providing a low energy pathway from SOZ to acids. Geometries and frequencies of all stationary points were obtained using the B3LYP/MG3S DFT model chemistry, and energies were refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. RRKM calculations were used to obtain microcanonical rate coefficients (k(E)) and the reservoir state method was used to obtain temperature and pressure dependent rate coefficients (k(T, P)) and product branching ratios. At atmospheric pressure, the yield of collisionally stabilized SOZ was found to increase in the order HCHO reactions were found to be the most sensitive parameters determining SOZ and organic acid yield.

  11. A thiamin-bound, pre-decarboxylation reaction intermediate analogue in the pyruvate dehydrogenase E1 subunit induces large scale disorder-to-order transformations in the enzyme and reveals novel structural features in the covalently bound adduct.

    Science.gov (United States)

    Arjunan, Palaniappa; Sax, Martin; Brunskill, Andrew; Chandrasekhar, Krishnamoorthy; Nemeria, Natalia; Zhang, Sheng; Jordan, Frank; Furey, William

    2006-06-02

    The crystal structure of the E1 component from the Escherichia coli pyruvate dehydrogenase multienzyme complex (PDHc) has been determined with phosphonolactylthiamin diphosphate (PLThDP) in its active site. PLThDP serves as a structural and electrostatic analogue of the natural intermediate alpha-lactylthiamin diphosphate (LThDP), in which the carboxylate from the natural substrate pyruvate is replaced by a phosphonate group. This represents the first example of an experimentally determined, three-dimensional structure of a thiamin diphosphate (ThDP)-dependent enzyme containing a covalently bound, pre-decarboxylation reaction intermediate analogue and should serve as a model for the corresponding intermediates in other ThDP-dependent decarboxylases. Regarding the PDHc-specific reaction, the presence of PLThDP induces large scale conformational changes in the enzyme. In conjunction with the E1-PLThDP and E1-ThDP structures, analysis of a H407A E1-PLThDP variant structure shows that an interaction between His-407 and PLThDP is essential for stabilization of two loop regions in the active site that are otherwise disordered in the absence of intermediate analogue. This ordering completes formation of the active site and creates a new ordered surface likely involved in interactions with the lipoyl domains of E2s within the PDHc complex. The tetrahedral intermediate analogue is tightly held in the active site through direct hydrogen bonds to residues His-407, Tyr-599, and His-640 and reveals a new, enzyme-induced, strain-related feature that appears to aid in the decarboxylation process. This feature is almost certainly present in all ThDP-dependent decarboxylases; thus its inclusion in our understanding of general thiamin catalysis is important.

  12. Analysis of EMG Signals in Aggressive and Normal Activities by Using Higher-Order Spectra

    Directory of Open Access Journals (Sweden)

    Necmettin Sezgin

    2012-01-01

    Full Text Available The analysis and classification of electromyography (EMG signals are very important in order to detect some symptoms of diseases, prosthetic arm/leg control, and so on. In this study, an EMG signal was analyzed using bispectrum, which belongs to a family of higher-order spectra. An EMG signal is the electrical potential difference of muscle cells. The EMG signals used in the present study are aggressive or normal actions. The EMG dataset was obtained from the machine learning repository. First, the aggressive and normal EMG activities were analyzed using bispectrum and the quadratic phase coupling of each EMG episode was determined. Next, the features of the analyzed EMG signals were fed into learning machines to separate the aggressive and normal actions. The best classification result was 99.75%, which is sufficient to significantly classify the aggressive and normal actions.

  13. Analysis of EMG Signals in Aggressive and Normal Activities by Using Higher-Order Spectra

    Science.gov (United States)

    Sezgin, Necmettin

    2012-01-01

    The analysis and classification of electromyography (EMG) signals are very important in order to detect some symptoms of diseases, prosthetic arm/leg control, and so on. In this study, an EMG signal was analyzed using bispectrum, which belongs to a family of higher-order spectra. An EMG signal is the electrical potential difference of muscle cells. The EMG signals used in the present study are aggressive or normal actions. The EMG dataset was obtained from the machine learning repository. First, the aggressive and normal EMG activities were analyzed using bispectrum and the quadratic phase coupling of each EMG episode was determined. Next, the features of the analyzed EMG signals were fed into learning machines to separate the aggressive and normal actions. The best classification result was 99.75%, which is sufficient to significantly classify the aggressive and normal actions. PMID:23193379

  14. Electrodeposition of Amorphous Molybdenum Chalcogenides from Ionic Liquids and Their Activity for the Hydrogen Evolution Reaction.

    Science.gov (United States)

    Redman, Daniel W; Rose, Michael J; Stevenson, Keith J

    2017-09-19

    This work reports on the general electrodeposition mechanism of tetrachalcogenmetallates from 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Both tetrathio- and tetraselenomolybdate underwent anodic electrodeposition and cathodic corrosion reactions as determined by UV-vis spectroelectrochemistry. Electrodeposition was carried out by cycling the potential between the anodic and cathodic regimes. This resulted in a film of densely packed nanoparticles of amorphous MoS x or MoSe x as determined by SEM, Raman, and XPS. The films were shown to have high activity for the hydrogen evolution reaction. The onset potential (J = 1 mA/cm 2 ) of the MoS x film was E = -0.208 V vs RHE, and that of MoSe x was E = -0.230 V vs RHE. The Tafel slope of MoS x was 42 mV/decade, and that of MoSe x was 59 mV/decade.

  15. Experimental study on active specific immunotherapy utilizing the immune reaction of low-dose irradiated tumor tissue

    International Nuclear Information System (INIS)

    Imanaka, Kazufumi; Tanaka, Koji; Sasai, Keisuke

    1984-01-01

    We have already reported the effectiveness of active specific immunotherapy based on the immune reaction of low-dose irradiated tumor tissue. In the present study, three kinds of immunotherapeutic methods subdivided by used cells were performed in order to compare each effectiveness. C3H/He mice bearing MM 46 tumor transplanted in the right hind paws received local irradiation with the dose of 3,000 rad on the 6th day, and the above-mentioned three methods, using tumor cells, lymphocytes, and tumor cells combining lymphocytes which were all separated from the topical tumor tissue exposed to 2,000 rad, were applied respectively on the 14 th day. The most effective data were obtained from two groups treated by the immunotherapy with tumor cells combining lymphocytes, which virtually caused the longest survival and best tumor growth control. (author)

  16. Ion channel activity of membrane vesicles released from sea urchin sperm during the acrosome reaction

    International Nuclear Information System (INIS)

    Schulz, Joseph R.; Vega-Beltran, Jose L. de la; Beltran, Carmen; Vacquier, Victor D.; Darszon, Alberto

    2004-01-01

    The sperm acrosome reaction (AR) involves ion channel activation. In sea urchin sperm, the AR requires Ca 2+ and Na + influx and K + and H + efflux. During the AR, the plasma membrane fuses with the acrosomal vesicle membrane forming hybrid membrane vesicles that are released from sperm into the medium. This paper reports the isolation and preliminary characterization of these acrosome reaction vesicles (ARVs), using synaptosome-associated protein of 25 kDa (SNAP-25) as a marker. Isolated ARVs have a unique protein composition. The exocytosis regulatory proteins vesicle-associated membrane protein and SNAP-25 are inside ARVs, as judged by protease protection experiments, and membrane associated based on Triton X-114 partitioning. ARVs fused with planar bilayers display three main types of single channel activity. The most frequently recorded channel is cationic, weakly voltage dependent and has a low open probability that increases with negative potentials. This channel is activated by cAMP, blocked by Ba 2+ , and has a PK + /PNa + selectivity of 4.5. ARVs represent a novel membrane preparation suitable to deepen our understanding of ion channel activity in the AR and during fertilization

  17. Catalytic activity of pyrite for coal liquefaction reaction; Tennen pyrite no shokubai seino ni kansuru kento

    Energy Technology Data Exchange (ETDEWEB)

    Hirano, K.; Kozu, M.; Okada, T.; Kobayashi, M. [Nippon Coal Oil Co. Ltd., Tokyo (Japan)

    1996-10-28

    Since natural pyrite is easy to obtain and cheap as coal liquefaction catalyst, it is to be used for the 150 t/d scale NEDOL process bituminous coal liquefaction pilot plant. NEDO and NCOL have investigated the improvement of catalytic activity of pulverized natural pyrite for enhancing performance and economy of the NEDOL process. In this study, coal liquefaction tests were conducted using natural pyrite catalyst pulverized by dry-type bowl mill under nitrogen atmosphere. Mechanism of catalytic reaction of the natural pyrite was discussed from relations between properties of the catalyst and liquefaction product. The natural pyrite provided an activity to transfer gaseous hydrogen into the liquefaction product. It was considered that pulverized pyrite promotes the hydrogenation reaction of asphaltene because pulverization increases its contact rate with reactant and the amount of active points on its surface. It was inferred that catalytic activity of pyrite is affected greatly by the chemical state of Fe and S on its surface. 3 refs., 4 figs., 1 tab.

  18. Instrumentation amplifier implements second-order active low-pass filter with high gain factor

    International Nuclear Information System (INIS)

    Blomqvist, Kim H; Eskelinen, Pekka; Sepponen, Raimo E

    2011-01-01

    A single-ended second-order active low-pass filter can simultaneously provide high gain factor and dc voltage subtraction. This makes it possible to reduce the number of components and signal processing stages needed in an application where small voltage changes are measured on the top of large dc voltage masked by a large amplitude oscillating carrier. The filter described in this paper is constructed from a conventional 3-op-amp instrumentation amplifier and five passive circuit elements. (technical design note)

  19. A numerical design approach for single amplifier, Active-RC Butterworth filter of order 5

    OpenAIRE

    Gaunholt, Hans

    2007-01-01

    A design method is presented for the design of all pole lowpass active-RC filters applying operational amplifiers. The operational amplifier model used is the integrator model: omegat/s where omegat is the unity gain frequency. The design method is used for the design of a fifth order Butterworth filter applying just one operational amplifier coupled as a unity gain amplifier. It is shown that the influence from the real operational amplifier may be reduced by trimming just one resistor in th...

  20. Identifying the Active Surfaces of Electrochemically Tuned LiCoO2 for Oxygen Evolution Reaction

    International Nuclear Information System (INIS)

    Lu, Zhiyi; Chen, Guangxu; Li, Yanbin; Wang, Haotian; Xie, Jin

    2017-01-01

    Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (1120) and polar (0112) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces and their OER activities can be understood by the increase of Co 4+ sites relative to Co 3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (~0.1 V in overpotential shift at 10 mA cm –2 ) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. In addition, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.

  1. Modeling of catalytically active metal complex species and intermediates in reactions of organic halides electroreduction.

    Science.gov (United States)

    Lytvynenko, Anton S; Kolotilov, Sergey V; Kiskin, Mikhail A; Eremenko, Igor L; Novotortsev, Vladimir M

    2015-02-28

    The results of quantum chemical modeling of organic and metal-containing intermediates that occur in electrocatalytic dehalogenation reactions of organic chlorides are presented. Modeling of processes that take place in successive steps of the electrochemical reduction of representative C1 and C2 chlorides - CHCl3 and Freon R113 (1,1,2-trifluoro-1,2,2-trichloroethane) - was carried out by density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2). It was found that taking solvation into account using an implicit solvent model (conductor-like screening model, COSMO) or considering explicit solvent molecules gave similar results. In addition to modeling of simple non-catalytic dehalogenation, processes with a number of complexes and their reduced forms, some of which were catalytically active, were investigated by DFT. Complexes M(L1)2 (M = Fe, Co, Ni, Cu, Zn, L1H = Schiff base from 2-pyridinecarbaldehyde and the hydrazide of 4-pyridinecarboxylic acid), Ni(L2) (H2L2 is the Schiff base from salicylaldehyde and 1,2-ethylenediamine, known as salen) and Co(L3)2Cl2, representing a fragment of a redox-active coordination polymer [Co(L3)Cl2]n (L3 is the dithioamide of 1,3-benzenedicarboxylic acid), were considered. Gradual changes in electronic structure in a series of compounds M(L1)2 were observed, and correlations between [M(L1)2](0) spin-up and spin-down LUMO energies and the relative energies of the corresponding high-spin and low-spin reduced forms, as well as the shape of the orbitals, were proposed. These results can be helpful for determination of the nature of redox-processes in similar systems by DFT. No specific covalent interactions between [M(L1)2](-) and the R113 molecule (M = Fe, Co, Ni, Zn) were found, which indicates that M(L1)2 electrocatalysts act rather like electron transfer mediators via outer-shell electron transfer. A relaxed surface scan of the adducts {M(L1)2·R113}(-) (M = Ni or Co) versus the distance between the

  2. Comparative study on the electrocatalytic activities of ordered mesoporous carbons and graphene

    International Nuclear Information System (INIS)

    Wang Huan; Qi Bin; Lu Baoping; Bo Xiangjie; Guo Liping

    2011-01-01

    In this work, a comparative study on the electrocatalytic activities of ordered mesoporous carbons (OMCs) and graphene (GR) is presented. Using voltammetry and amperometry as detection methods, four DNA bases, double-stranded DNA (dsDNA), six important electroactive compounds and various biomolecules were employed to investigate their electrochemical responses on OMC and GR modified glassy carbon electrodes (OMC/GCE and GR/GCE). The results show that OMC/GCE enhances the electron transfer kinetics of these compounds compared to GR/GCE. The discrepancy in electrochemical activities can be attributed to the different microstructures of OMC and GR, which were examined by transmission electron microscopy, X-ray photoelectron spectra, X-ray diffraction, Raman spectra and nitrogen adsorption-desorption.

  3. Electrocatalytic activity of LaNiO3 toward H2O2 reduction reaction: Minimization of oxygen evolution

    Science.gov (United States)

    Amirfakhri, Seyed Javad; Meunier, Jean-Luc; Berk, Dimitrios

    2014-12-01

    The catalytic activity of LaNiO3 toward H2O2 reduction reaction (HPRR), with a potential application in the cathode side of fuel cells, is studied in alkaline, neutral and acidic solutions by rotating disk electrode. The LaNiO3 particles synthesised by citrate-based sol-gel method have sizes between 30 and 70 nm with an active specific surface area of 1.26 ± 0.05 m2 g-1. LaNiO3 shows high catalytic activity toward HPRR in 0.1 M KOH solution with an exchange current density based on the active surface area (j0A) of (7.4 ± 1) × 10-6 A cm-2 which is noticeably higher than the j0A of N-doped graphene. The analysis of kinetic parameters suggests that the direct reduction of H2O2, H2O2 decomposition, O2 reduction and O2 desorption occur through HPRR on this catalyst. In order to control and minimize oxygen evolution from the electrode surface, the effects of catalyst loading, bulk concentration of H2O2, and using a mixture of LaNiO3 and N-doped graphene are studied. Although the mechanism of HPRR is independent of the aforementioned operating conditions, gas evolution decreases by increasing the catalyst loading, decreasing the bulk concentration of H2O2, and addition of N-doped graphene to LaNiO3.

  4. Linear free energy relationships between aqueous phase hydroxyl radical reaction rate constants and free energy of activation.

    Science.gov (United States)

    Minakata, Daisuke; Crittenden, John

    2011-04-15

    The hydroxyl radical (HO(•)) is a strong oxidant that reacts with electron-rich sites on organic compounds and initiates complex radical chain reactions in aqueous phase advanced oxidation processes (AOPs). Computer based kinetic modeling requires a reaction pathway generator and predictions of associated reaction rate constants. Previously, we reported a reaction pathway generator that can enumerate the most important elementary reactions for aliphatic compounds. For the reaction rate constant predictor, we develop linear free energy relationships (LFERs) between aqueous phase literature-reported HO(•) reaction rate constants and theoretically calculated free energies of activation for H-atom abstraction from a C-H bond and HO(•) addition to alkenes. The theoretical method uses ab initio quantum mechanical calculations, Gaussian 1-3, for gas phase reactions and a solvation method, COSMO-RS theory, to estimate the impact of water. Theoretically calculated free energies of activation are found to be within approximately ±3 kcal/mol of experimental values. Considering errors that arise from quantum mechanical calculations and experiments, this should be within the acceptable errors. The established LFERs are used to predict the HO(•) reaction rate constants within a factor of 5 from the experimental values. This approach may be applied to other reaction mechanisms to establish a library of rate constant predictions for kinetic modeling of AOPs.

  5. Ordering Dynamics in Neuron Activity Pattern Model: An Insight to Brain Functionality.

    Directory of Open Access Journals (Sweden)

    Jasleen Gundh

    Full Text Available We study the domain ordering kinetics in d = 2 ferromagnets which corresponds to populated neuron activities with both long-ranged interactions, V(r ∼ r-n and short-ranged interactions. We present the results from comprehensive Monte Carlo (MC simulations for the nonconserved Ising model with n ≥ 2, interaction range considering near and far neighbors. Our model results could represent the long-ranged neuron kinetics (n ≤ 4 in consistent with the same dynamical behaviour of short-ranged case (n ≥ 4 at far below and near criticality. We found that emergence of fast and slow kinetics of long and short ranged case could imitate the formation of connections among near and distant neurons. The calculated characteristic length scale in long-ranged interaction is found to be n independent (L(t ∼ t1/(n-2, whereas short-ranged interaction follows L(t ∼ t1/2 law and approximately preserve universality in domain kinetics. Further, we did the comparative study of phase ordering near the critical temperature which follows different behaviours of domain ordering near and far critical temperature but follows universal scaling law.

  6. Boosting the Performance of the Nickel Anode in the Oxygen Evolution Reaction by Simple Electrochemical Activation

    KAUST Repository

    Shinagawa, Tatsuya

    2017-03-27

    The development of cost-effective and active water-splitting electrocatalysts that work at mild pH is an essential step towards the realization of sustainable energy and material circulation in our society. Its success requires a drastic improvement in the kinetics of the anodic half-reaction of the oxygen evolution reaction (OER), which determines the overall system efficiency to a large extent. A simple electrochemical protocol has been developed to activate Ni electrodes, by which a stable NiOOH phase was formed, which could weakly bind to alkali-metal cations. The electrochemically activated (ECA) Ni electrode reached a current of 10 mA at <1.40 V vs. the reversible hydrogen electrode (RHE) at practical operation temperatures (>75 °C) and a mild pH of ca. 10 with excellent stability (>24 h), greatly surpassing that of the state-of-the-art NiFeOx electrodes under analogous conditions. Water electrolysis was demonstrated with ECA-Ni and NiMo, which required an iR-free overall voltage of only 1.44 V to reach 10 mA cmgeo(-2) .

  7. Boosting the performance of the nickel anode in the oxygen evolution reaction by simple electrochemical activation

    Energy Technology Data Exchange (ETDEWEB)

    Shinagawa, Tatsuya; Ng, Marcus Tze-Kiat; Takanabe, Kazuhiro [King Abdullah Univ. of Science and Technology (KAUST), KAUST Catalysis Center (KCC) and Physical Sciences and Engineering Div. PSE, Thuwal (Saudi Arabia)

    2017-04-24

    The development of cost-effective and active water-splitting electrocatalysts that work at mild pH is an essential step towards the realization of sustainable energy and material circulation in our society. Its success requires a drastic improvement in the kinetics of the anodic half-reaction of the oxygen evolution reaction (OER), which determines the overall system efficiency to a large extent. A simple electrochemical protocol has been developed to activate Ni electrodes, by which a stable NiOOH phase was formed, which could weakly bind to alkali-metal cations. The electrochemically activated (ECA) Ni electrode reached a current of 10 mA at <1.40 V vs. the reversible hydrogen electrode (RHE) at practical operation temperatures (>75 C) and a mild pH of ca. 10 with excellent stability (>24 h), greatly surpassing that of the state-of-the-art NiFeO{sub x} electrodes under analogous conditions. Water electrolysis was demonstrated with ECA-Ni and NiMo, which required an iR-free overall voltage of only 1.44 V to reach 10 mA cm{sub geo}{sup -2}. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Applications of the photo-nuclear reaction data for activation analysis

    International Nuclear Information System (INIS)

    Odsuren, M.; Khuukhenkhuu, G.; Turbold, A.; Davaa, S.; Baatarkhuu, D.

    2015-01-01

    In the relative method of activation analysis by continuum wide spectrum gamma-rays the same isotope is usually used for standard reference element and sample material in connection with different dependence of the reaction cross sections on the irradiation beam energy. But, in practice suitable isotopes for reference element are not always available. So, in this paper, we suggest a new method for photo-activation analysis in which is used the correction factor. This factor takes into account the difference in the photo-nuclear reaction cross section dependence on the gamma-ray energy for standard reference isotope and sample elements. The correction factor is determined by three methods of experimental, theoretical and TALYS evaluation. Pure metal foils of Au, Cu and Mo were irradiated by bremsstrahlung gamma-rays on the electron cyclic accelerator Microtron MT-22 at the Nuclear Research Center, National University of Mongolia. Gamma spectra of the activated metal foils were measured by HP-Ge detector to obtain element contents in the samples. It was shown that experimental results with correction factors are satisfactorily in agreement with real values of the element contents in the samples

  9. Controllable Fabrication of Ordered Mesoporous Bi2WO6 and Its High Photocatalytic Activity under Visible Light

    Directory of Open Access Journals (Sweden)

    Xueming Dang

    2014-01-01

    Full Text Available Ordered mesoporous Bi2WO6 was fabricated by nanocasting technique using SBA-15 as the template. The effect of the dosage of SBA-15 on the formation of the ordered structure and the photocatalytic ability of mesoporous Bi2WO6 was discussed. It was confirmed that the ordered mesoporous structure was obtained as the dosage of SBA-15 was 0.3 g. It was found that, compared to Bi2WO6, the RhB degradation rate with ordered mesoporous Bi2WO6 was enhanced under visible light (λ>400 nm by the photocatalytic measurements. The enhanced photocatalytic performance of ordered mesoporous Bi2WO6 was attributed to its particular ordered mesoporous structure which could increase the light-harvesting efficiency, reduce the recombination of the photogenerated charge carriers, and promote the surface reaction.

  10. Synthesis and catalytic activity of N-heterocyclic silylene (NHSi) cobalt hydride for Kumada coupling reactions.

    Science.gov (United States)

    Qi, Xinghao; Sun, Hongjian; Li, Xiaoyan; Fuhr, Olaf; Fenske, Dieter

    2018-02-20

    The electron-rich silylene Co(i) chloride 5 was obtained through the reaction of CoCl(PMe 3 ) 3 with chlorosilylene. Complex 5 reacted with 1,3-siladiazole HSiMe(NCH 2 PPh 2 ) 2 C 6 H 4 to give the silylene Co(iii) hydride 6 through chelate-assisted Si-H activation. To the best of our knowledge, complex 6 is the first example of Co(iii) hydride supported by N-heterocyclic silylene. Complexes 5 and 6 were fully characterized by spectroscopic methods and X-ray diffraction analysis. Complex 6 was used as an efficient precatalyst for Kumada cross-coupling reactions. Compared with the related complex 3 supported by only trimethylphosphine, complex 6 as a catalyst supported by both chlorosilylene and trimethylphosphine exhibits a more efficient performance for the Kumada cross-coupling reactions. A novel catalytic radical mechanism was suggested and experimentally verified. As an intermediate silylene cobalt(ii) chloride 6d was isolated and structurally characterized.

  11. Factors Controlling the Redox Activity of Oxygen in Perovskites: From Theory to Application for Catalytic Reactions

    Directory of Open Access Journals (Sweden)

    Chunzhen Yang

    2017-05-01

    Full Text Available Triggering the redox reaction of oxygens has become essential for the development of (electro catalytic properties of transition metal oxides, especially for perovskite materials that have been envisaged for a variety of applications such as the oxygen evolution or reduction reactions (OER and ORR, respectively, CO or hydrocarbons oxidation, NO reduction and others. While the formation of ligand hole for perovskites is well-known for solid state physicists and/or chemists and has been widely studied for the understanding of important electronic properties such as superconductivity, insulator-metal transitions, magnetoresistance, ferroelectrics, redox properties etc., oxygen electrocatalysis in aqueous media at low temperature barely scratches the surface of the concept of oxygen ions oxidation. In this review, we briefly explain the electronic structure of perovskite materials and go through a few important parameters such as the ionization potential, Madelung potential, and charge transfer energy that govern the oxidation of oxygen ions. We then describe the surface reactivity that can be induced by the redox activity of the oxygen network and the formation of highly reactive surface oxygen species before describing their participation in catalytic reactions and providing mechanistic insights and strategies for designing new (electro catalysts. Finally, we give a brief overview of the different techniques that can be employed to detect the formation of such transient oxygen species.

  12. Cross-section studies of relativistic deuteron reactions obtained by activation method

    CERN Document Server

    Wagner, V; Svoboda, O; Vrzalová, J; Majerle, M; Krása, A; Chudoba, P; Honusek, M; Kugler, A; Adam, J; Baldin, A; Furman, W; Kadykov, M; Khushvaktov, J; Sol-nyskhin, A; Tsoupko-Sitnikov, V; Závorka, L; Tyutyunnikov, S; Vladimirova, N

    2014-01-01

    The cross-sections of relativistic deuteron reactions on natural copper were studied in detail by means of activation method. The copper foils were irradiated during experiments with the big Quinta uranium target at Joint Institute for Nuclear Research (JINR) in Dubna, Russia. The deuteron beams with energies ranging from 1 GeV up to 8 GeV were produced by JINR Nuclotron. Residual nuclides were identified by the gamma spectrometry. Lack of such experimental cross-section values prevents the usage of copper foils from beam integral monitoring.

  13. Selective molecular recognition, C-H bond activation, and catalysis in nanoscale reaction vessels

    Energy Technology Data Exchange (ETDEWEB)

    Fiedler, Dorothea; Leung, Dennis H.; Raymond, Kenneth N.; Bergman, Robert G.

    2004-11-27

    Supramolecular chemistry represents a way to mimic enzyme reactivity by using specially designed container molecules. We have shown that a chiral self-assembled M{sub 4}L{sub 6} supramolecular tetrahedron can encapsulate a variety of cationic guests, with varying degrees of stereoselectivity. Reactive iridium guests can be encapsulated and the C-H bond activation of aldehydes occurs, with the host cavity controlling the ability of substrates to interact with the metal center based upon size and shape. In addition, the host container can act as a catalyst by itself. By restricting reaction space and preorganizing the substrates into reactive conformations, it accelerates the sigmatropic rearrangement of enammonium cations.

  14. Studies of photonuclear reactions and photon activation analysis in the giant dipole resonance region using microtrons

    International Nuclear Information System (INIS)

    Tran Duc Thiep; Nguyen Van Do; Nguyen Khac Thi; Truong Thi An; Nguyen Ngoc Son

    2004-01-01

    Microtrons are accelerators of electrons and are simultaneous source of Bremsstrahlung photon flux and fission neutrons. In 1982, a microtron of seventeen trajectories Microtron MT - 17 was put into operation at the National Institute of Physics of Vietnam. Though very modest, microtrons are very useful for developing countries such as Vietnam in both fundamental and applied physics research. During the recent years by using the above mentioned MT - 17 and microtrons from other institutes we have carried out different investigation. In this report we present some results obtained in the studies of photonuclear reactions and photon activation analysis in the giant dipole resonance region. (author)

  15. Characterization and development of an active scintillating target for nuclear reaction studies on actinides

    Energy Technology Data Exchange (ETDEWEB)

    Belier, Gilbert, E-mail: gilbert.belier@cea.fr [CEA, DAM, DIF, DPTA, Centre du Grand Rue, 91297 Arpajon (France); Aupiais, Jean; Varignon, Cyril; Vayre, Sylvain [CEA, DAM, DIF, DPTA, Centre du Grand Rue, 91297 Arpajon (France)

    2012-02-01

    This article presents the development of a new kind of active actinide target, based on organic liquid scintillators containing the dissolved isotope. Amongst many advantages one can mention the very high detection efficiency, the Pulse Shape Discrimination capability, the fast response allowing high count rates and good time resolution and the ease of fabrication. The response of this target to fission fragments has been studied. The discrimination of alpha, fission and proton recoil events is demonstrated. The alpha decay and fission detection efficiencies are simulated and compared to measurements. Finally the use of such a target in the context of fast neutron induced reactions is discussed.

  16. Characterization and development of an active scintillating target for nuclear reaction studies on actinides

    International Nuclear Information System (INIS)

    Belier, Gilbert; Aupiais, Jean; Varignon, Cyril; Vayre, Sylvain

    2012-01-01

    This article presents the development of a new kind of active actinide target, based on organic liquid scintillators containing the dissolved isotope. Amongst many advantages one can mention the very high detection efficiency, the Pulse Shape Discrimination capability, the fast response allowing high count rates and good time resolution and the ease of fabrication. The response of this target to fission fragments has been studied. The discrimination of alpha, fission and proton recoil events is demonstrated. The alpha decay and fission detection efficiencies are simulated and compared to measurements. Finally the use of such a target in the context of fast neutron induced reactions is discussed.

  17. Photooxidative removal of the herbicide Acid Blue 9 in the presence of hydrogen peroxide: modeling of the reaction for evaluation of electrical energy per order (E EO).

    Science.gov (United States)

    Khataee, Ali R; Khataee, Hamid R

    2008-09-01

    The present work deals with photooxidative removal of the herbicide, Acid Blue 9 (AB9), in water in the presence of hydrogen peroxide (H2O2) under UV light illumination (30 W). The influence of the basic operational parameters such as amount of H2O2, irradiation time and initial concentration of AB9 on the photodegradation efficiency of the herbicide was investigated. The degradation rate of AB9 was not appreciably high when the photolysis was carried out in the absence of H2O2 and it was negligible in the absence of UV light. The photooxidative removal of the herbicide was found to follow pseudo-first-order kinetic, and hence the figure-of-merit electrical energy per order (E Eo) was considered appropriate for estimating the electrical energy efficiency. A mathematical relation between the apparent reaction rate constant and H2O2 used was applied for prediction of the electricity consumption in the photooxidative removal of AB9. The results indicated that this kinetic model, based on the initial rates of degradation, provided good prediction of the E Eo values for a variety of conditions. The results also indicated that the UV/H2O2 process was appropriate as the effective treatment method for removal of AB9 from the contaminated wastewater.

  18. Quick Reaction Evaluation of Materials and Processes. Delivery Order 0011: Engineering Properties, Fatigue, and Crack Growth Data on SCS-6/Ti-6Al-4V Titanium Matrix Composite (16 Ply) Panels

    Science.gov (United States)

    2009-05-01

    tabs were bonded to the specimen using a TIG welding process to ensure adhesion of the tabs throughout the experiment. The shear specimens and the...AFRL-RX-WP-TR-2010-4175 QUICK REACTION EVALUATION OF MATERIALS AND PROCESSES Delivery Order 0011: Engineering Properties, Fatigue, and Crack...From - To) May 2009 Final 03 April 2006 – 29 May 2009 4. TITLE AND SUBTITLE QUICK REACTION EVALUATION OF MATERIALS AND PROCESSES Delivery Order

  19. A Ligand Structure-Activity Study of DNA-Based Catalytic Asymmetric Hydration and Diels-Alder Reactions

    NARCIS (Netherlands)

    Rosati, F.; Roelfes, J.G.

    A structure-activity relationship study of the first generation ligands for the DNA-based asymmetric hydration of enones and Diels-Alder reaction in water is reported. The design of the ligand was optimized resulting in a maximum ee of 83% in the hydration reaction and 75% in the Diels-Alder

  20. Reaction rate studies of glucose-6-phosphate dehydrogenase activity in sections of rat liver using four tetrazolium salts

    NARCIS (Netherlands)

    Butcher, R. G.; van Noorden, C. J.

    1985-01-01

    The reaction rate of glucose-6-phosphate dehydrogenase activity in liver sections from fed and starved rats has been monitored by the continuous measurement at 37 degrees C of the reaction product as it is formed using scanning and integrating microdensitometry. Control media lacked either substrate

  1. Pinostrobin Derivatives from PrenylationReaction and their Antibacterial Activity against Clinical Bacteria

    Science.gov (United States)

    Marliyana, S. D.; Mujahidin, D.; Syah, Y. M.

    2018-04-01

    Kaempferia pandurata (syn. Boesenbergia rotunda, B. pandurata (Roxb.)Schltr), locally known as "TemuKunci"in Indonesia, is one of the medicinal plants of the family Zingiberaceae. Phytochemical studies on the rhizome of K. pandurata showed the presence of flavonoid derivative, namely flavanones, which constitute as the main components of this plant. Bioactivity studies on this species exhibited various biological activities, such as antibacteria, anti-inflammatory, antitumor, antidiarrhea, antidisentri, anti-HIV, antioxidant, antipyretic, analgesic and insecticides. Among the biological activities, the antibacterial activity results are important as an attempt to answer the emergence of resistance of some bacteria against existing drugs, as well as the emergence of a number of outbreaks of disease caused by bacteria. Therefore, a search to find new compounds that are potential as an antibacterial is an urgent matter. The present study was aimed at the chemical transformation of pinostrobin (1) from K. pandurata rhizome and an antibacterial activity.The chemical transformation was performed through a prenylation reaction of pinostrobin (1) which is the main component of K. pandurata rhizome. The prenylation reaction was carried out by reacting pinostrobin (1) with prenyl bromide and potassium carbonat (K2CO3). The purification of product was done using the radial chromatography with mix solvent n-hexane and ethyl acetate (97.5:2.5; 9.5:0.5; 9.0:1.0.; 8.0:2.0). The purity test of isolated compound was analysedby TLC using different types of eluent. The identification of compounds was determined based on NMR data and mass spectra analysis. Five compounds were obtained from the prenylation reaction, i.e. monooxyprenylated pinostrobin (2), monooxyprenylated chalcone (3), diprenylated chalcone (4), triprenylated chalcone (5), and triprenylated cyclohexene chalcone (6). These compounds were tested for antibacterial activities against four clinical bacteria, namely

  2. ACT-XN: Revised version of an activation calculation code for fusion reactor analysis. Supplement of the function for the sequential reaction activation by charged particles

    International Nuclear Information System (INIS)

    Yamauchi, Michinori; Sato, Satoshi; Nishitani, Takeo; Konno, Chikara; Hori, Jun-ichi; Kawasaki, Hiromitsu

    2007-09-01

    The ACT-XN is a revised version of the ACT4 code, which was developed in the Japan Atomic Energy Research Institute (JAERI) to calculate the transmutation, induced activity, decay heat, delayed gamma-ray source etc. for fusion devices. The ACT4 code cannot deal with the sequential reactions of charged particles generated by primary neutron reactions. In the design of present experimental reactors, the activation due to sequential reactions may not be of great concern as it is usually buried under the activity by primary neutron reactions. However, low activation material is one of the important factors for constructing high power fusion reactors in future, and unexpected activation may be produced through sequential reactions. Therefore, in the present work, the ACT4 code was newly supplemented with the calculation functions for the sequential reactions and renamed the ACT-XN. The ACT-XN code is equipped with functions to calculate effective cross sections for sequential reactions and input them in transmutation matrix. The FISPACT data were adopted for (x,n) reaction cross sections, charged particles emission spectra and stopping powers. The nuclear reaction chain data library were revised to cope with the (x,n) reactions. The charged particles are specified as p, d, t, 3 He(h) and α. The code was applied to the analysis of FNS experiment for LiF and Demo-reactor design with FLiBe, and confirmed that it reproduce the experimental values within 15-30% discrepancies. In addition, a notice was presented that the dose rate due to sequential reaction cannot always be neglected after a certain period cooling for some of the low activation material. (author)

  3. Size-selective electrocatalytic activity of (Pt)n/MoS2for oxygen reduction reaction

    DEFF Research Database (Denmark)

    Bothra, Pallavi; Pandey, Mohnish; Pati, Swapan K.

    2016-01-01

    In the present work, we have investigated the electrocatalytic activity of the oxygen reduction reaction (ORR), O2 + 4H+ + 4e− → 2H2O, for (Pt)n clusters (n = 1, 2, 3, 5, 7, 10 and 12) adsorbed on semiconducting (2H) and metallic (1T) MoS2 monolayers using first principles density functional theory....... We have considered four elementary reactions involved in ORR within a unified electrochemical thermodynamic framework and the corresponding Gibbs adsorption free energies of the key intermediates (*OOH, *O, *OH) associated with each step have been calculated. The results indicate that the reduction...... of adsorbed hydroxyl (*OH) to water (*OH + H+ + e− → H2O) is the bottleneck step in the ORR process. The adsorption free energy of *OH (ΔG*OH) is found to be the thermodynamic descriptor for the present systems. Eventually, the ORR activity has been described as a function of ΔG*OH and a volcano plot...

  4. EFFECT OF FLUORINE AND CHLORINE IONS ON THE REACTION SINTERING OF MECHANICALLY ACTIVATED ZIRCON-ALUMINA MIXTURE

    Directory of Open Access Journals (Sweden)

    R. Zamani Foroshani

    2015-09-01

    Full Text Available The aim of this work was to study the effect of fluorine and chlorine ions on the formation of mullite during the reaction sintering of mechanically activated zircon-alumina powder mixture. The results showed that mechanical activation of zirconalumina powder mixture for 20 h led to grain refinement and partial amorphization. In the presence of fluorine and chlorine ions, complete formation of mullite in the mechanically activated sample occurred after 2 h of reaction sintering at 1300oC and 1400oC, respectively. In the sample lacking fluorine and chlorine ions, mullitization was not completed even after 2 h of reaction sintering at 1400oC. It was concluded that presence of fluorine and chlorine ions enhance the dissociation of zircon and formation of mullite during the reaction sintering of mechanically activated zircon-alumina mixture.

  5. Particle size dependence on oxygen reduction reaction activity of electrodeposited TaOx catalysts in acidic media

    KAUST Repository

    Seo, J.; Cha, Dong Kyu; Takanabe, Kazuhiro; Kubota, J.; Domen, K.

    2013-01-01

    The size dependence of the oxygen reduction reaction activity was studied for TaOx nanoparticles electrodeposited on carbon black for application to polymer electrolyte fuel cells (PEFCs). Compared with a commercial Ta2O5 material, the ultrafine

  6. Sensitive electrochemical assaying of DNA methyltransferase activity based on mimic-hybridization chain reaction amplified strategy.

    Science.gov (United States)

    Zhang, Linqun; Liu, Yuanjian; Li, Ying; Zhao, Yuewu; Wei, Wei; Liu, Songqin

    2016-08-24

    A mimic-hybridization chain reaction (mimic-HCR) amplified strategy was proposed for sensitive electrochemically detection of DNA methylation and methyltransferase (MTase) activity In the presence of methylated DNA, DNA-gold nanoparticles (DNA-AuNPs) were captured on the electrode by sandwich-type assembly. It then triggered mimic-HCR of two hairpin probes to produce many long double-helix chains for numerous hexaammineruthenium (III) chloride ([Ru(NH3)6](3+), RuHex) inserting. As a result, the signal for electrochemically detection of DNA MTase activity could be amplified. If DNA was non-methylated, however, the sandwich-type assembly would not form because the short double-stranded DNAs (dsDNA) on the Au electrode could be cleaved and digested by restriction endonuclease HpaII (HapII) and exonuclease III (Exo III), resulting in the signal decrement. Based on this, an electrochemical approach for detection of M.SssI MTase activity with high sensitivity was developed. The linear range for M.SssI MTase activity was from 0.05 U mL(-1) to 10 U mL(-1), with a detection limit down to 0.03 U mL(-1). Moreover, this detecting strategy held great promise as an easy-to-use and highly sensitive method for other MTase activity and inhibition detection by exchanging the corresponding DNA sequence. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Fractional Order PID Control of Rotor Suspension by Active Magnetic Bearings

    Directory of Open Access Journals (Sweden)

    Parinya Anantachaisilp

    2017-01-01

    Full Text Available One of the key issues in control design for Active Magnetic Bearing (AMB systems is the tradeoff between the simplicity of the controller structure and the performance of the closed-loop system. To achieve this tradeoff, this paper proposes the design of a fractional order Proportional-Integral-Derivative (FOPID controller. The FOPID controller consists of only two additional parameters in comparison with a conventional PID controller. The feasibility of FOPID for AMB systems is investigated for rotor suspension in both the radial and axial directions. Tuning methods are developed based on the evolutionary algorithms for searching the optimal values of the controller parameters. The resulting FOPID controllers are then tested and compared with a conventional PID controller, as well as with some advanced controllers such as Linear Quadratic Gausian (LQG and H ∞ controllers. The comparison is made in terms of various stability and robustness specifications, as well as the dimensions of the controllers as implemented. Lastly, to validate the proposed method, experimental testing is carried out on a single-stage centrifugal compressor test rig equipped with magnetic bearings. The results show that, with a proper selection of gains and fractional orders, the performance of the resulting FOPID is similar to those of the advanced controllers.

  8. Higher Order Loess Terracettes and Related Ungulate Activities in Western Pottawattamie County, Iowa

    Science.gov (United States)

    Weihs, B. J.

    2009-12-01

    Terracettes are small, quasi-parallel, staircase-like, stepped landforms. They are generally less than a meter in tread width and riser height and as long as 300 meters, located transversely along slopes. Many theories purport to explain the mechanisms that cause them, including animal disturbance, soil creep, solifluction (gelifluction), slumping and rotational slippage, regolith control, vegetation control, subsidence, and anthropogenic or tectonic activities. This thesis was aimed at morphologically characterizing terracettes in the western Iowa Loess Hills, with an emphasis on further classifying the forms morphogenetically. Onsite observations suggest that terracettes in this area are highly associated with anthropogenically induced grazing of domestic ungulates such as cattle, horses, and sheep, as well as deer. A new class of terracette (higher order or mega-terracette) is proposed that characterizes (and differentiates) the study area forms based on size, in that the study area contains terracettes that are an order above those discussed by other authors (sub-meter). This new addition to the current standard (tear terracettes-risers bare of vegetation, and normal terracettes-normal to the slope), as suggested by Anderson (1972), will add to the local understanding of the forms, and especially to the theory of polygenesis in which terracettes can result from a host of processes. This new class of terracette (mega) is higher magnitude, and directly related to ungulate activities such as geophagy, soil transport (from hooves), compaction, smearing, pawing, and wallowing (dust bathing) as well as the effects of variable soil moisture on erosion of the forms used by the animals. High magnitude terracettes in western Pottawattamie County, Iowa

  9. Influence of refreshment/activation cycles and temperature rise on the reaction rate of sodium hypochlorite with bovine dentine during ultrasonic activated irrigation.

    Science.gov (United States)

    Macedo, R G; Verhaagen, B; Wesselink, P R; Versluis, M; van der Sluis, L W M

    2014-02-01

    To evaluate the effect of multiple refreshment/activation cycles and temperature on the reaction rate of sodium hypochlorite (NaOCl) with bovine dentine during ultrasonic activated irrigation (UAI) under laboratory conditions. The root canal walls of 24 standardized root canals in bovine incisors were exposed to a standardized volume of NaOCl at different temperatures (24 °C and 38 °C) and exposure times (20, 60 and 180 s). The irrigant was refreshed and ultrasonically activated four times for 20 s followed by a 40 s rest interval, with no refreshment and no activation as the controls. The reaction rate was determined by measuring the amount of active chlorine in the NaOCl solution before and after being exposed to dentine during the specific experimental conditions. Calorimetry was used to measure the electrical-to-sonochemical conversion efficiency during ultrasonic activation. Refreshment, activation and exposure time all increased the reaction rate of NaOCl (P reaction rate of NaOCl (P > 0.125). The reaction rate of NaOCl with dentine is enhanced by refreshment, ultrasonic activation and exposure time. Temperature rise of irrigant during ultrasonic activation was not sufficient to alter the reaction rate. © 2013 International Endodontic Journal. Published by John Wiley & Sons Ltd.

  10. Cross section measurement and integral test for several activation reactions using T + d and thick-Li + d sources

    International Nuclear Information System (INIS)

    Dumais, J.R.; Tanaka, S.; Odano, N.; Iwasaki, S.; Sugiyama, K.

    1988-01-01

    Recent activities on the area of the cross section measurement for several activation reactions at Department of Nucl. Eng., Tohoku Univ. are described. The first subject is the cross section measurement for (n,2n) reaction on aluminum using the RTNS-II neutron source. Cross sections with rather small error band were obtained for the incident neutron energies from 14 to 14.7 MeV. The second one is the status of the program for the integral experiments on several reactions using the thick Li + d source at Tohoku Fast Neutron Lab. The experimental results showed the usefullness of the source as a tool for the cross section assessment. (author)

  11. Brain activity related to working memory for temporal order and object information.

    Science.gov (United States)

    Roberts, Brooke M; Libby, Laura A; Inhoff, Marika C; Ranganath, Charan

    2017-06-08

    Maintaining items in an appropriate sequence is important for many daily activities; however, remarkably little is known about the neural basis of human temporal working memory. Prior work suggests that the prefrontal cortex (PFC) and medial temporal lobe (MTL), including the hippocampus, play a role in representing information about temporal order. The involvement of these areas in successful temporal working memory, however, is less clear. Additionally, it is unknown whether regions in the PFC and MTL support temporal working memory across different timescales, or at coarse or fine levels of temporal detail. To address these questions, participants were scanned while completing 3 working memory task conditions (Group, Position and Item) that were matched in terms of difficulty and the number of items to be actively maintained. Group and Position trials probed temporal working memory processes, requiring the maintenance of hierarchically organized coarse and fine temporal information, respectively. To isolate activation related to temporal working memory, Group and Position trials were contrasted against Item trials, which required detailed working memory maintenance of visual objects. Results revealed that working memory encoding and maintenance of temporal information relative to visual information was associated with increased activation in dorsolateral PFC (DLPFC), and perirhinal cortex (PRC). In contrast, maintenance of visual details relative to temporal information was characterized by greater activation of parahippocampal cortex (PHC), medial and anterior PFC, and retrosplenial cortex. In the hippocampus, a dissociation along the longitudinal axis was observed such that the anterior hippocampus was more active for working memory encoding and maintenance of visual detail information relative to temporal information, whereas the posterior hippocampus displayed the opposite effect. Posterior parietal cortex was the only region to show sensitivity to temporal

  12. Comparison of BMI and physical activity between old order Amish children and non-Amish children.

    Science.gov (United States)

    Hairston, Kristen G; Ducharme, Julie L; Treuth, Margarita S; Hsueh, Wen-Chi; Jastreboff, Ania M; Ryan, Kathy A; Shi, Xiaolian; Mitchell, Braxton D; Shuldiner, Alan R; Snitker, Soren

    2013-04-01

    The Old Order Amish (OOA) is a conservative Christian sect of European origin living in Pennsylvania. Diabetes is rare in adult OOA despite a mean BMI rivaling that in the general U.S. non-Hispanic white population. The current study examines childhood factors that may contribute to the low prevalence of diabetes in the OOA by comparing OOA children aged 8-19 years with National Health and Nutrition Examination Survey (NHANES) data and children from Maryland's Eastern Shore (ES), a nearby, non-Amish, rural community. We hypothesized that pediatric overweight is less common in OOA children, that physical activity (PA) and BMI are inversely correlated, and that OOA children are more physically active than ES children. We obtained anthropometric data in 270 OOA children and 229 ES children (166 non-Hispanic white, 60 non-Hispanic black, 3 Hispanic). PA was measured by hip-worn accelerometers in all ES children and in 198 OOA children. Instrumentation in 43 OOA children was identical to ES children. OOA children were approximately 3.3 times less likely than non-Hispanic white ES children and NHANES estimates to be overweight (BMI ≥85th percentile, Centers for Disease Control and Prevention). Time spent in moderate/vigorous PA (MVPA) was inversely correlated to BMI z-score (r = -0.24, P = 0.0006). PA levels did not differ by ethnicity within the ES group, but OOA children spent an additional 34 min/day in light activity (442 ± 56 vs. 408 ± 75, P = 0.005) and, impressively, an additional 53 min/day in MVPA (106 ± 54 vs. 53 ± 32, P < 0.0001) compared with ES children. In both groups, boys were more active than girls but OOA girls were easily more active than ES boys. We confirmed all three hypotheses. Together with our previous data, the study implies that the OOA tend to gain their excess weight relatively late in life and that OOA children are very physically active, both of which may provide some long-term protection against diabetes.

  13. Exquisite Modulation of the Active Site of Methanocaldococcus jannaschii Adenylosuccinate Synthetase in Forward Reaction Complexes.

    Science.gov (United States)

    Karnawat, Vishakha; Mehrotra, Sonali; Balaram, Hemalatha; Puranik, Mrinalini

    2016-05-03

    In enzymes that conduct complex reactions involving several substrates and chemical transformations, the active site must reorganize at each step to complement the transition state of that chemical step. Adenylosuccinate synthetase (ADSS) utilizes a molecule each of guanosine 5'-monophosphate (GTP) and aspartate to convert inosine 5'-monophosphate (IMP) into succinyl adenosine 5'-monophosphate (sAMP) through several kinetic intermediates. Here we followed catalysis by ADSS through high-resolution vibrational spectral fingerprints of each substrate and intermediate involved in the forward reaction. Vibrational spectra show differential ligand distortion at each step of catalysis, and band positions of substrates are influenced by binding of cosubstrates. We found that the bound IMP is distorted toward its N1-deprotonated form even in the absence of any other ligands. Several specific interactions between GTP and active-site amino acid residues result in large Raman shifts and contribute substantially to intrinsic binding energy. When both IMP and GTP are simultaneously bound to ADSS, IMP is converted into an intermediate 6-phosphoryl inosine 5'-monophosphate (6-pIMP). The 6-pIMP·ADSS complex was found to be stable upon binding of the third ligand, hadacidin (HDA), an analogue of l-aspartate. We find that in the absence of HDA, 6-pIMP is quickly released from ADSS, is unstable in solution, and converts back into IMP. HDA allosterically stabilizes ADSS through local conformational rearrangements. We captured this complex and determined the spectra and structure of 6-pIMP in its enzyme-bound state. These results provide important insights into the exquisite tuning of active-site interactions with changing substrate at each kinetic step of catalysis.

  14. Effects of transpiration on unsteady MHD flow of an upper convected Maxwell (UCM) fluid passing through a stretching surface in the presence of a first order chemical reaction

    International Nuclear Information System (INIS)

    Mukhopadhyay, Swati; Arif, M. Golam; Pk M Wazed Ali

    2013-01-01

    The aim of this article is to present the effects of transpiration on the unsteady two-dimensional boundary layer flow of non-Newtonian fluid passing through a stretching sheet in the presence of a first order constructive/destructive chemical reaction. The upper-convected Maxwell (UCM) model is used here to characterize the non-Newtonian behavior of the fluid. Using similarity solutions, the governing nonlinear partial differential equations are transformed into ordinary ones and are then solved numerically by the shooting method. The flow fields and mass transfer are significantly influenced by the governing parameters. The fluid velocity initially decreases as the unsteadiness parameter increases and the concentration decreases significantly due to the increase in the unsteadiness. The effect of increasing values of transpiration (suction) and the Maxwell parameter is to suppress the velocity field; however, the concentration is enhanced as transpiration (suction) and the Maxwell parameter increase. Also, it is found that the fluid velocity decreases as the magnetic parameter increases; however, the concentration increases in this case. (electromagnetism, optics, acoustics, heat transfer, classical mechanics, and fluid dynamics)

  15. Directed surfaces structures and interfaces for enhanced electrocatalyst activity, selectivity, and stability for energy conversion reactions

    Energy Technology Data Exchange (ETDEWEB)

    Jaramillo, Thomas F. [Stanford Univ., CA (United States). Dept. of Chemical Engineering. Shriram Center

    2016-04-20

    In this project, we have employed a systematic approach to develop active, selective, and stable catalyst materials for important electrochemical reactions involving energy conversion. In particular, we have focused our attention on developing active catalyst materials for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). HER: We have synthesized and investigated several highly active and acid stable non-precious metal HER catalysts, including: [Mo3S13]2- nanoclusters (Nature Chemistry, 2014) and molybdenum phosphosulfide (MoP|S) (Angewandte Chemie, 2014). We have also aimed to engineer these catalyst formulations in a membrane electrode assembly (MEA) for fundamental studies of water electrolysis at high current densities, approximately 1 A/cm2 (ChemSusChem, 2015). We furthermore investigated transition metal phosphide (TMP) catalysts for HER by a combined experimental–theoretical approach (Energy & Environmental Science, 2015). By synthesizing different TMPs and comparing experimentally determined HER activities with the hydrogen adsorption free energies, ΔGH, calculated by density functional theory, we showed that the TMPs follow a volcano relationship for the HER. Using our combined experimental–theoretical model, we predicted that the mixed metal TMP, Fe0.5Co0.5P, should have a near-optimal ΔGH. We synthesized several mixtures of Co and Fe phosphides alloys and confirmed that Fe0.5Co0.5P exhibits the highest HER activity of the investigated TMPs (Energy & Environmental Science, 2015). The understanding gained as to how to improve catalytic activity for the HER, particularly for non-precious metal materials, is important to DOE targets for sustainable H2 production. OER: We have developed a SrIrO3/IrOx catalyst for acidic conditions (submitted, 2016). The Sr

  16. Effect of one step KOH activation and CaO modified carbon in transesterification reaction

    Science.gov (United States)

    Yacob, Abd Rahim; Zaki, Muhammad Azam Muhammad

    2017-11-01

    In this work, one step activation was introduced using potassium hydroxide (KOH) and calcium oxide (CaO) modified palm kernel shells. Various concentration of calcium oxide was used as catalyst while maintaining the same concentration of potassium hydroxide to activate and impregnate the palm kernel shell before calcined at 500°C for 5 hours. All the prepared samples were characterized using Fourier Transform Infrared (FTIR) and Field Emission Scanning Electron Microscope (FESEM). FTIR analysis of raw palm kernel shell showed the presence of various functional groups. However, after activation, most of the functional groups were eliminated. The basic strength of the prepared samples were determined using back titration method. The samples were then used as base heterogeneous catalyst for the transesterification reaction of rice bran oil with methanol. Analysis of the products were performed using Gas Chromatography Flame Ionization Detector (GC-FID) to calculate the percentage conversion of the biodiesel products. This study shows, as the percentage of one step activation potassium and calcium oxide doped carbon increases thus, the basic strength also increases followed by the increase in biodiesel production. Optimization study shows that the optimum biodiesel production was at 8 wt% catalyst loading, 9:1 methanol: oil molar ratio at 65°C and 6 hours which gives a conversion up to 95%.

  17. Evidence for the Active Phase of Heterogeneous Catalysts through In Situ Reaction Product Imaging and Multiscale Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Matera, S.; Blomberg, S.; Hoffmann, M. J.; Zetterberg, J.; Gustafson, J.; Lundgren, E.; Reuter, K.

    2015-06-17

    We use multiscale modeling to analyze laser-induced fluorescence (LIF) measurements of the CO oxidation reaction over Pd(100) at near-ambient reaction conditions. Integrating density functional theory-based kinetic Monte Carlo simulations of the active catalyst into fluid-dynamical simulations of the mass transport inside the reactor chamber, we calculate the reaction product concentration directly above the catalyst surface. Comparing corresponding data calculated for different surface models against the measured LIF signals, we can discriminate the one that predominantly actuates the experimentally measured catalytic activity. For the probed CO oxidation reaction conditions, the experimental activity is due to pristine Pd(100) possibly coexisting with other (oxidic) domains on the surface.

  18. Micro-Membrane Electrode Assembly Design to Precisely Measure the in Situ Activity of Oxygen Reduction Reaction Electrocatalysts for PEMFC.

    Science.gov (United States)

    Long, Zhi; Li, Yankai; Deng, Guangrong; Liu, Changpeng; Ge, Junjie; Ma, Shuhua; Xing, Wei

    2017-06-20

    An in situ micro-MEA technique, which could precisely measure the performance of ORR electrocatalyst using Nafion as electrolyte, was designed and compared with regular thin-film rotating-disk electrode (TFRDE) (0.1 M HClO 4 ) and normal in situ membrane electrode assembly (MEA) tests. Compared to the traditional TFRDE method, the micro-MEA technique makes the acquisition of catalysts' behavior at low potential values easily achieved without being limited by the solubility of O 2 in water. At the same time, it successfully mimics the structure of regular MEAs and obtains similar results to a regular MEA, thus providing a new technique to simply measure the electrode activity without being bothered by complicated fabrication of regular MEA. In order to further understand the importance of in situ measurement, Fe-N-C as a typical oxygen reduction reaction (ORR) free-Pt catalyst was evaluated by TFRDE and micro-MEA. The results show that the half wave potential of Fe-N-C only shifted negatively by -135 mV in comparison with state-of-the-art Pt/C catalysts from TFRDE tests. However, the active site density, mass transfer of O 2 , and the proton transfer conductivity are found to strongly influence the catalyst activity in the micro-MEA, thereby resulting in a much lower limiting current density than Pt/C (8.7 times lower). Hence, it is suggested that the micro-MEA is better in evaluating the in situ ORR performance, where the catalysts are characterized more thoroughly in terms of intrinsic activity, active site density, proton transfer, and mass transfer properties.

  19. Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds

    Directory of Open Access Journals (Sweden)

    Burkhard Koenig

    2011-01-01

    Full Text Available N-Arylated aliphatic and aromatic amines are important substituents in many biologically active compounds. In the last few years, transition-metal-mediated N-aryl bond formation has become a standard procedure for the introduction of amines into aromatic systems. While N-arylation of simple aromatic halides by simple amines works with many of the described methods in high yield, the reactions may require detailed optimization if applied to the synthesis of complex molecules with additional functional groups, such as natural products or drugs. We discuss and compare in this review the three main N-arylation methods in their application to the synthesis of biologically active compounds: Palladium-catalysed Buchwald–Hartwig-type reactions, copper-mediated Ullmann-type and Chan–Lam-type N-arylation reactions. The discussed examples show that palladium-catalysed reactions are favoured for large-scale applications and tolerate sterically demanding substituents on the coupling partners better than Chan–Lam reactions. Chan–Lam N-arylations are particularly mild and do not require additional ligands, which facilitates the work-up. However, reaction times can be very long. Ullmann- and Buchwald–Hartwig-type methods have been used in intramolecular reactions, giving access to complex ring structures. All three N-arylation methods have specific advantages and disadvantages that should be considered when selecting the reaction conditions for a desired C–N bond formation in the course of a total synthesis or drug synthesis.

  20. Investigation of the Maillard Reaction between Polysaccharides and Proteins from Longan Pulp and the Improvement in Activities.

    Science.gov (United States)

    Han, Miao-Miao; Yi, Yang; Wang, Hong-Xun; Huang, Fei

    2017-06-05

    The purpose of this study was to investigate the Maillard reaction between polysaccharides and proteins from longan pulp and the effects of reaction on their in vitro activities. The polysaccharide-protein mixtures of fresh longan pulp (LPPMs) were co-prepared by an alkali extraction-acid precipitation method. They were then dry-heated under controlled conditions for monitoring the characterization of the Maillard reaction by the measurement of the free amino group content, ultraviolet-visible spectrum, Fourier transform infrared spectrum and molecular weight distribution. All the physicochemical analyses indicated the development of the Maillard reaction between polysaccharides and proteins. The in vitro activity evaluation indicated that the Maillard reaction could effectively enhance the antioxidant, antitumor and immunostimulating activities of LPPMs. The enhancement of 1,1-diphenyl-2-picrylhydrazyl radical scavenging activity and ferric reducing antioxidant power displayed both a positive correlation with the reaction time ( p Maillard-type intermacromolecular interaction is suggested to be an effective and controllable method for improving the functional activities of polysaccharides and proteins from longan pulp.

  1. Temperature dependent halogen activation by N2O5 reactions on halide-doped ice surfaces

    Directory of Open Access Journals (Sweden)

    J. A. Thornton

    2012-06-01

    Full Text Available We examined the reaction of N2O5 on frozen halide salt solutions as a function of temperature and composition using a coated wall flow tube technique coupled to a chemical ionization mass spectrometer (CIMS. The molar yield of photo-labile halogen compounds was near unity for almost all conditions studied, with the observed reaction products being nitryl chloride (ClNO2 and/or molecular bromine (Br2. The relative yield of ClNO2 and Br2 depended on the ratio of bromide to chloride ions in the solutions used to form the ice. At a bromide to chloride ion molar ratio greater than 1/30 in the starting solution, Br2 was the dominant product otherwise ClNO2 was primarily produced on these near pH-neutral brines. We demonstrate that the competition between chlorine and bromine activation is a function of the ice/brine temperature presumably due to the preferential precipitation of NaCl hydrates from the brine below 250 K. Our results provide new experimental confirmation that the chemical environment of the brine layer changes with temperature and that these changes can directly affect multiphase chemistry. These findings have implications for modeling air-snow-ice interactions in polar regions and likely in polluted mid-latitude regions during winter as well.

  2. Screening of catalytic oxygen reduction reaction activity of metal-doped graphene by density functional theory

    International Nuclear Information System (INIS)

    Chen, Xin; Chen, Shuangjing; Wang, Jinyu

    2016-01-01

    Highlights: • The screened M-G structures are very thermodynamically stable, and the stability is even higher than that of the corresponding bulk metal surfaces. • The binding energies of ORR intermediates suggest that they are not linear dependence, which are different form the cases found on some metal-based catalysts. • The Au-, Co-, and Ag-G structures could be used as the ORR catalysts. - Abstract: Graphene doping is a promising direction for developing effective oxygen reduction reaction (ORR) catalysts. In this paper, we computationally investigated the ORR performance of 10 kinds of metal-doped graphene (M-G) catalysts, namely, Al-, Si-, Mn-, Fe-, Co-, Ni-, Pd-, Ag-, Pt-, and Au-G. The results shown that the binding energies of the metal atoms incorporated into the graphene vacancy are higher than their bulk cohesive energies, indicating the formed M-G catalysts are even more stable than the corresponding bulk metal surfaces, and thus avoid the metals dissolution in the reaction environment. We demonstrated that the linear relation among the binding energies of the ORR intermediates that found on metal-based materials does not hold for the M-G catalysts, therefore a single binding energy of intermediate alone is not sufficient to evaluate the ORR activity of an arbitrary catalyst. By analysis of the detailed ORR processes, we predicted that the Au-, Co-, and Ag-G materials can be used as the ORR catalysts.

  3. Electrocatalytic activity of cobalt phosphide-modified graphite felt toward VO2+/VO2+ redox reaction

    Science.gov (United States)

    Ge, Zhijun; Wang, Ling; He, Zhangxing; Li, Yuehua; Jiang, Yingqiao; Meng, Wei; Dai, Lei

    2018-04-01

    A novel strategy for improving the electro-catalytic properties of graphite felt (GF) electrode in vanadium redox flow battery (VRFB) is designed by depositing cobalt phosphide (CoP) onto GF surface. The CoP powder is synthesized by direct carbonization of Co-based zeolitic imidazolate framework (ZIF-67) followed by phosphidation. Cyclic voltammetry results confirm that the CoP-modified graphite felt (GF-CoP) electrode has excellent reversibility and electro-catalytic activity to the VO2+/VO2+ cathodic reaction compared with the pristine GF electrode. The cell using GF-CoP electrode shows apparently higher discharge capacity over that based on GF electrode. The cell using GF-CoP electrode has the capacity of 67.2 mA h at 100 mA cm-2, 32.7 mA h larger than that using GF electrode. Compared with cell using GF electrode, the voltage efficiency of the cell based on GF-CoP electrode increases by 5.9% and energy efficiency by 5.4% at a current density of 100 mA cm-2. The cell using GF-CoP electrode can reach 94.31% capacity retention after 50 cycles at a current density of 30 mA cm-2. The results show that the CoP can effectively promote the VO2+/VO2+ redox reaction, implying that metal phosphides are a new kind of potential catalytic materials for VRFB.

  4. Dynamics of activity free radical oxidation reactions in students with cerebral palsy results over the course of the educational process

    Directory of Open Access Journals (Sweden)

    Makarova E.V.

    2012-12-01

    Full Text Available The dynamics of changes activity of reactions is studied freely radical oxidize for students with the consequences of child's cerebral paralysis. 20 students took part in an experiment. Found that the course of study they have more active free radical oxidation reactions and decreases the activity of antiradical protection. Given the use of additional physical activity in aerobic training indicators intracellular antioxidant defense system increased, decreased content of reaction products of lipid peroxidation. However, increased rates of maximum oxygen consumption and increased tolerance of students with cerebral palsy to the consequences of physical activity. It is set that the pathological changes of metabolism for students ground the necessity of application of the differentiated physical loadings. The optimum forms of physical rehabilitation of the aerobic training is the dosed walking, medical swimming, dosed after distance, sometimes and by the corner of getting up pedestrian ascents. Loading is increased due to a volume, but not intensity of exercises.

  5. SABER: a computational method for identifying active sites for new reactions.

    Science.gov (United States)

    Nosrati, Geoffrey R; Houk, K N

    2012-05-01

    A software suite, SABER (Selection of Active/Binding sites for Enzyme Redesign), has been developed for the analysis of atomic geometries in protein structures, using a geometric hashing algorithm (Barker and Thornton, Bioinformatics 2003;19:1644-1649). SABER is used to explore the Protein Data Bank (PDB) to locate proteins with a specific 3D arrangement of catalytic groups to identify active sites that might be redesigned to catalyze new reactions. As a proof-of-principle test, SABER was used to identify enzymes that have the same catalytic group arrangement present in o-succinyl benzoate synthase (OSBS). Among the highest-scoring scaffolds identified by the SABER search for enzymes with the same catalytic group arrangement as OSBS were L-Ala D/L-Glu epimerase (AEE) and muconate lactonizing enzyme II (MLE), both of which have been redesigned to become effective OSBS catalysts, demonstrated by experiments. Next, we used SABER to search for naturally existing active sites in the PDB with catalytic groups similar to those present in the designed Kemp elimination enzyme KE07. From over 2000 geometric matches to the KE07 active site, SABER identified 23 matches that corresponded to residues from known active sites. The best of these matches, with a 0.28 Å catalytic atom RMSD to KE07, was then redesigned to be compatible with the Kemp elimination using RosettaDesign. We also used SABER to search for potential Kemp eliminases using a theozyme predicted to provide a greater rate acceleration than the active site of KE07, and used Rosetta to create a design based on the proteins identified. Copyright © 2012 The Protein Society.

  6. Heat Capacity Changes and Disorder-to-Order Transitions in Allosteric Activation.

    Science.gov (United States)

    Cressman, William J; Beckett, Dorothy

    2016-01-19

    Allosteric coupling in proteins is ubiquitous but incompletely understood, particularly in systems characterized by coupling over large distances. Binding of the allosteric effector, bio-5'-AMP, to the Escherichia coli biotin protein ligase, BirA, enhances the protein's dimerization free energy by -4 kcal/mol. Previous studies revealed that disorder-to-order transitions at the effector binding and dimerization sites, which are separated by 33 Å, are integral to functional coupling. Perturbations to the transition at the ligand binding site alter both ligand binding and coupled dimerization. Alanine substitutions in four loops on the dimerization surface yield a range of energetic effects on dimerization. A glycine to alanine substitution at position 142 in one of these loops results in a complete loss of allosteric coupling, disruption of the disorder-to-order transitions at both functional sites, and a decreased affinity for the effector. In this work, allosteric communication between the effector binding and dimerization surfaces in BirA was further investigated by performing isothermal titration calorimetry measurements on nine proteins with alanine substitutions in three dimerization surface loops. In contrast to BirAG142A, at 20 °C all variants bind to bio-5'-AMP with free energies indistinguishable from that measured for wild-type BirA. However, the majority of the variants exhibit altered heat capacity changes for effector binding. Moreover, the ΔCp values correlate with the dimerization free energies of the effector-bound proteins. These thermodynamic results, combined with structural information, indicate that allosteric activation of the BirA monomer involves formation of a network of intramolecular interactions on the dimerization surface in response to bio-5'-AMP binding at the distant effector binding site.

  7. Oxygen reduction activity of carbon fibers cathode, and application for current generation from the NAD+ and NADH recycling reaction

    Directory of Open Access Journals (Sweden)

    H. Maeda

    2012-03-01

    Full Text Available Carbon fibers treated at 700 oC for 10 min were found to have O2 reduction activity when being used as a cathode. The special type of partition combined with both cationic and anionic exchange membranes was applied between anode cell and cathode cell in order to use a highly acidic solution such as 0.5 M H2SO4 as an electrolyte of the cathode cell for increasing the efficiency of O2 reduction activity. The current generation from NAD+ and NADH recycling system combined with D-gluconolactone production from 500 mg of D-glucose was performed by applying only carbon fibers for both anode and cathode. The total current volume obtained was 81.4 mAh during the reaction for 10 h, and the current efficiency was 93%. One gram of carbon fibers was pressed with Nafion paste on a piece of carbon paper(area : 50 mm×50mm with heating to prepare the cathode, and this construct was combined with conventional fuel cell. The power density was 3.6 mW/cm2, and the total power volume was calculated to be 90 mW per 1 g of carbon fibers.

  8. Non-Fermi Liquids as Highly Active Oxygen Evolution Reaction Catalysts.

    Science.gov (United States)

    Hirai, Shigeto; Yagi, Shunsuke; Chen, Wei-Tin; Chou, Fang-Cheng; Okazaki, Noriyasu; Ohno, Tomoya; Suzuki, Hisao; Matsuda, Takeshi

    2017-10-01

    The oxygen evolution reaction (OER) plays a key role in emerging energy conversion technologies such as rechargeable metal-air batteries, and direct solar water splitting. Herein, a remarkably low overpotential of ≈150 mV at 10 mA cm -2 disk in alkaline solutions using one of the non-Fermi liquids, Hg 2 Ru 2 O 7 , is reported. Hg 2 Ru 2 O 7 displays a rapid increase in current density and excellent durability as an OER catalyst. This outstanding catalytic performance is realized through the coexistence of localized d-bands with the metallic state that is unique to non-Fermi liquids. The findings indicate that non-Fermi liquids could greatly improve the design of highly active OER catalysts.

  9. [Delayed reactions of active avoidance in white rats under conditions of an alternative choice].

    Science.gov (United States)

    Ioseliani, T K; Sikharulidze, N I; Kadagishvili, A Ia; Mitashvili, E G

    1995-01-01

    It was shown that if the rats had been learned and then tested using conventional pain punishment of erroneous choice they were able to solve the problem of alternative choice only in the period of immediate action of conditioned stimuli. If the pain punishment for erroneously chosen compartment had not been applied in animal learning and testing, rats successfully solved the problem of alternative choice even after 5-second delay. Introduction of pain punishment led to the frustration of earlier elaborated delayed avoidance reactions. Analysis of the obtained results allows us to argue that the apparent incapability of white rats for solving the problems of delayed avoidance is caused by simultaneous action of two different mechanisms, i.e., those of the active and passive avoidance rather than short-term memory deficit.

  10. Reaction pathway and oxidation mechanisms of dibutyl phthalate by persulfate activated with zero-valent iron

    Energy Technology Data Exchange (ETDEWEB)

    Li, Huanxuan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); Wan, Jinquan, E-mail: ppjqwan@scut.edu.cn [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Ma, Yongwen [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China); State Key Lab Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640 (China); Wang, Yan [School of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, China, Guangzhou 510640 (China)

    2016-08-15

    This study investigated reaction pathway and oxidation mechanisms of dibutyl phthalate (DBP) by persulfate (PS) activated with zero-valent iron (ZVI). The DBP degradation was studied at three pH values (acidic, neutral and basic) in the presence of different organic scavengers. Using a chemical probe method, both sulfate radical (SO{sub 4}·{sup −}) and hydroxyl radical (·OH) were found to be primary oxidants at pH 3.0 and pH 7.0, respectively while ·OH was the major specie to oxidize DBP at pH 11.0. A similar result was found in an experiment of Electron Spin Resonance spin-trapping where in addition to ·OH, superoxide radical (O{sub 2}·{sup −}) was detected at pH 11.0. The transformation of degradation products including dimethyl phthalate (DMP), diethyl phthalate (DEP), phthalic anhydride, and acetophenone exhibited diverse variation during the reaction processes. The phthalic anhydride concentration appeared to be maximum at all pHs. Another eleven intermediate products were also found at pH 3.0 by GC–MS and HPLC analysis, and their degradation mechanisms and pathways were proposed. It was suggested that dealkylation, hydroxylation, decarboxylation and hydrogen extraction were the dominant degradation mechanisms of DBP at pH 3.0. - Highlights: • Both SO{sub 4}{sup −}· and ·OH were found to be the major active species at pH 3.0 and pH 7.0. • ·OH and ·O2– were the primary oxidants pH 11.0. • The intermediate products were investigated as well as the degradation pathway. • Dealkylation, hydroxylation, decarboxylation, H-extraction were the major mechanisms.

  11. Enhanced electrocatalytic activity of MoSx on TCNQ-treated electrode for hydrogen evolution reaction

    KAUST Repository

    Chang, Yunghuang

    2014-10-22

    Molybdenum sulfide has recently attracted much attention because of its low cost and excellent catalytical effects in the application of hydrogen evolution reaction (HER). To improve the HER efficiency, many researchers have extensively explored various avenues such as material modification, forming hybrid structures or modifying geometric morphology. In this work, we reported a significant enhancement in the electrocatalytic activity of the MoSx via growing on Tetracyanoquinodimethane (TCNQ) treated carbon cloth, where the MoSx was synthesized by thermolysis from the ammonium tetrathiomolybdate ((NH4)2MoS4) precursor at 170 °C. The pyridinic N- and graphitic N-like species on the surface of carbon cloth arising from the TCNQ treatment facilitate the formation of Mo5+ and S2 2- species in the MoSx, especially with S2 2- serving as an active site for HER. In addition, the smaller particle size of the MoSx grown on TCNQ-treated carbon cloth reveals a high ratio of edge sites relative to basal plane sites, indicating the richer effective reaction sites and superior electrocatalytic characteristics. Hence, we reported a high hydrogen evolution rate for MoSx on TCNQ-treated carbon cloth of 6408 mL g-1 cm-2 h-1 (286 mmol g-1 cm-2 h-1) at an overpotential of V = 0.2 V. This study provides the fundamental concepts useful in the design and preparation of transition metal dichalcogenide catalysts, beneficial in the development in clean energy.

  12. [High activity antiretroviral therapy change associated to adverse drug reactions in a specialized center in Venezuela].

    Science.gov (United States)

    Subiela, José D; Dapena, Elida

    2016-03-01

    Adverse drug reactions (ADRs) represent the first cause of change of the first-line highly active antiretroviral therapy (HAART) regimen, therefore, they constitute the main limiting factor in the long-term follow up of HIV patients in treatment. A retrospective study was carried out in a specialized center in Lara State, Venezuela, including 99 patients over 18 years of age who had change of first-line HAART regimen due to ADRs, between 2010 and 2013. The aims of this research were to describe the sociodemographic and clinical variables, frequency of ADRs related to change of HAART, duration of the first-line HAART regimen, to determine the drugs associated with ARVs and to identify the risk factors. The ADRs constituted 47.5% of all causes of change of first-line HAART regimen, the median duration was 1.08±0.28 years. The most frequent ADRs were anemia (34.3%), hypersensitivity reactions (20.2%) and gastrointestinal intolerance (13.1%). The most frequent ARV regimen type was the protease inhibitors-based regimen (59.6%), but zidovudine was the ARV most linked to ADRs (41.4%). The regression analysis showed increased risk of ADRs in singles and students in the univariate analysis and heterosexuals and homosexuals in multivariate analysis; and decreased risk in active workers. The present work shows the high prevalence of ADRs in the studied population and represents the first case-based study that describes the pharmacoepidemiology of a cohort of HIV-positive patients treated in Venezuela.

  13. The effect of toxic carbon source on the reaction of activated sludge in the batch reactor.

    Science.gov (United States)

    Wu, Changyong; Zhou, Yuexi; Zhang, Siyu; Xu, Min; Song, Jiamei

    2018-03-01

    The toxic carbon source can cause higher residual effluent dissolved organic carbon than easily biodegraded carbon source in activated sludge process. In this study, an integrated activated sludge model is developed as the tool to understand the mechanism of toxic carbon source (phenol) on the reaction, regarding the carbon flows during the aeration period in the batch reactor. To estimate the toxic function of phenol, the microbial cells death rate (k death ) is introduced into the model. The integrated model was calibrated and validated by the experimental data and it was found the model simulations matched the all experimental measurements. In the steady state, the toxicity of phenol can result in higher microbial cells death rate (0.1637 h -1 vs 0.0028 h -1 ) and decay rate coefficient of biomass (0.0115 h -1 vs 0.0107 h -1 ) than acetate. In addition, the utilization-associated products (UAP) and extracellular polymeric substances (EPS) formation coefficients of phenol are higher than that of acetate, indicating that more carbon flows into the extracellular components, such as soluble microbial products (SMP), when degrading toxic organics. In the non-steady state of feeding phenol, the yield coefficient for growth and maximum specific growth rate are very low in the first few days (1-10 d), while the decay rate coefficient of biomass and microbial cells death rate are relatively high. The model provides insights into the difference of the dynamic reaction with different carbon sources in the batch reactor. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Activation cross-section data for -particle-induced nuclear reactions ...

    Indian Academy of Sciences (India)

    B M ALI

    2018-02-20

    particle-induced nuclear reactions on natural vanadium up to 20 MeV. It should be mentioned that this study represents a part of (a supplement) systematical study of charged particles-induced nuclear reactions. Earlier studies were.

  15. Sub-4 nm PtZn Intermetallic Nanoparticles for Enhanced Mass and Specific Activities in Catalytic Electrooxidation Reaction

    International Nuclear Information System (INIS)

    Qi, Zhiyuan

    2017-01-01

    Atomically ordered intermetallic nanoparticles (iNPs) have sparked considerable interest in fuel cell applications by virtue of their exceptional electronic and structural properties. However, the synthesis of small iNPs in a controllable manner remains a formidable challenge because of the high temperature generally required in the formation of intermetallic phases. Here in this paper we report a general method for the synthesis of PtZn iNPs (3.2 ± 0.4 nm) on multiwalled carbon nanotubes (MWNT) via a facile and capping agent free strategy using a sacrificial mesoporous silica (mSiO 2 ) shell. The as-prepared PtZn iNPs exhibited ca. 10 times higher mass activity in both acidic and basic solution toward the methanol oxidation reaction (MOR) compared to larger PtZn iNPs synthesized on MWNT without the mSiO 2 shell. Density functional theory (DFT) calculations predict that PtZn systems go through a “non-CO” pathway for MOR because of the stabilization of the OH* intermediate by Zn atoms, while a pure Pt system forms highly stable COH* and CO* intermediates, leading to catalyst deactivation. Experimental studies on the origin of the backward oxidation peak of MOR coincide well with DFT predictions. Moreover, the calculations demonstrate that MOR on smaller PtZn iNPs is energetically more favorable than larger iNPs, due to their high density of corner sites and lower-lying energetic pathway. Therefore, smaller PtZn iNPs not only increase the number but also enhance the activity of the active sites in MOR compared with larger ones. This work opens a new avenue for the synthesis of small iNPs with more undercoordinated and enhanced active sites for fuel cell applications.

  16. Improving the electrocatalytic performance of carbon nanotubes for VO"2"+/VO_2"+ redox reaction by KOH activation

    International Nuclear Information System (INIS)

    Dai, Lei; Jiang, Yingqiao; Meng, Wei; Zhou, Huizhu; Wang, Ling; He, Zhangxing

    2017-01-01

    Highlights: • KOH-activated carbon nanotubes (CNTs) was investigated as superior catalyst for VO"2"+/VO_2"+ redox reaction for vanadium redox flow battery (VRFB) for the first time. • KOH activation for CNTs can result in the chemical etching of surface and improved wettability, accelerating the mass transfer of vanadium ions. • KOH activation can introduce many oxygen-containing groups as active sites on the surface of CNTs. • KOH-activated CNTs as positive catalyst could increase the comprehensive energy storage performance of VRFB. - Abstract: In this paper, carbon nanotubes (CNTs) was activated by KOH treatment at high temperature and investigated as catalyst for VO"2"+/VO_2"+ redox reaction for vanadium redox flow battery (VRFB). X-ray photoelectron spectroscopy results suggest that the oxygen-containing groups can be introduced on CNTs by KOH activation. The mass transfer of vanadium ions can be accelerated by chemical etching by KOH activation and improved wettability due to the introduction of hydrophilic groups. The electrochemical properties of VO"2"+/VO_2"+ redox reaction can be enhanced by introduced oxygen-containing groups as active sites. The sample treated at 900 °C with KOH/CNTs mass ratio of 3:1 (CNTs-3) exhibits the highest electrocatalytic activity for VO"2"+/VO_2"+ redox reaction. The cell using CNTs-3 as positive catalyst demonstrates the smallest electrochemical polarization, the highest capacity and efficiency among the samples. Using KOH-activated CNTs-3 can increase the average energy efficiency of the cell by 4.4%. This work suggests that KOH-activated CNTs is a low-cost, efficient and promising catalyst for VO"2"+/VO_2"+ redox reaction for VRFB system.

  17. A robust fractional-order PID controller design based on active queue management for TCP network

    Science.gov (United States)

    Hamidian, Hamideh; Beheshti, Mohammad T. H.

    2018-01-01

    In this paper, a robust fractional-order controller is designed to control the congestion in transmission control protocol (TCP) networks with time-varying parameters. Fractional controllers can increase the stability and robustness. Regardless of advantages of fractional controllers, they are still not common in congestion control in TCP networks. The network parameters are time-varying, so the robust stability is important in congestion controller design. Therefore, we focused on the robust controller design. The fractional PID controller is developed based on active queue management (AQM). D-partition technique is used. The most important property of designed controller is the robustness to the time-varying parameters of the TCP network. The vertex quasi-polynomials of the closed-loop characteristic equation are obtained, and the stability boundaries are calculated for each vertex quasi-polynomial. The intersection of all stability regions is insensitive to network parameter variations, and results in robust stability of TCP/AQM system. NS-2 simulations show that the proposed algorithm provides a stable queue length. Moreover, simulations show smaller oscillations of the queue length and less packet drop probability for FPID compared to PI and PID controllers. We can conclude from NS-2 simulations that the average packet loss probability variations are negligible when the network parameters change.

  18. Mechanically activated SHS reaction in the Fe-Al system: in-situ time resolved diffraction using synchrotron radiation

    International Nuclear Information System (INIS)

    Gaffet, E.; Charlot, F.; Klein, D.; Bernard, F.; Niepce, J.C.

    1998-01-01

    The mechanical activation self propagating high temperature synthesis (M.A.S.H.S.) processing is a new way to produce nanocrystalline iron aluminide intermetallic compounds. This process is maily the combination of two steps; in the one hand, a mechanical activation where the Fe - Al powder mixture was milled during a short time at given energy and frequency of shocks and in the other hand, a self propagating high temperature synthesis (S.H.S.) reaction, for which the exothermicity of the Fe + Al reaction is used. This fast propagated MASHS reaction has been in-situ investigated using the time resolved X-ray diffraction (TRXRD) using a X-ray synchrotron beam and an infrared thermography camera, allowing the coupling of the materials structure and the temperature field. The effects of the initial mean compositions, of the milling conditions as well as of the compaction parameters on the MASHS reaction are reported. (orig.)

  19. Activation cross section and isomeric cross section ratios for the (n ,2 n ) reaction on 153Eu

    Science.gov (United States)

    Luo, Junhua; Jiang, Li; Li, Suyuan

    2017-10-01

    The 153Eu(n ,2 n ) m1,m2,g152Eu cross section was measured by means of the activation technique at three neutron energies in the range 13-15 MeV. The quasimonoenergetic neutron beam was formed via the 3H(d ,n ) 4He reaction, in the Pd-300 Neutron Generator at the Chinese Academy of Engineering Physics (CAEP). The activities induced in the reaction products were measured using high-resolution γ-ray spectroscopy. The cross section of the population of the second high-spin (8-) isomeric state was measured along with the reaction cross section populating both the ground (3-) and the first isomeric state (0-). Cross sections were also evaluated theoretically using the numerical code TALYS-1.8, with different level density options at neutron energies varying from the reaction threshold to 20 MeV. Results are discussed and compared with the corresponding literature.

  20. Reanalysis of Rate Data for the Reaction CH3 + CH3 → C2H6 Using Revised Cross Sections and a Linearized Second-Order Master Equation.

    Science.gov (United States)

    Blitz, M A; Green, N J B; Shannon, R J; Pilling, M J; Seakins, P W; Western, C M; Robertson, S H

    2015-07-16

    Rate coefficients for the CH3 + CH3 reaction, over the temperature range 300-900 K, have been corrected for errors in the absorption coefficients used in the original publication ( Slagle et al., J. Phys. Chem. 1988 , 92 , 2455 - 2462 ). These corrections necessitated the development of a detailed model of the B̃(2)A1' (3s)-X̃(2)A2″ transition in CH3 and its validation against both low temperature and high temperature experimental absorption cross sections. A master equation (ME) model was developed, using a local linearization of the second-order decay, which allows the use of standard matrix diagonalization methods for the determination of the rate coefficients for CH3 + CH3. The ME model utilized inverse Laplace transformation to link the microcanonical rate constants for dissociation of C2H6 to the limiting high pressure rate coefficient for association, k∞(T); it was used to fit the experimental rate coefficients using the Levenberg-Marquardt algorithm to minimize χ(2) calculated from the differences between experimental and calculated rate coefficients. Parameters for both k∞(T) and for energy transfer ⟨ΔE⟩down(T) were varied and optimized in the fitting procedure. A wide range of experimental data were fitted, covering the temperature range 300-2000 K. A high pressure limit of k∞(T) = 5.76 × 10(-11)(T/298 K)(-0.34) cm(3) molecule(-1) s(-1) was obtained, which agrees well with the best available theoretical expression.

  1. Towards the Development of a Second-Order Approximation in Activity Coefficient Models Based on Group Contributions

    DEFF Research Database (Denmark)

    Abildskov, Jens; Constantinou, Leonidas; Gani, Rafiqul

    1996-01-01

    A simple modification of group contribution based models for estimation of liquid phase activity coefficients is proposed. The main feature of this modification is that contributions estimated from the present first-order groups in many instances are found insufficient since the first-order groups...... correlation/prediction capabilities, distinction between isomers and ability to overcome proximity effects....

  2. Interfacial reactions between sapphire and Ag–Cu–Ti-based active braze alloys

    International Nuclear Information System (INIS)

    Ali, Majed; Knowles, Kevin M.; Mallinson, Phillip M.; Fernie, John A.

    2016-01-01

    The interfacial reactions between two commercially available Ag–Cu–Ti-based active braze alloys and sapphire have been studied. In separate experiments, Ag–35.3Cu–1.8Ti wt.% and Ag–26.7Cu–4.5Ti wt.% alloys have been sandwiched between pieces of R-plane orientated sapphire and heated in argon to temperatures between 750 and 900 °C for 1 min. The phases at the Ag–Cu–Ti/sapphire interfaces have been studied using selected area electron diffraction, energy dispersive X-ray spectroscopy and electron energy loss spectroscopy. Gradual and subtle changes at the Ag–Cu–Ti/sapphire interfaces were observed as a function of temperature, along with the formation of a transient phase that permitted wetting of the sapphire. Unequivocal evidence is shown that when the active braze alloys melt, titanium first migrates to the sapphire and reacts to dissolve up to ∼33 at.% oxygen, forming a nanometre-size polycrystalline layer with a chemical composition of Ti 2 O 1–x (x ≪ 1). Ti 3 Cu 3 O particles subsequently nucleate behind the Ti 2 O 1–x layer and grow to become a continuous micrometre-size layer, replacing the Ti 2 O 1–x layer. Finally at 845 °C, a nanometre-size γ-TiO layer forms on the sapphire to leave a typical interfacial structure of Ag–Cu/Ti 3 Cu 3 O/γ-TiO/sapphire consistent with that seen in samples of polycrystalline alumina joined to itself with these active braze alloys. These experimental observations have been used to establish a definitive bonding mechanism for the joining of sapphire with Ag–Cu alloys activated by small amounts of titanium.

  3. Neuronal Activity in the Visual Cortex Reveals the Temporal Order of Cognitive Operations

    NARCIS (Netherlands)

    Moro, S.I.; Tolboom, M.; Khayat, P.S.; Roelfsema, P.R.

    2010-01-01

    Most mental processes consist of a number of processing steps that are executed sequentially. The timing of the individual mental operations can usually only be estimated indirectly, from the pattern of reaction times. In vision, however, many processing steps are associated with the modulation of

  4. Neuronal activity in the visual cortex reveals the temporal order of cognitive operations

    NARCIS (Netherlands)

    Moro, Sancho I.; Tolboom, Michiel; Khayat, Paul S.; Roelfsema, Pieter R.

    2010-01-01

    Most mental processes consist of a number of processing steps that are executed sequentially. The timing of the individual mental operations can usually only be estimated indirectly, from the pattern of reaction times. In vision, however, many processing steps are associated with the modulation of

  5. Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.

    Science.gov (United States)

    Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A

    2017-11-21

    Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important

  6. Effect of support on the activity of MoVCeZr catalyst for propane ammoxidation reaction

    International Nuclear Information System (INIS)

    Anita Ramli; Farinaa Md Jamil; Ishak Ahmad

    2010-01-01

    Mixed metal oxide catalysts based on Mo-V have been known as the most active and selective in the ammoxidation of propane to ACN. A series of MoVCeZr (5 % wt/ wt) supported with MOR, TiO 2 and MgO have been prepared by incipient wetness impregnation method for propane ammoxidation reaction to ACN. The catalyst was calcined in a two step calcination process in static air between 350 - 600 degree Celsius for 10 hour. The surface area and pore size of these catalysts were measured using physical adsorption of nitrogen following Brunauer, Emmet and Teller (BET) equation. The textural and morphological of these catalysts were determined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). The activities of all catalysts were tested using a fixed-bed reactor with online gas chromatography (GC) at 420 degree Celsius and atmospheric pressure in the presence of 0.5 ml catalyst with composition consisting of 5.8:7:17.4 (propane: ammonia: air) and helium as carrier to give a total flow of 120 ml. Result shows that MoVCeZr support gives a better conversion due to the surface area and pore size characteristic of the catalyst. (author)

  7. Reaction of misonidazole with DNA radicals and its effect on the template activity of DNA

    International Nuclear Information System (INIS)

    Endoh, Daiji; Kuwabara, Mikinori; Sato, Fumiaki; Yoshii, Giichi.

    1985-01-01

    After calf thymus DNA was gamma-irradiated in the solid state in vacuo and subsequently dissolved in aqueous solution containing misonidazole (3 mM) under hypoxic condition, the frequency of single-strand breaks and alkali-labile sites in DNA and the amount of misonidazole bound to DNA were measured. The presence of misonidazole converted the precursor radicals, which otherwise results in single-strand breaks, to alkali-labile sites, and the amount of alkali-labile sites increased linearly with increasing radiation dose. The amount of misonidazole bound to DNA also increased linearly with increasing radiation dose. The biological meaning of the changes in the frequency of single-strand breaks and alkali-labile sites by the reaction of misonidazole with DNA radicals and of binding misonidazole with DNA was examined using a model system to measure the template activity of DNA for RNA synthesis in vitro. The conversion of DNA radicals to alkali-labile sites protected the radiation-induced decrease in the template activity of DNA, while the adduct formation of misonidazole had no effect on it. (author)

  8. Structural ordering of disordered ligand-binding loops of biotin protein ligase into active conformations as a consequence of dehydration.

    Directory of Open Access Journals (Sweden)

    Vibha Gupta

    Full Text Available Mycobacterium tuberculosis (Mtb, a dreaded pathogen, has a unique cell envelope composed of high fatty acid content that plays a crucial role in its pathogenesis. Acetyl Coenzyme A Carboxylase (ACC, an important enzyme that catalyzes the first reaction of fatty acid biosynthesis, is biotinylated by biotin acetyl-CoA carboxylase ligase (BirA. The ligand-binding loops in all known apo BirAs to date are disordered and attain an ordered structure only after undergoing a conformational change upon ligand-binding. Here, we report that dehydration of Mtb-BirA crystals traps both the apo and active conformations in its asymmetric unit, and for the first time provides structural evidence of such transformation. Recombinant Mtb-BirA was crystallized at room temperature, and diffraction data was collected at 295 K as well as at 120 K. Transfer of crystals to paraffin and paratone-N oil (cryoprotectants prior to flash-freezing induced lattice shrinkage and enhancement in the resolution of the X-ray diffraction data. Intriguingly, the crystal lattice rearrangement due to shrinkage in the dehydrated Mtb-BirA crystals ensued structural order of otherwise flexible ligand-binding loops L4 and L8 in apo BirA. In addition, crystal dehydration resulted in a shift of approximately 3.5 A in the flexible loop L6, a proline-rich loop unique to Mtb complex as well as around the L11 region. The shift in loop L11 in the C-terminal domain on dehydration emulates the action responsible for the complex formation with its protein ligand biotin carboxyl carrier protein (BCCP domain of ACCA3. This is contrary to the involvement of loop L14 observed in Pyrococcus horikoshii BirA-BCCP complex. Another interesting feature that emerges from this dehydrated structure is that the two subunits A and B, though related by a noncrystallographic twofold symmetry, assemble into an asymmetric dimer representing the ligand-bound and ligand-free states of the protein, respectively. In

  9. Surface-enhanced Raman scattering active gold nanostructure fabricated by photochemical reaction of synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Yamaguchi, Akinobu, E-mail: yamaguti@lasti.u-hyogo.ac.jp [Laboratory of Advance Science and Technology for Industry, University of Hyogo, 3-1-2 Koto, Kamigori, Ako, Hyogo 678-1205 (Japan); Matsumoto, Takeshi [Laboratory of Advance Science and Technology for Industry, University of Hyogo, 3-1-2 Koto, Kamigori, Ako, Hyogo 678-1205 (Japan); Okada, Ikuo; Sakurai, Ikuya [Synchrotoron Radiation Research Center, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan); Utsumi, Yuichi [Laboratory of Advance Science and Technology for Industry, University of Hyogo, 3-1-2 Koto, Kamigori, Ako, Hyogo 678-1205 (Japan)

    2015-06-15

    The deposition of gold nanoparticles in an electroplating solution containing gold (I) trisodium disulphite under synchrotron X-ray radiation was investigated. The nanoparticles grew and aggregated into clusters with increasing radiation time. This behavior is explained by evaluating the effect of Derjaguin-Landau-Verweyand-Overbeek (DLVO) interactions combining repulsive electrostatic and attractive van der Waals forces on the particle deposition process. The surface-enhanced Raman scattering (SERS) of 4,4′ -bipyridine (4bpy) in aqueous solution was measured using gold nanoparticles immobilized on silicon substrates under systematically-varied X-ray exposure. The substrates provided an in situ SERS spectrum for 1 nM 4bpy. This demonstration creates new opportunities for chemical and environmental analyses through simple SERS measurements. - Highlights: • Gold nanoparticles were produced by photochemical reaction of synchrotron radiation. • The gold nanoparticles grew and aggregated into the higher-order nanostructure. • The behavior is qualitatively explained by analytical estimation. • The surface-enhanced Raman spectroscopy of 4,4′-bipyridine (4bpy) was demonstrated. • The substrate fabricated in a suitable condition provides in situ SERS for 1 nM 4bpy.

  10. Sr-doped nanowire modification of Ca-Si-based coatings for improved osteogenic activities and reduced inflammatory reactions

    Science.gov (United States)

    Li, Kai; Hu, Dandan; Xie, Youtao; Huang, Liping; Zheng, Xuebin

    2018-02-01

    Biomedical coatings for orthopedic implants should facilitate osseointegration and mitigate implant-induced inflammatory reactions. In our study, Ca-Si coatings with Sr-containing nanowire-like structures (NW-Sr-CS) were achieved via hydrothermal treatment. In order to identify the effect of nanowire-like topography and Sr dopant on the biological properties of Ca-Si-based coatings, the original Ca-Si coating, Ca-Si coatings modified with nanoplate (NP-CS) and similar nanowire-like structure (NW-CS) were fabricated as the control. Surface morphology, phase composition, surface area, zeta potential and ion release of these coatings were characterized. The in vitro osteogenic activities and immunomodulatory properties were evaluated with bone marrow stromal cells (BMSCs) and RAW 264.7 cells, a mouse macrophage cell line. Compared with the CS and NP-CS coatings, the NW-CS coating possessed a larger surface area and pore volume, beneficial protein adsorption, up-regulated the expression levels of integrin β1, Vinculin and focal adhesion kinase and promoted cell spreading. Furthermore, the NW-CS coating significantly enhanced the osteogenic differentiation and mineralization as indicated by the up-regulation of ALP activity, mineralized nodule formation and osteoblastogenesis-related gene expression. With the introduction of Sr, the NW-Sr-CS coatings exerted a greater effect on the BMSC proliferation rate, calcium sensitive receptor gene expression as well as PKC and ERK1/2 phosphorylation. In addition, the Sr-doped coatings significantly up-regulated the ratio of OPG/RANKL in the BMSCs. The NW-Sr-CS coatings could modulate the polarization of macrophages towards the wound-healing M2 phenotype, reduce the mRNA expression levels of pro-inflammatory cytokines (TNF-α, IL-1β, IL-6) and enhance anti-inflammatory cytokines (IL-1ra, IL-10). The Sr-doped nanowire modification may be a valuable approach to enhance osteogenic activities and reduce inflammatory reactions.

  11. Eco-friendly synthesis of silver nanoparticles using green algae (Caulerpa serrulata): reaction optimization, catalytic and antibacterial activities.

    Science.gov (United States)

    Aboelfetoh, Eman F; El-Shenody, Rania A; Ghobara, Mohamed M

    2017-07-01

    Stable colloidal silver nanoparticles (AgNPs) were synthesized using Caulerpa serrulata (green marine algae) aqueous extract as an efficient reducing and stabilizing agent. This method is considered to be a sustainable alternate to the more complicated chemical procedures. To achieve the optimization synthesis of AgNPs, several effects such as extract concentration, contact time, pH values, and temperature were examined. The synthesized AgNPs were characterized by UV-Vis spectroscopy, FT-IR, XRD, and HR-TEM. The synthesized AgNPs showed an intense surface plasmon resonance band at 412 nm at the optimal conditions (20% (v/v) extract and 95 °C). TEM reveal that higher extract concentration and higher temperature leading to the formation of spherical AgNPs with an average particle size of 10 ± 2 nm. The synthesized AgNPs showed excellent catalytic reduction activity of Congo red (CR) dye from aqueous solutions. The degradation percentage of CR with AgNPs accelerated by increasing either NaBH 4 concentration or catalytic dosage. The AgNPs synthesized at higher temperature (e.g., 10Ag-95) exhibited the highest catalytic activity. The reaction kinetics was found to be pseudo first order with respect to the dye concentration. Moreover, the AgNPs displayed antibacterial activity at lower concentration against Staphylococcus aureus, Pseudomonas aeruginosa, Shigella sp., Salmonella typhi, and Escherichia coli and may be a good alternative therapeutic approach. The outcomes of the current study confirmed that the synthesized AgNPs had an awesome guarantee for application in catalysis and wastewater treatment.

  12. The Synthesis and Electrocatalytic Activities of Molybdenum Sulfide for Hydrogen Evolution Reaction

    KAUST Repository

    Li, Zhengxing

    2014-07-01

    In the context of the future hydrogen economy, effective production of hydrogen (H2) from readily available and sustainable resources is of crucial importance. Hydrogen generation via water splitting by solar energy or electricity has attracted great attention in recent years. In comparison with photocatalytic water-splitting directly using solar light, which is ideal but the relevant technologies are not yet mature, electrolysis of water with catalyst is more practical at the current stage. The Pt-group noble metals are the most effective electrocatalysts for hydrogen evolution reaction (HER) from water, but their high costs limit their applications. Due to the earth-abundance and low price, MoS2 is expected to be a good alternative of the Pt-group metals for HER. Plenty of researches have been conducted for improving the HER activities of MoS2 by optimizing its synthesis method. However, it remains challenging to prepare MoS2 catalysts with high and controllable activity, and more investigations are still needed to better understand the structure-performance correlation in this system. In this thesis, we report a new strategy for fabricating MoS2 eletrocatalysts which gives rise to much improved HER performance and allows us to tune the electrocatalytic activity by varying the preparation conditions. Specifically, we sulfurized molybdenum oxide on the surface of a Ti foil electrode via a facile chemical vapor deposition (CVD) method, and directly used the electrode for HER testing. Depending on the CVD temperature, the MoO2-MoS2 nanocomposites show different HER activities. Under the optimal synthesis condition (400ºC), the resulting catalyst exhibited excellent HER activity: an onset potential (overpotential) of 0.095 V versus RHE and the Tafel slope of 40 mv/dec. Such a performance exceeds those of most reported MoS2 based HER electrocatalysts. We demonstrated that the CVD temperature has significant influence on the catalysts in crystallinity degree, particle

  13. Strength of figure-ground activity in monkey primary visual cortex predicts saccadic reaction time in a delayed detection task.

    Science.gov (United States)

    Supèr, Hans; Lamme, Victor A F

    2007-06-01

    When and where are decisions made? In the visual system a saccade, which is a fast shift of gaze toward a target in the visual scene, is the behavioral outcome of a decision. Current neurophysiological data and reaction time models show that saccadic reaction times are determined by a build-up of activity in motor-related structures, such as the frontal eye fields. These structures depend on the sensory evidence of the stimulus. Here we use a delayed figure-ground detection task to show that late modulated activity in the visual cortex (V1) predicts saccadic reaction time. This predictive activity is part of the process of figure-ground segregation and is specific for the saccade target location. These observations indicate that sensory signals are directly involved in the decision of when and where to look.

  14. Cationic Pd(II-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies

    Directory of Open Access Journals (Sweden)

    Takashi Nishikata

    2016-05-01

    Full Text Available Cationic palladium(II complexes have been found to be highly reactive towards aromatic C–H activation of arylureas at room temperature. A commercially available catalyst [Pd(MeCN4](BF42 or a nitrile-free cationic palladium(II complex generated in situ from the reaction of Pd(OAc2 and HBF4, effectively catalyzes C–H activation/cross-coupling reactions between aryl iodides, arylboronic acids and acrylates under milder conditions than those previously reported. The nature of the directing group was found to be critical for achieving room temperature conditions, with the urea moiety the most effective in promoting facile coupling reactions at an ortho C–H position. This methodology has been utilized in a streamlined and efficient synthesis of boscalid, an agent produced on the kiloton scale annually and used to control a range of plant pathogens in broadacre and horticultural crops. Mechanistic investigations led to a proposed catalytic cycle involving three steps: (1 C–H activation to generate a cationic palladacycle; (2 reaction of the cationic palladacycle with an aryl iodide, arylboronic acid or acrylate, and (3 regeneration of the active cationic palladium catalyst. The reaction between a cationic palladium(II complex and arylurea allowed the formation and isolation of the corresponding palladacycle intermediate, characterized by X-ray analysis. Roles of various additives in the stepwise process have also been studied.

  15. Birth Order and Participation in School Sports and Other Extracurricular Activities

    Science.gov (United States)

    Rees, Daniel I.; Lopez, Elizabeth; Averett, Susan L.; Argys, Laura M.

    2008-01-01

    Argys, L.M., Rees, D.I., Averett S.L., & Witoonchart, B. (2006). Birth order and risky adolescent behavior. "Economic Inquiry", 44(2), 215-233 demonstrated that a strong link exists between birth order and adolescent risky behavior. Using data on 10th graders from the National Education Longitudinal Study of 1988, we extend the work of Argys et…

  16. Improving biomass-derived carbon by activation with nitrogen and cobalt for supercapacitors and oxygen reduction reaction

    Science.gov (United States)

    Zhang, Man; Jin, Xin; Wang, Linan; Sun, Mengjia; Tang, Yang; Chen, Yongmei; Sun, Yanzhi; Yang, Xiaojin; Wan, Pingyu

    2017-07-01

    Biomass-derived carbon by activation with nitrogen and cobalt (denoted as NPACCo) was prepared by one-pot pyrolysis of pomelo peel with melamine, cobalt nitrate and potassium hydroxide, followed by acid leaching. NPACCo possesses high content of quaternary-N (2.5%) and pyridinic-N (1.7%), co-existences of amorphous and short-range ordered carbon, high specific surface area and pore structure with majority of micropores and small mesopores. As electrode material of supercapacitors, NPACCo exhibits high specific capacitance and good rate capability. At ultrahigh rate of 50 A g-1 (135 mA cm-2), the capacitance of NPACCo remains 246 F g-1, which is 6.3, 1.9 and 3.2 times as high as that of other three materials (PC, PAC and NPAC). The as-assembled symmetric supercapacitor of NPACCo delivers high energy density, high power density and excellent cycling stability. With respect to oxygen reduction reaction (ORR), NPACCo exhibits high onset potential (0.87 V), high half-wave potential (0.78 V), excellent methanol tolerance and low yield of H2O2. The ORR properties of NPACCo are comparable or superior to those of commercial Pt/C. This investigation of pomelo peel-based NPACCo would be valuable for development of both supercapacitor and ORR.

  17. Digallane with redox-active diimine ligand: dualism of electron-transfer reactions.

    Science.gov (United States)

    Fedushkin, Igor L; Skatova, Alexandra A; Dodonov, Vladimir A; Chudakova, Valentina A; Bazyakina, Natalia L; Piskunov, Alexander V; Demeshko, Serhiy V; Fukin, Georgy K

    2014-05-19

    The reactivity of digallane (dpp-Bian)Ga-Ga(dpp-Bian) (1), which consists of redox-active ligand 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-Bian), has been studied. The reaction of 1 with I2 proceeds via one-electron oxidation of each of two dpp-Bian ligands to a radical-anionic state and affords complex (dpp-Bian)IGa-GaI(dpp-Bian) (2). Dissolution of complex 2 in pyridine (Py) gives monomeric compound (dpp-Bian)GaI(Py) (3) as a result of a solvent-induced intramolecular electron transfer from the metal-metal bond to the dpp-Bian ligands. Treatment of compound 3 with B(C6F5)3 leads to removal of pyridine and restores compound 2. The reaction of compound 1 with 3,6-di-tert-butyl-ortho-benzoquinone (3,6-Q) proceeds with oxidation of all the redox-active centers in 1 (the Ga-Ga bond and two dpp-Bian dianions) and results in mononuclear catecholate (dpp-Bian)Ga(Cat) (4) (Cat = [3,6-Q](2-)). Treatment of 4 with AgBF4 gives a mixture of [(dpp-Bian)2Ag][BF4] (5) and (dpp-Bian)GaF(Cat) (6), which both consist of neutral dpp-Bian ligands. The reduction of benzylideneacetone (BA) with 1 generates the BA radical-anions, which dimerize, affording (dpp-Bian)Ga-(BA-BA)-Ga(dpp-Bian) (7). In this case the Ga-Ga bond remains unchanged. Within 10 min at 95 °C in solution compound 7 undergoes transformation to paramagnetic complex (dpp-Bian)Ga(BA-BA) (8) and metal-free compound C36H40N2 (9). The latter is a product of intramolecular addition of the C-H bond of one of the iPr groups to the C═N bond in dpp-Bian. Diamagnetic compounds 3, 5, 6, and 9 have been characterized by NMR spectroscopy, and paramagnetic complexes 2, 4, 7, and 8 by ESR spectroscopy. Molecular structures of 2-7 and 9 have been established by single-crystal X-ray analysis.

  18. Activation energies as the validity criterion of a model for complex reactions that can be in oscillatory states

    Directory of Open Access Journals (Sweden)

    Anić S.

    2007-01-01

    Full Text Available Modeling of any complex reaction system is a difficult task. If the system under examination can be in various oscillatory dynamic states, the apparent activation energies corresponding to different pathways may be of crucial importance for this purpose. In that case the activation energies can be determined by means of the main characteristics of an oscillatory process such as pre-oscillatory period, duration of the oscillatory period, the period from the beginning of the process to the end of the last oscillation, number of oscillations and others. All is illustrated on the Bray-Liebhafsky oscillatory reaction.

  19. Esterification of Glycerol with Acetic Acid over Highly Active and Stable Alumina-based Catalysts: A Reaction Kinetics Study

    OpenAIRE

    Rane, S. A.; Pudi, S. M.; Biswas, P.

    2016-01-01

    The catalytic activity of Cu- or Ni monometallic and Cu-Ni bimetallic (Cu/Ni ratio = 3, 1, 0.33) catalysts supported on γ-Al2O3 and SO42–/γ-Al2O3 catalysts were evaluated for esterification of glycerol. The reactions were performed in a batch reactor under reflux at standard reaction conditions: temperature 110 °C, atmospheric pressure, glycerol to acetic acid molar ratio 1:9, and catalyst loading 0.25 g. The best catalytic activity was observed over 2 M SO42–/γ-Al2O3 catalyst, which showed t...

  20. Friedel-Crafts reaction of benzyl fluorides: selective activation of C-F bonds as enabled by hydrogen bonding.

    Science.gov (United States)

    Champagne, Pier Alexandre; Benhassine, Yasmine; Desroches, Justine; Paquin, Jean-François

    2014-12-08

    A Friedel-Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1-diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C-F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C-F bonds in the presence of other benzylic leaving groups. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Application of Molecular Topology for the Prediction of Reaction Yields and Anti-Inflammatory Activity of Heterocyclic Amidine Derivatives

    Directory of Open Access Journals (Sweden)

    Ramón García-Domenech

    2011-02-01

    Full Text Available Topological-mathematical models based on multiple linear regression analyses have been built to predict the reaction yields and the anti-inflammatory activity of a set of heterocylic amidine derivatives, synthesized under environmental friendly conditions, using microwave irradiation. Two models with three variables each were selected. The models were validated by cross-validation and randomization tests. The final outcome demonstrates a good agreement between the predicted and experimental results, confirming the robustness of the method. These models also enabled the screening of virtual libraries for new amidine derivatives predicted to show higher values of reaction yields and anti-inflammatory activity.

  2. Invasion-wave-induced first-order phase transition in systems of active particles.

    Science.gov (United States)

    Ihle, Thomas

    2013-10-01

    An instability near the transition to collective motion of self-propelled particles is studied numerically by Enskog-like kinetic theory. While hydrodynamics breaks down, the kinetic approach leads to steep solitonlike waves. These supersonic waves show hysteresis and lead to an abrupt jump of the global order parameter if the noise level is changed. Thus they provide a mean-field mechanism to change the second-order character of the phase transition to first order. The shape of the wave is shown to follow a scaling law and to quantitatively agree with agent-based simulations.

  3. Roles of the redox-active disulfide and histidine residues forming a catalytic dyad in reactions catalyzed by 2-ketopropyl coenzyme M oxidoreductase/carboxylase.

    Science.gov (United States)

    Kofoed, Melissa A; Wampler, David A; Pandey, Arti S; Peters, John W; Ensign, Scott A

    2011-09-01

    NADPH:2-ketopropyl-coenzyme M oxidoreductase/carboxylase (2-KPCC), an atypical member of the disulfide oxidoreductase (DSOR) family of enzymes, catalyzes the reductive cleavage and carboxylation of 2-ketopropyl-coenzyme M [2-(2-ketopropylthio)ethanesulfonate; 2-KPC] to form acetoacetate and coenzyme M (CoM) in the bacterial pathway of propylene metabolism. Structural studies of 2-KPCC from Xanthobacter autotrophicus strain Py2 have revealed a distinctive active-site architecture that includes a putative catalytic triad consisting of two histidine residues that are hydrogen bonded to an ordered water molecule proposed to stabilize enolacetone formed from dithiol-mediated 2-KPC thioether bond cleavage. Site-directed mutants of 2-KPCC were constructed to test the tenets of the mechanism proposed from studies of the native enzyme. Mutagenesis of the interchange thiol of 2-KPCC (C82A) abolished all redox-dependent reactions of 2-KPCC (2-KPC carboxylation or protonation). The air-oxidized C82A mutant, as well as wild-type 2-KPCC, exhibited the characteristic charge transfer absorbance seen in site-directed variants of other DSOR enzymes but with a pK(a) value for C87 (8.8) four units higher (i.e., four orders of magnitude less acidic) than that for the flavin thiol of canonical DSOR enzymes. The same higher pK(a) value was observed in native 2-KPCC when the interchange thiol was alkylated by the CoM analog 2-bromoethanesulfonate. Mutagenesis of the flavin thiol (C87A) also resulted in an inactive enzyme for steady-state redox-dependent reactions, but this variant catalyzed a single-turnover reaction producing a 0.8:1 ratio of product to enzyme. Mutagenesis of the histidine proximal to the ordered water (H137A) led to nearly complete loss of redox-dependent 2-KPCC reactions, while mutagenesis of the distal histidine (H84A) reduced these activities by 58 to 76%. A redox-independent reaction of 2-KPCC (acetoacetate decarboxylation) was not decreased for any of the

  4. Influence of refreshment/activation cycles and temperature rise on the reaction rate of sodium hypochlorite with bovine dentine during ultrasonic activated irrigation

    NARCIS (Netherlands)

    Macedo, R.G.; Verhaagen, B.; Wesselink, P.R.; Versluis, Michel; van der Sluis, L.W.M.

    2014-01-01

    Aim To evaluate the effect of multiple refreshment/activation cycles and temperature on the reaction rate of sodium hypochlorite (NaOCl) with bovine dentine during ultrasonic activated irrigation (UAI) under laboratory conditions. Methodology The root canal walls of 24 standardized root canals in

  5. Radical-scavenging Activity of the Reaction Products of Isoeugenol with Thiol, Thiophenol, Mercaptothiazoline or Mercaptomethylimidazole Using the Induction Period Method

    Directory of Open Access Journals (Sweden)

    Seiichiro Fujisawa

    2007-08-01

    Full Text Available The reaction products in the presence of Lewis acid of isoeugenol (1 with ethanethiol, thiophenol, 2-mercaptothiazoline or 2-mercapto-1-methylimidazole (ISO-S1 – ISO-S-4 were obtained. The radical-scavenging activity of these compounds was investigated using the induction period method for polymerization of methyl methacrylate (MMA initiated by thermal decomposition of 2,2'-azobisisobutyronitrile (AIBN and benzoyl peroxide (BPO and monitored by differential scanning calorimetry (DSC. For BPO, the stoichiometric factor (number of free radicals trapped by one mole of antioxidant moiety, n declined in the order isoeugenol (1.8 > ISO-S-1 (1.6 > ISO-S-2 (1.2 > ISOS- 3 (0.9 > ISO-S-4 (0.3, whereas for AIBN, their n values were about 1, except for ISOS- 3 (0.6. The ratio of the rate constant of inhibition to that of propagation (kinh/kp for BPO declined in the order ISO-S-4 (56 > ISO-S-3 (15 > ISO-S-2 (11 >ISO-S-1 (9 > isoeugenol (8. Similarly, for AIBN the kinh/kp of the reaction products (33-57 was greater than that of isoeugenol (31. The reaction products of isoeugenol with a SH group showed greater inhibition rate constants (kinh than the parent compound isoeugenol.

  6. Reactions of OH radicals with 2-methyl-1-butyl, neopentyl and 1-hexyl nitrates. Structure-activity relationship for gas-phase reactions of OH with alkyl nitrates: An update

    Science.gov (United States)

    Bedjanian, Yuri; Morin, Julien; Romanias, Manolis N.

    2018-05-01

    The kinetics of the reactions 2-methyl-1-butyl (2M1BNT), neopentyl (NPTNT) and 1-hexyl nitrates (1HXNT) with OH radicals has been studied using a low pressure flow tube reactor combined with a quadrupole mass spectrometer. The rate constants of the title reactions were determined under pseudo-first order conditions from kinetics of OH consumption in excess of nitrates. The overall rate coefficients, k2M1BNT = 1.54 × 10-14 (T/298)4.85 exp (1463/T) (T = 278-538 K), kNPTNT = 1.39 × 10-14 (T/298)4.89 exp (1189/T) (T = 278-500 K) and k1HXNT = 2.23 × 10-13 (T/298)2.83 exp (853/T) cm3molecule-1s-1 (T = 306-538 K) (with conservative 15% uncertainty), were determined at a total pressure of 1 Torr of helium. The yield of trimethylacetaldehyde ((CH3)3CCHO), resulting from the abstraction by OH of an α-hydrogen atom in neopentyl nitrate, followed by α-substituted alkyl radical decomposition, was determined as 0.31 ± 0.06 at T = 298 K. The calculated tropospheric lifetimes of 2M1BNT, NPTNT and 1HXNT indicate that reaction of these nitrates with OH represents an important sink of these compounds in the atmosphere. Based on the available kinetic data, we have updated the structure-activity relationship (SAR) for reactions of alkyl nitrates with OH at T = 298 K. Good agreement (within 20%) is obtained between experimentally measured rate constants (total and that for H-atom abstraction from α carbon) and those calculated from SAR using new substituents factors for almost all the experimental data available.

  7. Acute effects of exercise and active video games on adults' reaction time and perceived exertion.

    Science.gov (United States)

    Guzmán, José F; López-García, Jesús

    2016-11-01

    The purpose of the present study was to examine the acute effects of resting, aerobic exercise practised alone, and aerobic exercise with active video games (AVG), on complex reaction time (CRT) and the post-exercise acute rate of perceived exertion (RPE) in young healthy adults. The experimental group was composed of 92 healthy young adults, 78 males and 13 females (age M = 21.9 ± 2.7 years) who completed two sessions, A and B. In session A, participants rode 30 min on an ergometer, while in session B they exercised for 30 min on an ergometer while playing an AVG on a Wii. The control group was composed of 30 young adults, 26 males and 4 females (age M = 21.4 ± 2.9 years) who rested for 30 min. In each session, a CRT task was performed before and after exercising or resting, and post-exercise global RPE was noted. Repeated measures general linear model (GLM) and Wilcoxon tests were performed. (1) Both aerobic exercise alone and aerobic exercise combined with AVG improved CRT, while resting did not; (2) aerobic exercise combined with AVG did not improve CRT more than aerobic exercise only; and (3) RPE was lower after aerobic exercise combined with AVG compared with aerobic exercise only. In young adults, exercise produces acute benefits on CRT, and practising exercise with AVG helps to decrease RPE.

  8. Investigation of activation cross-sections of alpha-induced nuclear reactions on natural cadmium

    Energy Technology Data Exchange (ETDEWEB)

    Khandaker, Mayeen Uddin [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Department of Physics, University of Malaya, 50603 Kuala Lumpur (Malaysia); Kim, Kwangsoo [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Lee, Manwoo [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Research Center, Dongnam Institute of Radiological and Medical Science, Busan 619-953 (Korea, Republic of); Kim, Guinyun, E-mail: gnkim@knu.ac.kr [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

    2014-08-15

    We measured production cross-sections of Sn, In, and Cd radionuclides from alpha-induced reactions on {sup nat}Cd from their respective threshold to 45 MeV by using a stacked-foil activation technique at the MC-50 cyclotron of the Korea Institute of Radiological and Medical Sciences. The results were compared with the earlier measurements as well as with the theoretical values obtained from the TENDL-2012 library based on the TALYS 1.4 code. Our measurements for the {sup 110,113g,117m}Sn, {sup 108m,108g,109g,110m,110g,111g,113m,114m,115m,116m,117m,117g}In, and {sup 111m,115g}Cd radionuclides in the energy region from the threshold energy to 45 MeV are in general good agreement with the other experimental data and calculated results. The integral yields for thick target were also deduced using the measured cross-sections and the stopping power of natural cadmium target and found in agreement with the directly measured yields available in the literature. The measured cross-sections find importance in various practical applications including nuclear medicine and improvement of nuclear model calculations.

  9. Postural vascular response in human skin: passive and active reactions to alteration of transmural pressure.

    Science.gov (United States)

    Jepsen, H; Gaehtgens, P

    1993-09-01

    Laser-Doppler (LD) fluxmetry was performed in the palmar finger skin of healthy subjects to study the mechanisms contributing to the postural vascular response. Local transmural pressure in the skin blood vessels of the region studied was altered for 1 min in two experimental series either by passive movement of the arm to different vertical hand positions relative to heart level or by application of external pressure (-120-180 mmHg) to the finger. Heart and respiratory rate, arterial blood pressure, and LD flux in the contralateral finger (kept at heart level) were measured. The measurements suggest a compound reaction of local (myogenic) and systemic (neurogenic) mechanisms: the local regulatory component appears as a graded active vascular response elicited by passive vessel distension or compression. A systemic component, associated with a single deep inspiration, is frequently observed during the actual movement of the arm. In addition, prolonged holding of the test hand in a given vertical position also elicits a delayed vascular response in the control hand at heart level, which may be generated by volume receptors in the intrathoracic low-pressure system.

  10. Synergetic pretreatment of waste activated sludge by hydrodynamic cavitation combined with Fenton reaction for enhanced dewatering.

    Science.gov (United States)

    Cai, Meiqiang; Hu, Jianqiang; Lian, Guanghu; Xiao, Ruiyang; Song, Zhijun; Jin, Micong; Dong, Chunying; Wang, Quanyuan; Luo, Dewen; Wei, Zongsu

    2018-04-01

    The dewatering of waste activated sludge by integrated hydrodynamic cavitation (HC) and Fenton reaction was explored in this study. We first investigated the effects of initial pH, sludge concentration, flow rate, and H 2 O 2 concentration on the sludge dewaterability represented by water content, capillary suction time and specific resistance to filtration. The results of dewatering tests showed that acidic pH and low sludge concentration were favorable to improve dewatering performance in the HC/Fenton system, whereas optimal flow rate and H 2 O 2 concentration applied depended on the system operation. To reveal the synergism of HC/Fenton treatment, a suite of analysis were implemented: three-dimensional excitation emission matrix (3-DEEM) spectra of extracellular polymeric substances (EPS) such as proteins and polysaccharides, zeta potential and particle size of sludge flocs, and SEM/TEM imaging of sludge morphology. The characterization results indicate a three-step mechanism, namely HC fracture of different EPS in sludge flocs, Fenton oxidation of the released EPS, and Fe(III) re-flocculation, that is responsible for the synergistically enhanced sludge dewatering. Results of current study provide a basis to improve our understanding on the sludge dewatering performance by HC/Fenton treatment and possible scale-up of the technology for use in wastewater treatment plants. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Measurements of activation reaction rate distributions on a mercury target bombarded with high-energy protons at AGS

    Energy Technology Data Exchange (ETDEWEB)

    Takada, Hiroshi; Kasugai, Yoshimi; Nakashima, Hiroshi; Ikeda, Yujiro [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Ino, Takashi; Kawai, Masayoshi [High Energy Accelerator Research Organization, Tsukuba, Ibaraki (Japan); Jerde, Eric; Glasgow, David [Oak Ridge National Laboratory, Oak Ridge, TN (United States)

    2000-02-01

    A neutronics experiment was carried out using a thick mercury target at the Alternating Gradient Synchrotron (AGS) facility of Brookhaven National Laboratory in a framework of the ASTE (AGS Spallation Target Experiment) collaboration. Reaction rate distributions around the target were measured by the activation technique at incident proton energies of 1.6, 12 and 24 GeV. Various activation detectors such as the {sup 115}In(n,n'){sup 115m}In, {sup 93}Nb(n,2n){sup 92m}Nb, and {sup 209}Bi(n,xn) reactions with threshold energies ranging from 0.3 to 70.5 MeV were employed to obtain the reaction rate data for estimating spallation source neutron characteristics of the mercury target. It was found from the measured {sup 115}In(n,n'){sup 115m}In reaction rate distribution that the number of leakage neutrons becomes maximum at about 11 cm from the top of hemisphere of the mercury target for the 1.6-GeV proton incidence and the peak position moves towards forward direction with increase of the incident proton energy. The similar result was observed in the reaction rate distributions of other activation detectors. The experimental procedures and a full set of experimental data in numerical form are summarized in this report. (author)

  12. Measurements of activation reaction rate distributions on a mercury target bombarded with high-energy protons at AGS

    International Nuclear Information System (INIS)

    Takada, Hiroshi; Kasugai, Yoshimi; Nakashima, Hiroshi; Ikeda, Yujiro; Jerde, Eric; Glasgow, David

    2000-02-01

    A neutronics experiment was carried out using a thick mercury target at the Alternating Gradient Synchrotron (AGS) facility of Brookhaven National Laboratory in a framework of the ASTE (AGS Spallation Target Experiment) collaboration. Reaction rate distributions around the target were measured by the activation technique at incident proton energies of 1.6, 12 and 24 GeV. Various activation detectors such as the 115 In(n,n') 115m In, 93 Nb(n,2n) 92m Nb, and 209 Bi(n,xn) reactions with threshold energies ranging from 0.3 to 70.5 MeV were employed to obtain the reaction rate data for estimating spallation source neutron characteristics of the mercury target. It was found from the measured 115 In(n,n') 115m In reaction rate distribution that the number of leakage neutrons becomes maximum at about 11 cm from the top of hemisphere of the mercury target for the 1.6-GeV proton incidence and the peak position moves towards forward direction with increase of the incident proton energy. The similar result was observed in the reaction rate distributions of other activation detectors. The experimental procedures and a full set of experimental data in numerical form are summarized in this report. (author)

  13. Optimization of the THP-1 activation assay to detect pharmaceuticals with potential to cause immune mediated drug reactions.

    Science.gov (United States)

    Corti, Daniele; Galbiati, Valentina; Gatti, Nicolò; Marinovich, Marina; Galli, Corrado L; Corsini, Emanuela

    2015-10-01

    Despite important impacts of systemic hypersensitivity induced by pharmaceuticals, for such endpoint no reliable preclinical approaches are available. We previously established an in vitro test to identify contact and respiratory allergens based on interleukin-8 (IL-8) production in THP-1 cells. Here, we challenged it for identification of pharmaceuticals associated with systemic hypersensitivity reactions, with the idea that drug sensitizers share common mechanisms of cell activation. Cells were exposed to drugs associated with systemic hypersensitivity reactions (streptozotocin, sulfamethoxazole, neomycin, probenecid, clonidine, procainamide, ofloxacin, methyl salicylate), while metformin was used as negative drug. Differently to chemicals, drugs tested were well tolerated, except clonidine and probenecid, with no signs of cytotoxicity up to 1-2mg/ml. THP-1 activation assay was adjusted, and conditions, that allow identification of all sensitizing drugs tested, were established. Next, using streptozotocin and selective inhibitors of PKC-β and p38 MAPK, two pathways involved in chemical allergen-induced cell activation, we tested the hypothesis that similar pathways were also involved in drug-induced IL-8 production and CD86 upregulation. Results indicated that drugs and chemical allergens share similar activation pathways. Finally, we made a structure-activity hypothesis related to hypersensitivity reactions, trying to individuate structural requisite that can be involved in immune mediated adverse reactions. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Study of activation cross-sections of deuteron induced reactions on rhodium up to 40 MeV

    International Nuclear Information System (INIS)

    Ditroi, F.; Tarkanyi, F.; Takacs, S.; Hermanne, A.; Yamazaki, H.; Baba, M.; Mohammadi, A.; Ignatyuk, A.V.

    2011-01-01

    Highlights: → Excitation function measurement of deuteron induced reactions on rhodium up to 40 MeV. → Model code calculations with EMPIRE, ALICE and TALYS. → Integral production yield calculation. → Thin layer activation (TLA) with the produced isotopes. - Abstract: In the frame of a systematic study of the activation cross-sections of deuteron induced nuclear reactions, excitation functions of the 103 Rh(d,x) 100,101,103 Pd, 100g,101m,101g,102m,102g Rh and 103g Ru reactions were determined up to 40 MeV. Cross-sections were measured with the activation method using a stacked foil irradiation technique. Excitation functions of the contributing reactions were calculated using the ALICE-IPPE, EMPIRE-II and TALYS codes. From the measured cross-section data integral production yields were calculated and compared with experimental integral yield data reported in the literature. From the measured cross-sections and previous data, activation curves were deduced to support thin layer activation (TLA) on rhodium and Rh containing alloys.

  15. Synthesis, reactions and biological activity of some new bis-heterocyclic ring compounds containing sulphur atom

    Science.gov (United States)

    2013-01-01

    Background The derivatives of thieno[2,3-b]thiophene belong to a significant category of heterocyclic compounds, which have shown a wide spectrum of medical and industrial application. Results A new building block with two electrophilic center of thieno[2,3-b]thiophene derivatives 2 has been reported by one-pot reaction of diketone derivative 1 with Br2/AcOH in excellent yield. A variety of heteroaromatics having bis(1H-imidazo[1,2a] benzimidazole), bis(1H-imidazo[1,2-b][1,2,4]triazole)-3-methyl-4-phenylthieno[2,3-b]thiophene derivatives, dioxazolo-, dithiazolo-, and 1H-imidazolo-3-methyl-4-phenylthieno[2,3-b]thiophene derivatives as well pyrrolo, thiazolo -3-methyl-4-phenylthieno[2,3-b]thiophene derivatives have been designed, synthesized, characterized, and evaluated for their biological activity. Compounds 3–9 showed good bioassay result. These new derivatives were evaluated for anti-cancer activity against PC-3 cell lines, in vitro antioxidant potential and β-glucuronidase and α-glucosidase inhibitory activities. Compound 3 (IC50 = 56.26 ± 3.18 μM) showed a potent DPPH radical scavenging antioxidant activity and found to be more active than standard N-acetylcystein (IC50 = 105.9 ± 1.1 μM). Compounds 8a (IC50 = 13.2 ± 0.34 μM) and 8b (IC50 = 14.1 ± 0.28 μM) found as potent inhibitor of α-glucusidase several fold more active than the standard acarbose (IC50 = 841 ± 1.73 μM). Most promising results were obtained in β-glucuronidase enzyme inhibition assay. Compounds 5 (IC50 = 0.13 ± 0.019 μM), 6 (IC50 = 19.9 ± 0.285 μM), 8a (IC50 = 1.2 ± 0.0785 μM) and 9 (IC50 = 0.003 ± 0.09 μM) showed a potent inhibition of β-glucuronidase. Compound 9 was found to be several hundred fold more active than standard D-Saccharic acid 1,4-lactone (IC50 = 45.75 ± 2.16 μM). Conclusions Synthesis, characterization, and in vitro biological activity of a series of

  16. Reaction invariant-based reduction of the activated sludge model ASM1 for batch applications

    DEFF Research Database (Denmark)

    Santa Cruz, Judith A.; Mussati, Sergio F.; Scenna, Nicolás J.

    2016-01-01

    In any system, there are some properties, quantities or relationships that remain unchanged despite the applied transformations (system invariants). For a batch reaction system with n linearly independent reactions and m components (n

  17. Ene-ene-yne Reactions: Activation Strain Analysis and Role of Aromaticity

    NARCIS (Netherlands)

    Fernandez, I.; Bickelhaupt, F.M.; Cossío, F.P.

    2014-01-01

    The trend in reactivity of the thermal cycloisomerization reactions of 1,3-hexadien-5-ynes, A=B-C=D-E≡F, were explored and analyzed by using density functional theory at the M06-2X/def2-TZVPP level. These reactions proceed through formally aromatic transition states to form a bent-allene

  18. Evaluation of prolidase activity and oxidative stress in patients with oral lichen planus and oral lichenoid contact reactions.

    Science.gov (United States)

    Batu, Şule; Ofluoğlu, Duygu; Ergun, Sertan; Warnakulasuriya, Saman; Uslu, Ezel; Güven, Yegane; Tanyeri, Hakkı

    2016-04-01

    The aim of this study was to evaluate prolidase activity and oxidative stress in patients with oral lichen planus (OLP) and oral lichenoid contact reactions (OLCR) using serum and salivary samples and to compare these biomarkers with each other as well as with a group of healthy subjects in order to be able to opine their role in the estimation of OLP and OLCR. Eighteen recently diagnosed patients with OLP, 32 patients with OLCR and 18 healthy controls with matched periodontal status were recruited to the study. Prolidase activity, lipid peroxidation product malondialdehyde (MDA), sialic acid (SA), and advanced oxidation protein products (AOPPs) levels in both serum and saliva were determined. Additionally, salivary flow rate and its buffering capacity were estimated. Statistical analyses were performed using the chi-square test, t-test, Mann-Whitney U-test, and Spearman's rho correlation coefficient. No statistically significant differences were observed between the study groups and the control group regarding to the basic characteristics and the periodontal status (P > 0.05). There were no statistically significant differences between OLP and OLCR groups regarding to the distribution of lesions' type, severity, and location (P > 0.05). No significant differences were found between the two study groups with regard to Prolidase activity, MDA, SA, and AOPPs (P ˃ 0.05), whereas statistically significant differences were found between the two study groups and the control group with regard to all evaluated parameters except of serum prolidase (P ˂ 0.01). Moderate correlation was found between salivary MDA and the OLP/OLCR lesion severity, whereas a weak correlation was observed between serum SA and the OLP/OLCR lesion severity (P ˂ 0.05). The findings of this study suggest an increased prolidase activity and oxidative stress and imbalance in the antioxidant defense system in biological fluids of patients with OLP and OLCR when compared with the healthy subjects

  19. Specific inflammatory response of Anemonia sulcata (Cnidaria) after bacterial injection causes tissue reaction and enzymatic activity alteration.

    Science.gov (United States)

    Trapani, M R; Parisi, M G; Parrinello, D; Sanfratello, M A; Benenati, G; Palla, F; Cammarata, M

    2016-03-01

    The evolution of multicellular organisms was marked by adaptations to protect against pathogens. The mechanisms for discriminating the ''self'' from ''non-self" have evolved into a long history of cellular and molecular strategies, from damage repair to the co-evolution of host-pathogen interactions. We investigated the inflammatory response in Anemonia sulcata (Cnidaria: Anthozoa) following injection of substances that varied in type and dimension, and observed clear, strong and specific reactions, especially after injection of Escherichia coli and Vibrio alginolyticus. Moreover, we analyzed enzymatic activity of protease, phosphatase and esterase, showing how the injection of different bacterial strains alters the expression of these enzymes and suggesting a correlation between the appearance of the inflammatory reaction and the modification of enzymatic activities. Our study shows for the first time, a specific reaction and enzymatic responses following injection of bacteria in a cnidarian. Copyright © 2016 Elsevier Inc. All rights reserved.

  20. Reduced order generalized integrators with phase compensation for three-phase active power filter

    DEFF Research Database (Denmark)

    Xie, Chuan; Li, Kai; Zhao, Xin

    2017-01-01

    -order generalized integrators (SOGIs) are utilized to achieve those objectives. However, it will increase the computational burden due to calculation of the multiple paralleled SOGIs. To overcome this issue, phase compensated reduced order generalized integrator (ROGI) is proposed in this paper. Compared...... paralleled ROGIs in positive and negative resonant frequencies. Moreover, the controller parameters are designed and optimized by means of Nyquist diagrams and sensitivity functions in z-domain for directly digital implementation. Finally, the laboratory tests of APF are performed to validate the feasibility...

  1. High-order harmonic generation in solid slabs beyond the single-active-electron approximation

    Science.gov (United States)

    Hansen, Kenneth K.; Deffge, Tobias; Bauer, Dieter

    2017-11-01

    High-harmonic generation by a laser-driven solid slab is simulated using time-dependent density functional theory. Multiple harmonic plateaus up to very high harmonic orders are observed already at surprisingly low field strengths. The full all-electron harmonic spectra are, in general, very different from those of any individual Kohn-Sham orbital. Freezing the Kohn-Sham potential instead is found to be a good approximation for the laser intensities and harmonic orders considered. The origins of the plateau cutoffs are explained in terms of band gaps that can be reached by Kohn-Sham electrons and holes moving through the band structure.

  2. An In Vitro Model for Studying Neutrophil Activation During Cardiopulmonary Bypass by Using a Polymerase Chain Reaction Thermocycler

    NARCIS (Netherlands)

    Tang, Min; Zhao, Xiao-Gang; Gu, Y. John; Chen, Chang-Zhi

    The accurate temperature control of a polymerase chain reaction (PCR) thermocycler was exploited in developing an in vitro model to study neutrophil activation during cardiopulmonary bypass. Neutrophils from 12 volunteers underwent temperature changes in a PCR thermocycler (37 degrees C for 30

  3. Synthesis and Biological Activity of Some 3,5-Diaryl-1-Benzothiazolopyrazoline Derivatives: Reaction of Chalcones with 2-Hyrazinobenzothiazoles

    Directory of Open Access Journals (Sweden)

    Vandana Sharma

    2009-01-01

    Full Text Available A series of 3,5-diaryl-1-benzothiazolopyrazoline derivatives were synthesized by the reaction of appropriately substituted chalcones and 2-hydrazinobenzothiazole in ethanol. The synthesized heterocycles have been characterized on the basis of their chemical properties and spectroscopic data. These compounds were tested for biological activity against a variety of test organisms.

  4. Synthesis and Biological Activity of Some 3, 5-Diarylisoxazoline Derivatives: Reaction of Substituted Chalcones with Hydroxylamine Hydrochloride

    Directory of Open Access Journals (Sweden)

    Vandana Sharma

    2010-01-01

    Full Text Available A series of 3-aryl-5-styrylisoxazoline/ 3,5-diarylisoxazoline derivatives were synthesized by the reaction of appropriately substituted chalcones and hydroxylamine hydrochloride in presence of alkali in ethanol. The synthesized heterocycles have been characterized on the basis of their chemical properties and spectroscopic data. These compounds were tested for biological activity against a variety of test organisms

  5. Reactions of 4-nitro-1,2,3-triazole with alkylating agents and compounds with activated multiple bonds

    Energy Technology Data Exchange (ETDEWEB)

    Vereshchagin, L.I.; Kuznetsova, N.I.; Kirillova, L.P.; Shcherbakov, V.V.; Sukhanov, G.T.; Gareev, G.A.

    1987-01-01

    When 4-nitro-1,2,3-triazole is alkylated, a mixture of N1- and N2-isomers is formed, with the latter usually predominating. The same behavior is also observed in addition reactions of 4-nitrotriazole to activated multiple bonds.

  6. Particle size dependence on oxygen reduction reaction activity of electrodeposited TaOx catalysts in acidic media

    KAUST Repository

    Seo, J.

    2013-11-13

    The size dependence of the oxygen reduction reaction activity was studied for TaOx nanoparticles electrodeposited on carbon black for application to polymer electrolyte fuel cells (PEFCs). Compared with a commercial Ta2O5 material, the ultrafine oxide nanoparticles exhibited a distinctively high onset potential different from that of the bulky oxide particles.

  7. New ways enhancing the vital activity of plants in order to increase crop yields and to suppress radionuclide accumulation

    International Nuclear Information System (INIS)

    Goncharova, N. V; Zebrakova, I. V.; Matsko, V. P.; Kislushko, P. M.

    1994-01-01

    After Chernobyl nuclear accident it has become very important to seek new ways of enhancing the vital activity of plants in order to increase crop yields and to suppress radionuclide accumulation. It is found that by optimizing the vital activity processes in plants, is possible to reduce radionuclide uptake. A great number of biologically active compounds have been tested, which increased the disease resistance of plants and simultaneously activated the physiological and biochemical processes that control the transport of micro- and macroelements (radionuclide included) and their 'soil-root-stem-leaf' redistribution. (author)

  8. Activation cross-sections of deuteron induced nuclear reactions on neodymium up to 50 MeV

    International Nuclear Information System (INIS)

    Tárkányi, F.; Takács, S.; Ditrói, F.; Hermanne, A.; Yamazaki, H.; Baba, M.; Mohammadi, A.; Ignatyuk, A.V.

    2014-01-01

    Highlights: • Experimental excitation function of deuteron induced reactions on natural Nd. • Model code calculations with EMPIRE-D, ALICE-D and TALYS (TENDL-2012). • Physical yield calculation and comparison. • Discussion of medical and industrial applications. - Abstract: In the frame of a systematic study of activation cross sections of deuteron induced nuclear reactions on rare earths, the reactions on neodymium for production of therapeutic radionuclides were measured for the first time. The excitation functions of the nat Nd(d,x) 151,150,149,148m,148g,146,144,143 Pm, 149,147,139m Nd, 142 Pr and 139g Ce nuclear reactions were assessed by using the stacked foil activation technique and high resolution γ-spectrometry. The experimental excitation functions were compared to the theoretical predictions calculated with the modified model codes ALICE-IPPE-D and EMPIRE-II-D and with the data in the TENDL-2012 library based on latest version of the TALYS code. The application of the data in the field of medical isotope production and nuclear reaction theory is discussed

  9. Promotional effect of phosphorus doping on the activity of the Fe-N/C catalyst for the oxygen reduction reaction

    DEFF Research Database (Denmark)

    Hu, Yang; Zhu, Jianbin; Lv, Qing

    2015-01-01

    Cost-effective, active and stable electrocatalysts for the oxygen reduction reaction (ORR) are highly desirable for the wide-spread adoption of technologies such as fuel cells and metal-air batteries. Among the already reported non-precious metal catalysts, carbon-supported transition metal...... to that for the undoped Fe-N/C catalyst. The activity and durability of the catalysts are demonstrated in direct methanol fuel cells....

  10. The Reduction Reaction of Dissolved Oxygen in Water by Hydrazine over Platinum Catalyst Supported on Activated Carbon Fiber

    Energy Technology Data Exchange (ETDEWEB)

    Park, K.K.; Moon, J.S. [Korea Electric Power Research Institute, Taejon (Korea)

    1999-07-01

    The reduction reaction of dissolved oxygen (DO) by hydrazine was investigated on activated carbon fiber (ACF) and Pt/ACF catalysts using a batch reactor with an external circulating loop. The ACF itself showed catalytic activity and this was further improved by supporting platinum on ACF. The catalytic role platinum is ascribed to its acceleration of hydrazine decomposition, based on electric potential and current measurements as well as the kinetic study. (author). 15 refs., 13 figs.

  11. Kinetics, Reaction Orders, Rate Laws, and Their Relation to Mechanisms: A Hands-On Introduction for High School Students Using Portable Spectrophotometry

    Science.gov (United States)

    Carraher, Jack M.; Curry, Sarah M.; Tessonnier, Jean-Philippe

    2016-01-01

    Teaching complex chemistry concepts such as kinetics using inquiry-based learning techniques can be challenging in a high school classroom setting. Access to expensive laboratory equipment such as spectrometers is typically limited and most reaction kinetics experiments have been designed for advanced placement (AP) or first-year undergraduate…

  12. Electrocatalytic Activity of Carbonized Nanostructured Polyanilines for Oxidation Reactions: Sensing of Nitrite Ions and Ascorbic Acid

    International Nuclear Information System (INIS)

    Micić, Darko; Šljukić, Biljana; Zujovic, Zoran; Travas-Sejdic, Jadranka; Ćirić-Marjanović, Gordana

    2014-01-01

    Highlights: • Carbonized PANIs prepared from various nanostructured PANI precursors • Electroanalytical performances of carbonized PANIs evaluated using voltammetry • Study of carbonized PANIs physico-chemical properties related to electroactivity • The lowest over-potential for NO 2 − oxidation at c-PANI (+0.87 V vs. SCE) • The lowest over-potential for ascorbic acid oxidation at both c-PANI and c-PANI-SSA - Abstract: A comparative study of the electrocatalytic activity of nitrogen-containing carbon nanomaterials, prepared by the carbonization of nanostructured polyaniline (PANI) salts, for the electrooxidation reactions is presented. Nanostructured PANI salts were synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in an aqueous solution in the presence of 5-sulfosalicylic acid (PANI-SSA), 3,5-dinitrosalicylic acid (PANI-DNSA) as well as without added acid (PANI), and subsequently carbonized to c-PANI-SSA, c-PANI-DNSA and c-PANI, respectively. Glassy carbon tip was modified with nanostructured c-PANIs and used for the investigation of sensing of nitrite and ascorbic acid in aqueous solutions as model analytes by linear sweep voltammetry. All three types of the investigated c-PANIs gave excellent response to the nitrite ions and ascorbic acid electrooxidation. The lowest peak potential for nitrite ion oxidation exhibited c-PANI (+0.87 V vs. SCE), and for ascorbic acid oxidation both c-PANI and c-PANI-SSA (ca. + 0.13 V vs. SCE). Electrochemical data were correlated with structural and textural data obtained by Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, elemental and nitrogen sorption analysis

  13. Transition metal catalyzed carbonylation reactions carbonylative activation of C-X bonds

    CERN Document Server

    Beller, Matthias

    2014-01-01

    This book provides students and researchers in organic synthesis with a detailed discussion of carbonylation from the basics through to applications. It discusses the past, present and future of carbonylation reactions.

  14. New dinuclear palladium(II) complexes: Studies of the nucleophilic substitution reactions, DNA/BSA interactions and cytotoxic activity.

    Science.gov (United States)

    Ćoćić, Dušan; Jovanović, Snežana; Nišavić, Marija; Baskić, Dejan; Todorović, Danijela; Popović, Suzana; Bugarčić, Živadin D; Petrović, Biljana

    2017-10-01

    Six new dinuclear Pd(II) complexes, [{Pd(2,2'-bipy)Cl} 2 (μ-pz)](ClO 4 ) 2 (Pd1), [{Pd(dach)Cl} 2 (μ-pz)](ClO 4 ) 2 (Pd2), [{Pd(en)Cl} 2 (μ-pz)](ClO 4 ) 2 (Pd3), [{Pd(2,2'-bipy)Cl} 2 (μ-4,4'-bipy)](ClO 4 ) 2 (Pd4), [{Pd(dach)Cl} 2 (μ-4,4'-bipy)](ClO 4 ) 2 (Pd5) and [{Pd(en)Cl} 2 (μ-4,4'-bipy)](ClO 4 ) 2 (Pd6) (where 2,2'-bipy=2,2'-bipyridyl, pz=pyrazine, dach=trans-(±)-1,2-diaminocyclohexane, en=ethylenediamine, 4,4'-bipy=4,4'-bipyridyl) have been synthesized and characterized by elemental microanalysis, IR, 1 H NMR and MALDI-TOF mass spectrometry. The pK a values of corresponding diaqua complexes were determined by spectrophotometric pH titration. Substitution reactions with thiourea (Tu), l-methionine (l-Met), l-cysteine (l-Cys), l-histidine (l-His) and guanosine-5'-monophosphate (5'-GMP) were studied under the pseudo-first order conditions at pH7.2. Reactions of Pd1 with Tu, l-Met and l-Cys were followed by decomposition of complexes, while structures of dinuclear complexes were preserved during the substitution with nitrogen donors. Interactions with calf-thymus DNA (CT-DNA) were followed by absorption spectroscopy and fluorescence quenching measurements. All complexes can bind to CT-DNA exhibiting high intrinsic binding constants (K b =10 4 -10 5 M -1 ). Competitive studies with ethidium bromide (EB) have shown that complexes can displace DNA-bound EB. High values of binding constants towards bovine serum albumin protein (BSA) indicate good binding affinity. Finally, all complexes showed moderate to high cytotoxic activity against HeLa (human cervical epithelial carcinoma cell lines) and MDA-MB-231 (human breast epithelial carcinoma cell lines) tumor cell lines inducing apoptotic type cell death, whereas normal fibroblasts were significantly less sensitive. The impact on cell cycle of these cells was distinctive, where Pd4, Pd5 and Pd6 showed the most prominent effect arresting MDA-MB-231 (human lung fibroblast cell lines) cell in G1/S phase of cell

  15. Using Activity Theory to Design Constructivist Online Learning Environments for Higher Order Thinking: A Retrospective Analysis

    Directory of Open Access Journals (Sweden)

    Dirk Morrison

    2003-10-01

    Full Text Available Abstract. This paper examined a particular online learning activity, embedded within a computer supported collaborative learning (CSCL environment incorporated as part of the larger context of participation in a unique national agricultural leadership development program. Process outcomes such as a high level of collaboration and active peer facilitation as well as demonstration by participants of a variety of holistic thinking skills were observed via a transcript analysis of online interactions. This led to speculations that the particular design features embedded within the context of the online collaborative issues analysis project (IAP, were thought to clearly reflect a constructivist approach. Methods to confirm this included evaluating the learning activity in light of nine characteristics of an authentic task in CSCL environments, and using activity theory as a conceptual framework with which to further examine the extent to which the IAP reflected the values and principles of a constructivist online learning environment.

  16. Ordered micro/macro porous K-OMS-2/SiO2 nanocatalysts: Facile synthesis, low cost and high catalytic activity for diesel soot combustion

    Science.gov (United States)

    Yu, Xuehua; Zhao, Zhen; Wei, Yuechang; Liu, Jian

    2017-04-01

    A series of novel oxide catalysts, which contain three-dimensionally ordered macroporous (3DOM) and microporous structure, were firstly designed and successfully synthesized by simple method. In the as-prepared catalysts, 3DOM SiO2 is used as support and microporous K-OMS-2 oxide nanoparticles are supported on the wall of SiO2. 3DOM K-OMS-2/SiO2 oxide catalysts were firstly used in soot particle oxidation reaction and they show very high catalytic activities. The high activities of K-OMS-2/SiO2 oxide catalysts can be assigned to three possible reasons: macroporous effect of 3DOM structure for improving contact between soot and catalyst, microporous effect of K-OMS-2 for adsorption of small gas molecules and interaction of K and Mn for activation of gas molecules. The catalytic activities of catalysts are comparable to or even higher than noble metal catalyst in the medium and high temperature range. For example, the T50 of K-OMS-2/SiO2-50, 328 °C, is much lower than those of Pt/Al2O3 and 3DOM Au/LaFeO3, 464 and 356 °C,respectively. Moreover, catalysts exhibited high catalytic stability. It is attributed to that the K+ ions are introduced into the microporous structure of OMS-2 and stabilized in the catalytic reaction. Meanwhile, the K+ ions play an important role in templating and stabilizing the tunneled framework of OMS-2.

  17. Optimal control of a Cope rearrangement by coupling the reaction path to a dissipative bath or a second active mode

    International Nuclear Information System (INIS)

    Chenel, A.; Meier, C.; Dive, G.; Desouter-Lecomte, M.

    2015-01-01

    We compare the strategy found by the optimal control theory in a complex molecular system according to the active subspace coupled to the field. The model is the isomerization during a Cope rearrangement of Thiele’s ester that is the most stable dimer obtained by the dimerization of methyl-cyclopentadienenylcarboxylate. The crudest partitioning consists in retaining in the active space only the reaction coordinate, coupled to a dissipative bath of harmonic oscillators which are not coupled to the field. The control then fights against dissipation by accelerating the passage across the transition region which is very wide and flat in a Cope reaction. This mechanism has been observed in our previous simulations [Chenel et al., J. Phys. Chem. A 116, 11273 (2012)]. We compare here, the response of the control field when the reaction path is coupled to a second active mode. Constraints on the integrated intensity and on the maximum amplitude of the fields are imposed limiting the control landscape. Then, optimum field from one-dimensional simulation cannot provide a very high yield. Better guess fields based on the two-dimensional model allow the control to exploit different mechanisms providing a high control yield. By coupling the reaction surface to a bath, we confirm the link between the robustness of the field against dissipation and the time spent in the delocalized states above the transition barrier

  18. 75 FR 10526 - In the Matter of Mr. Lawrence E. Grimm; Order Prohibiting Involvement in NRC-Licensed Activities

    Science.gov (United States)

    2010-03-08

    ... NUCLEAR REGULATORY COMMISSION [IA-09-068; NRC-2010-0085] In the Matter of Mr. Lawrence E. Grimm; Order Prohibiting Involvement in NRC-Licensed Activities I Mr. Lawrence E. Grimm was employed as a... NIST-Boulder facility in accordance with the conditions specified therein. Mr. Grimm was listed on the...

  19. Laplace-transformed multi-reference second-order perturbation theories in the atomic and active molecular orbital basis

    NARCIS (Netherlands)

    Helmich-Paris, B.; Knecht, Stefan

    2017-01-01

    In the present article, we show how to formulate the partially contracted n-electron valence second-order perturbation theory (NEVPT2) energies in the atomic and active molecular orbital basis by employing the Laplace transformation of orbital-energy denominators (OEDs). As atomic-orbital (AO) basis

  20. Activation cross-sections of deuteron induced nuclear reactions on manganese up to 40 MeV

    International Nuclear Information System (INIS)

    Ditroi, F.; Tarkanyi, F.; Takacs, S.; Hermanne, A.; Yamazaki, H.; Baba, M.; Mohammadi, A.; Ignatyuk, A.V.

    2011-01-01

    In the frame of a systematic study on activation cross-sections of deuteron induced reactions experimental excitation functions on 55 Mn were measured with the activation method using the stacked foil irradiation technique up to 40 MeV. By using high resolution γ-ray spectrometry, cross-section data for the production of 56,54,52 Mn and 51 Cr were determined. Comparison with the earlier published data and with the results predicted by the ALICE-IPPE and EMPIRE-II theoretical codes - improved for more reliable calculations for d-induced reactions - and with data in the TENDL 2010 libraries are also included. Thick target yields were calculated from a fit to our experimental excitation curves and implications for practical applications in industrial (Thin Layer Activation) accelerator technology are discussed.

  1. Odors generated from the Maillard reaction affect autonomic nervous activity and decrease blood pressure through the olfactory system.

    Science.gov (United States)

    Zhou, Lanxi; Ohata, Motoko; Owashi, Chisato; Nagai, Katsuya; Yokoyama, Issei; Arihara, Keizo

    2018-02-01

    Systolic blood pressure (SBP) of rats decreases significantly following exposure to the odor generated from the Maillard reaction of protein digests with xylose. This study identified active odorants that affect blood pressure and demonstrated the mechanism of action. Among the four potent odorants that contribute most to the odor of the Maillard reaction sample, 2,5-dimethyl-4-hydroxy-3(2H)-furanone (DMHF) and 5-methyl-2-pyrazinemethanol (MPM) decreased SBP significantly. The earliest decrease in blood pressure was observed 5 min after exposure to DMHF. Application of zinc sulfate to the nasal cavity eliminated the effect. Furthermore, gastric vagal (parasympathetic) nerve activity was elevated and renal sympathetic nerve activity was lowered after exposure to DMHF. It is indicated that DMHF affects blood pressure through the olfactory system, and the mechanism for the effect of DMHF on blood pressure involves the autonomic nervous system. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  2. Study of photo-activated electron transfer reactions in the first excited singlet state by picosecond and nanosecond laser spectroscopy

    International Nuclear Information System (INIS)

    Doizi, Denis

    1983-01-01

    Picosecond laser spectroscopy has been used to study two photo-activated electron transfer reactions: - a bimolecular electron transfer reaction between a sensitizer, DODCI, and an electron acceptor, methylviologen. The two radical ions created with an electron transfer efficiency γ ≅ 0.07 have been identified in picosecond and nanosecond laser absorption spectroscopy by adding selective solutes such as para-benzoquinone (an electron acceptor) or L(+) ascorbic acid (an electron donor). - an intramolecular electron transfer reaction in a triad molecule consisting of a tetra-aryl-porphyrin covalently linked to both a carotenoid and a quinone. The photoinduced charge separation occurs within 30 ps and leads, with a yield of 25 pc, to the formation of a zwitterion whose half-life is 2.5 μs. The experimental results obtained in these two studies show an effective decrease in the recombination rate of the two radical ions created in the encounter pair. (author) [fr

  3. Extension of activation cross section data of deuteron induced nuclear reactions on rhodium up to 50 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Hermanne, A. [Cyclotron Laboratory, Vrije Universiteit Brussel, Brussels (Belgium); Tárkányi, F.; Takács, S.; Ditrói, F. [Institute of Nuclear Research of the Hungarian Academy of Sciences, Debrecen (Hungary)

    2015-11-01

    In the frame of the systematical study of light ion induced nuclear reactions activation cross sections for deuteron induced reactions on monoisotopic {sup 103}Rh were extended to 50 MeV incident energy. Excitation functions were measured in the 49.8–36.6 MeV energy range for the {sup 103}Rh(d,xn){sup 100,101}Pd, {sup 103}Rh(d,pxn){sup 99m,99g,100,101m,101g,102m,102g}Rh and {sup 103}Rh(d,x){sup 97,103}Ru reactions by using the stacked foil irradiation technique and off-line high resolution γ-ray spectrometry. The experimental results are compared to our previous results and to the theoretical predictions in the TENDL-2014 library (TALYS 1.6 code).

  4. Antioxidant activity and sensory characteristics of Maillard reaction products derived from different peptide fractions of soybean meal hydrolysate.

    Science.gov (United States)

    Yu, Min; He, Shudong; Tang, Mingming; Zhang, Zuoyong; Zhu, Yongsheng; Sun, Hanju

    2018-03-15

    Four peptide fractions PF1 (>5;kDa), PF2 (3-5;kDa), PF3 (1-3;kDa), PF4 (Maillard reaction products (MRPF1, MRPF2, MRPF3 and MRPF4) were evaluated, respectively. Peptides with low molecular weight showed higher contribution to the changes of pH, colour and browning intensity during Maillard reaction. The DPPH radical-scavenging activity of PF4 was significantly improved after Maillard reaction. Aroma volatiles and PLSR analysis suggested MRPF3 had the best sensory characteristics with higher contents of umami amino acids and lower of bitter amino acids, therefore it could be deduced that the umami and meaty characteristics were correlated with the peptides of 1-3;kDa. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Synthesis and characterization of Ag@Cu nano/microstructure ordered arrays as SERS-active substrates

    Science.gov (United States)

    Zhang, Pinhua; Cui, Guangliang; Xiao, Chuanhai; Zhang, Mingzhe; Chen, Li; Shi, Changmin

    2016-06-01

    We fabricated an Ag decorated Cu (Ag@Cu) nano/microstructure ordered array by facile template-free 2D electrodeposition combined with a galvanic reduction method for SERS applications. The Cu nano/microstructure ordered arrays were first synthesized by a 2D electrodeposition method, then Ag nanocubes were decorated on the arrays by galvanic reduction without any capping agent. The pollution-free surface and edge-to-face heterostructure of Ag nanocubes and Cu nano/microstructure arrays provide the powerful field-enhancements for SERS performance. The results verified that the Ag@Cu nano/microstructure ordered arrays have excellent activity for 4-Mercaptopyridine, and the sensitivity limit is as low as 10-8 M. Therefore, this facile route provides a useful platform for the fabrication of a SERS substrate based on nano/microstructure ordered arrays.

  6. Verification of dosimetry cross sections above 10 MeV based on measurement of activation reaction rates in fission neutron field

    International Nuclear Information System (INIS)

    Odano, Naoteru; Miura, Toshimasa; Yamaji, Akio.

    1996-01-01

    To validate the dosimetry cross sections in fast neutron energy range, activation reaction rates were measured for 5 types of dosimetry cross sections which have sensitivity in the energy rage above 10 MeV utilizing JRR-4 reactor of JAERI. The measured reaction rates were compared with the calculations reaction rates by a continuous energy monte carlo code MVP. The calculated reaction rates were based on two dosimetry files, JENDL Dosimetry File and IRDF-90.2. (author)

  7. Supervisors' attitudes and skills for active listening with regard to working conditions and psychological stress reactions among subordinate workers.

    Science.gov (United States)

    Mineyama, Sachiko; Tsutsumi, Akizumi; Takao, Soshi; Nishiuchi, Kyoko; Kawakami, Norito

    2007-03-01

    We investigated whether supervisors' listening attitudes and skills were related to working conditions and psychological stress reactions among their subordinates. The subjects included 41 male supervisors and their immediate subordinates (n=203). The supervisors completed a short version of the Active Listening Attitude Scale (ALAS) consisting of two subscales: Listening Attitude and Listening Skill for Active Listening. The subordinates rated working conditions and their psychological stress reactions using selected scales of the Job Content Questionnaire and the Brief Job Stress Questionnaire. Those subordinates who worked under supervisors with a higher score of Listening Attitude and Listening Skill reported a more favorable psychological stress reaction than those who worked under supervisors with a lower score of Listening Attitude and Listening Skill. Those subordinates who worked under supervisors with a higher score of Listening Skill reported higher worksite support than those who worked under supervisors with a lower score of Listening Skill. Those subordinates who worked under supervisors with a higher score of Listening Attitude reported higher job control than those who worked under supervisors with a lower score of Listening Attitude. A supervisor's listening attitude and skill appeared to affect psychological stress reactions predominantly among male subordinates than among female subordinates. Psychological stress reactions were lower among younger subordinates who worked under supervisors with high listening skill, while no statistically difference was observed among older subordinates. These findings suggest that a supervisor's listening attitude and skill have an effect on working conditions and psychological stress reactions among subordinates and that the effects vary according to the subordinates' sex and age.

  8. Brain activity related to serial cognitive performance resembles circuitry of higher order motor control

    NARCIS (Netherlands)

    de Jong, BM; vanZomeren, AH; Willemsen, ATM; Paans, AMJ

    Differences between two states of cerebral activation were studied in eight subjects by positron emission tomography (PET) of regional cerebral blood flow (rCBF) and subsequent statistical parameter mapping. Subjects had to respond to a row of numbers presented on tape. In one condition they had to

  9. New ways in enhancing the vital activity of plants in order to increase crop yields and to suppress radionuclide accumulation

    International Nuclear Information System (INIS)

    Goncharova, N.; Kislushko, P.; Znebrakova, I.; Matsko, V.

    1994-01-01

    Soil contamination with long-lived isotopes as a result of Chernobyl nuclear accident necessitates substantially of crop raising procedures. It is found that by optimizing the vital activity processes in plants, is possible to reduce radionuclide uptake. In particular application of Fisher's mineral mix in concentration of 100, 200, 300, g/m 2 to soil decreased the 137 Cs accumulation in green material of lupine (Lupinus luteus L.) 1.1:1.3 and 2.2 times respectively and 1.2:1.1 and 1.1 times, respectively in green material of barley (Hordeum Vulgaris L.). The decrease of 90 Sr accumulation in green material of barley and lupine was similar. On the other hand chloroplasts isolated from showed higher activities of photochemical reactions and the light-dependent ATP enzyme. During the whole growing period of such plants the chlorophyll and protein concentration per wet unit mass were higher than those in control, therefore the high vital activity period in the former case was substantially extended. It has been also found that application of biologically active compounds and trace elements enhances photosynthetic and production activities of plants, reducing level radionuclide accumulation in the harvest. It is found that application of protectants and growth regulators to rye crops also reduces 137 Cs accumulation in green material in booting and earing phases. This finding suggests that this compounds activate the photosynthetic apparatus, reducing level radionuclide accumulation. (author)

  10. A new type of active actinide target for studying fission and (n,xn) reactions

    International Nuclear Information System (INIS)

    Belier, G.; Aupiais, J.; Varignon, C.; Vayre, S.

    2011-01-01

    A new type of active target for the detection of fission of actinides has been developed, it is based on α spectrometry through liquid scintillation. The target uses the liquid-liquid extraction in order to mix the actinide with the liquid organic scintillator. The actinide to be detected is inside the detector itself which maximises the efficiency of the detector. The use of an organic scintillator allows the identification of the particles emitted. Indeed, the time delay for the transfer of the energy deposited in the solvent towards the scintillating molecules depends on the type of the energy deposits: instantaneous fluorescence is obtained for direct excitation while delayed fluorescence is obtained for energy deposits through ionization. By discriminating the different slow and quick components of the photomultiplier signal it is then possible to identify the particle: beta, alpha or fission products. This target has been tested with Cf 252 irradiated with 18 MeV neutrons, the experimental data show different peaks corresponding to alpha decay (97%), spontaneous fission (3%), beta decay and recoil protons due to neutron emissions. (A.C.)

  11. Advanced foil activation techniques for the measurement of within-pin distributions of the 63Cu(n,γ)64Cu reaction rate in nuclear fuel

    International Nuclear Information System (INIS)

    Macku, K.; Jatuff, F.; Murphy, M.F.; Joneja, O.P.; Bischofberger, R.; Chawla, R.

    2006-01-01

    Different foil activation techniques have been used for measuring spatial distributions of the 63 Cu(n,γ) 64 Cu reaction within two pins of a SVEA-96 Optima2 boiling water reactor fuel assembly, at the critical facility PROTEUS. This reaction is of interest because its 1/v cross-section gives it a good representation of the 235 U fission rate. Initially, radial capture rate profiles were measured with mechanically punched copper foils. More detailed profiles were then determined by using a 0.2 mm copper wire spiral (∼200 μm resolution), as well as 5-, 10-, and 20-ring UV-lithography, electroplating, and molding (UV-LIGA) foils (up to a 100 μm resolution). For azimuthal measurements, apart from manually cut activation foils (into 8 sectors), 8- and 12-sector LIGA foils were used. The highly versatile LIGA foils have the additional advantage of being very easily separated into individual pieces after irradiation without the use of punches or other cutting tools. In order to account for the invasive character of the foil activation techniques, corrections to account for sample perturbations and for self-shielding effects were determined via simplified Monte Carlo (MCNP4C) modeling of the experimental setup. The final results from the various measurements of 63 Cu(n,γ) 64 Cu within-pin distributions have been compared with MCNP computations employing a detailed model of the full SVEA Optima2 fuel assembly

  12. Effect of dual task activity on reaction time in males and females.

    Science.gov (United States)

    Kaur, Manjinder; Nagpal, Sangeeta; Singh, Harpreet; Suhalka, M L

    2014-01-01

    The present study was designed to compare the auditory and visual reaction time on an Audiovisual Reaction Time Machine with the concomitant use of mobile phones in 52 women and 30 men in the age group of 18-40 years. Males showed significantly (p multitasking, in hand held (24.38% & 18.70% respectively) and hands free modes (36.40% & 18.40% respectively) of the use of cell phone. VRT increased non significantly during multitasking in both the groups. However, the multitasking per se has detrimental effect on the reaction times in both the groups studied. Hence, it should best be avoided in crucial and high attention demanding tasks like driving.

  13. Fluorescent Carbon Dots Derived from Maillard Reaction Products: Their Properties, Biodistribution, Cytotoxicity, and Antioxidant Activity.

    Science.gov (United States)

    Li, Dongmei; Na, Xiaokang; Wang, Haitao; Xie, Yisha; Cong, Shuang; Song, Yukun; Xu, Xianbing; Zhu, Bei-Wei; Tan, Mingqian

    2018-02-14

    Food-borne nanoparticles have received great attention because of their unique physicochemical properties and potential health risk. In this study, carbon dots (CDs) formed during one of the most important chemical reactions in the food processing field, the Maillard reaction from the model system including glucose and lysine, were investigated. The CDs purified from Maillard reaction products emitted a strong blue fluorescence under ultraviolet light with a fluorescent quantum yield of 16.30%. In addition, they were roughly spherical, with sizes of around 4.3 nm, and mainly composed of carbon, oxygen, hydrogen, and nitrogen. Their surface groups such as hydroxyl, amino, and carboxyl groups were found to possibly enable CDs to scavenge DPPH and hydroxyl radicals. Furthermore, the cytotoxicity assessment of CDs showed that they could readily enter HepG2 cells while causing negligible cell death at low concentration. However, high CDs concentrations were highly cytotoxic and led to cell death via interference of the glycolytic pathway.

  14. Endoscopy and homogeneous-heterogeneous reactions in MHD radiative peristaltic activity of Ree-Eyring fluid

    Science.gov (United States)

    Hayat, Tasawar; Akram, Javaria; Alsaedi, Ahmed; Zahir, Hina

    2018-03-01

    Endoscopic and homogeneous-heterogeneous reactions in MHD peristalsis of Ree-Eyring fluid are addressed. Mathematical modeling and analysis have been performed by utilizing cylindrical coordinates. Nonlinear thermal radiation is present. Impact of slip boundary conditions on temperature and velocity on outer tube are taken into consideration. Lubrication approach is employed. The nonlinear system is executed numerically for solutions of velocity, temperature and concentration. Graphical results are obtained to predict physical interpretation of various embedded parameters. It is noted that homogeneous and heterogeneous reactions affect the concentration alternatively. Moreover Brinkman number rises the temperature and heat transfer coefficient whereas thermal slip drops temperature and heat transfer rate.

  15. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1980-February 14, 1981

    International Nuclear Information System (INIS)

    1981-02-01

    The stereochemistry of high energy 18 F, /sup 34m/Cl, and 76 Br substitution reactions involving enantiomeric molecules in the gas and condensed phase is studied. The gas to condensed state transition in halogen high energy chemistry, involving chlorine, bromine, and iodine activated by the (n,γ) and (I.T.) processes in halomethanes, saturated and unsaturated hydrocarbons is being investigated in more detail. Special attention is given to defining the nature of the enhancement yields in the condensed phase. High energy halogen reactions in liquid and frozen aqueous solutions of organic and biomolecular solutes are studied in an attempt to learn more about these reactions. The applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Special attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as indicators of solute-solute interactions in liquid and frozen aqueous solutions of halogenated bases and nucleosides are being developed. Experiments are designed to explain the mechanisms of the radioprotection offered biomolecular solutes trapped within the frozen ice lattice. Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular solutes in liquid and frozen aqueous solutions are studied. The high energy reactions of iodine with the isomers of pentene have been studied in low pressure gaseous systems employing additives and rare gas moderators and liquid systems. Reactivity of excited complex formation and structural effects of electrophilic iodine attack on the pi-bond systems are studied

  16. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1980-February 14, 1981

    Energy Technology Data Exchange (ETDEWEB)

    1981-02-01

    The stereochemistry of high energy /sup 18/F, /sup 34m/Cl, and /sup 76/Br substitution reactions involving enantiomeric molecules in the gas and condensed phase is studied. The gas to condensed state transition in halogen high energy chemistry, involving chlorine, bromine, and iodine activated by the (n,..gamma..) and (I.T.) processes in halomethanes, saturated and unsaturated hydrocarbons is being investigated in more detail. Special attention is given to defining the nature of the enhancement yields in the condensed phase. High energy halogen reactions in liquid and frozen aqueous solutions of organic and biomolecular solutes are studied in an attempt to learn more about these reactions. The applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Special attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as indicators of solute-solute interactions in liquid and frozen aqueous solutions of halogenated bases and nucleosides are being developed. Experiments are designed to explain the mechanisms of the radioprotection offered biomolecular solutes trapped within the frozen ice lattice. Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular solutes in liquid and frozen aqueous solutions are studied. The high energy reactions of iodine with the isomers of pentene have been studied in low pressure gaseous systems employing additives and rare gas moderators and liquid systems. Reactivity of excited complex formation and structural effects of electrophilic iodine attack on the pi-bond systems are studied.

  17. Optimised formation of blue Maillard reaction products of xylose and glycine model systems and associated antioxidant activity.

    Science.gov (United States)

    Yin, Zi; Sun, Qian; Zhang, Xi; Jing, Hao

    2014-05-01

    A blue colour can be formed in the xylose (Xyl) and glycine (Gly) Maillard reaction (MR) model system. However, there are fewer studies on the reaction conditions for the blue Maillard reaction products (MRPs). The objective of this study is to investigate characteristic colour formation and antioxidant activities in four different MR model systems and to determine the optimum reaction conditions for the blue colour formation in a Xyl-Gly MR model system, using the random centroid optimisation program. The blue colour with an absorbance peak at 630 nm appeared before browning in the Xyl-Gly MR model system, while no blue colour formation but only browning was observed in the xylose-alanine, xylose-aspartic acid and glucose-glycine MR model systems. The Xyl-Gly MR model system also showed higher antioxidant activity than the other three model systems. The optimum conditions for blue colour formation were as follows: xylose and glycine ratio 1:0.16 (M:M), 0.20 mol L⁻¹ NaHCO₃, 406.1 mL L⁻¹ ethanol, initial pH 8.63, 33.7°C for 22.06 h, which gave a much brighter blue colour and a higher peak at 630 nm. A characteristic blue colour could be formed in the Xyl-Gly MR model system and the optimum conditions for the blue colour formation were proposed and confirmed. © 2013 Society of Chemical Industry.

  18. Virtual Instrument for Determining Rate Constant of Second-Order Reaction by pX Based on LabVIEW 8.0.

    Science.gov (United States)

    Meng, Hu; Li, Jiang-Yuan; Tang, Yong-Huai

    2009-01-01

    The virtual instrument system based on LabVIEW 8.0 for ion analyzer which can measure and analyze ion concentrations in solution is developed and comprises homemade conditioning circuit, data acquiring board, and computer. It can calibrate slope, temperature, and positioning automatically. When applied to determine the reaction rate constant by pX, it achieved live acquiring, real-time displaying, automatical processing of testing data, generating the report of results; and other functions. This method simplifies the experimental operation greatly, avoids complicated procedures of manual processing data and personal error, and improves veracity and repeatability of the experiment results.

  19. Active control on high-order coherence and statistic characterization on random phase fluctuation of two classical point sources.

    Science.gov (United States)

    Hong, Peilong; Li, Liming; Liu, Jianji; Zhang, Guoquan

    2016-03-29

    Young's double-slit or two-beam interference is of fundamental importance to understand various interference effects, in which the stationary phase difference between two beams plays the key role in the first-order coherence. Different from the case of first-order coherence, in the high-order optical coherence the statistic behavior of the optical phase will play the key role. In this article, by employing a fundamental interfering configuration with two classical point sources, we showed that the high- order optical coherence between two classical point sources can be actively designed by controlling the statistic behavior of the relative phase difference between two point sources. Synchronous position Nth-order subwavelength interference with an effective wavelength of λ/M was demonstrated, in which λ is the wavelength of point sources and M is an integer not larger than N. Interestingly, we found that the synchronous position Nth-order interference fringe fingerprints the statistic trace of random phase fluctuation of two classical point sources, therefore, it provides an effective way to characterize the statistic properties of phase fluctuation for incoherent light sources.

  20. Cross-section studies of relativistic deuteron reactions on copper by activation method

    Czech Academy of Sciences Publication Activity Database

    Suchopár, Martin; Wagner, Vladimír; Svoboda, Ondřej; Vrzalová, Jitka; Chudoba, Petr; Kugler, Andrej; Adam, Jindřich; Závorka, L.; Baldine, A.; Furman, W.; Kadykov, M. G.; Khushvaktov, J.; Solnyshkin, A. A.; Tsoupko-Sitnikov, V. V.; Tyutyunnikov, S. I.

    2015-01-01

    Roč. 344, FEB (2015), s. 63-69 ISSN 0168-583X R&D Projects: GA MŠk LG14004 Institutional support: RVO:61389005 Keywords : relativistic deuteron reactions * cross-sections * copper Subject RIV: BG - Nuclear , Atomic and Molecular Physics, Colliders Impact factor: 1.389, year: 2015

  1. Influence of limestone powder on the reaction kinetics and mechanical properties of sodium carbonate activated slag

    NARCIS (Netherlands)

    Yuan, B.; Yu, Q.; Brouwers, H.J.H.

    2016-01-01

    The effects of limestone powder (LP) on the performance of Portland cement based composites have been extensively studied, considering that LP not only acts as nuclei sites, but that it is also chemically involved in the hydration process, which improves the reaction degree at the early age. In high

  2. Patterns of adverse drug reaction signals in NAFDAC Pharmacovigilance activities from September to November, 2014.

    Science.gov (United States)

    Awodele, Olufunsho; Ibrahim, Ali; Orhii, Paul

    2016-03-16

    Adverse drug reaction signals are reported information on possible causal relationships between an adverse event and a drug. The National Pharmacovigilance Centre (NPC) in Nigeria has over 3,000 reported adverse drug reaction cases which have been adequately entered into the ADR data bank. Data mining of ADR reports from September to November, 2014 were carried out in this present study with the intention to describe the pattern of ADRs and generate possible signals. A total of about 100 reported cases with arrays of adverse drug reactions were reported between September and November, 2014 and the data were analyzed using SPSS version 17. Efavirenz/Tenofovir/Lamivudine combination was the highest reported drugs (24.2%) while efavirenz alone was reported in 8 times (8.8%) and HIV (63.3%) was the highest reported indication of drug use. Efavirenz caused central nervous system adverse reactions as revealed in the ADRs analyses. Zidovudine/Lamivudine/Nevirapine combination in concomitant use with Cotrimoxazole were reported 8 times with generalized maculopapular rashes on the trunk with some area of hyper pigmentation with intense itching documented twice and big/swollen rashes all over the faces. Zidovudine was also reported four times to cause severe anaemia. More surveillance is advocated so as to ascertain the consistency of the observed ADRs and thereafter establish appropriate signals.

  3. Activation cross-section measurements of some proton induced reactions on Ni, Co and Mo for proton activation analysis (PAA) purposes

    International Nuclear Information System (INIS)

    Alharbi, A.A.; Alzahrani, J.; Azzam, A.; Nuclear Research Center, Cairo

    2011-01-01

    The experimental proton induced reaction cross sections on some elements of the Havar alloy were measured using the activation method and the well established stacked-foil technique combined with high resolution gamma-ray spectroscopy. They included the reactions nat Ni(p,x) 57 Ni, nat Co(p,x) 58(m+g) Co and nat Mo(p,x) 94g,95g,96(m+g) Tc, the aim being to obtain reliable data in the proton energy range up to 26 MeV for some important reactions to be used in the proton activation analysis of steel or other alloys. Irradiations were performed using the CS-30 Cyclotron at KFSH and RC, Riyadh, Saudi Arabia. The activity measurements were carried out in PNU laboratories, Riyadh, Saudi Arabia. The experimental excitation functions for the investigated reactions were constructed and compared with the performed computed theoretical nuclear model calculations using two different codes: ALICE-IPPE and TALYS. A comparison between our measured cross-section values and the available published data is also presented, with a view to checking the consistency of the reported experimental work from various laboratories.

  4. High-flux white neutron source based on p(35)-Be reactions for activation experiments at NPI

    Czech Academy of Sciences Publication Activity Database

    Štefánik, Milan; Bém, Pavel; Götz, Miloslav; Katovsky, K.; Majerle, Mitja; Novák, Jan; Šimečková, Eva

    2014-01-01

    Roč. 104, NOV (2014), s. 306-309 ISSN 0969-806X. [1st International Conference on Dosimetry and its Applications (ICDA). Prague, 23.6.2013-28.6.2013] R&D Projects: GA MŠk(XE) LM2011019 Institutional support: RVO:61389005 Keywords : neutron generator * accelerator * dosimetry foils activation method * neutron spectrometry * Gamma-spectrometry * reaction rate Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 1.380, year: 2014

  5. Rhodium(III)-catalyzed three-component reaction of imines, alkynes, and aldehydes through C-H activation.

    Science.gov (United States)

    Huang, Ji-Rong; Song, Qiang; Zhu, Yu-Qin; Qin, Liu; Qian, Zhi-Yong; Dong, Lin

    2014-12-15

    An efficient rhodium(III)-catalyzed tandem three-component reaction of imines, alkynes and aldehydes through CH activation has been developed. High stereo- and regioselectivity, as well as good yields were obtained in most cases. The simple and atom-economical approach offers a broad scope of substrates, providing polycyclic skeletons with potential biological properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Peripheral Blood Leukocytes and Serum Nested Polymerase Chain Reaction Are Complementary Methods for Monitoring Active Cytomegalovirus Infection in Transplant Patients

    Directory of Open Access Journals (Sweden)

    PD Andrade

    2013-01-01

    Full Text Available BACKGROUND: Human cytomegalovirus is an important cause of morbidity and mortality in immunocompromised patients. Qualitative polymerase chain reaction (PCR has proven to be a sensitive and effective technique in defining active cytomegalovirus infection, in addition to having low cost and being a useful test for situations in which there is no need for quantification. Real-time PCR has the advantage of quantification; however, the high cost of this methodology makes it impractical for routine use.

  7. Catalytic Activity of μ-Carbido-Dimeric Iron(IV) Octapropylporphyrazinate in the 3,5,7,2',4'-Pentahydroxyflavone Oxidation Reaction with tert-Butyl Hydroperoxide

    Science.gov (United States)

    Tyurin, D. V.; Zaitseva, S. V.; Kudrik, E. V.

    2018-05-01

    It is found for the first time that μ-carbido-dimeric iron(IV) octapropylporphyrazinate displays catalytic activity in the oxidation reaction of natural flavonol morin with tert-butyl hydroperoxide, with the catalyst being stable under conditions of the reaction. The kinetics of this reaction are studied. It is shown the reaction proceeds via tentative formation of a complex between the catalyst and the oxidant, followed by O‒O bond homolytic cleavage. The kinetics of the reaction is described in the coordinates of the Michaelis-Menten equation. A linear dependence of the apparent reaction rate constant on the concentration of the catalyst is observed, testifying to its participation in the limiting reaction step. The equilibrium constants and rates of interaction are found. A mechanism is proposed for the reaction on the basis of the experimental data.

  8. ANALYSIS OF MARKETING TOOLS AND ACTIVITIES WITHIN EDUCATIONAL SERVICES ORGANIZATIONS, IN ORDER TO INCREASE THEIR EFFICIENCY

    Directory of Open Access Journals (Sweden)

    Barbu Andreea Mihaela

    2012-07-01

    Full Text Available Romanian education, which is an important pillar for human resource forming process and the basis for economic development, suffered a lot of changes in the last decades. The main factors that have influenced the undergraduate and university training programs are the political and social-cultural ones. Educational services organizations are facing various challenges as: creating and maintaining a good institutional image, managing all types of resources efficiently, motivating the academic personnel, satisfying the community needs and supporting the public policy. The marketing tools and activities help these entities to improve the educational programs and adapt them to the individual needs of the clients, to keep under control the production costs, which are limited by the small public budget and to perform and promote these services efficiently, leading to an increased organizational performance. The paper begins by presenting the current situation of higher education in Romania, underlining the fierce competition among the universities, the increased market potential and the financing sources. It continues by mentioning the advantages of strategic marketing planning for universities, as superior results and effectiveness, improved decision making and multiple benefits for the people involved. The paper reveals also the characteristics of segmenting and positioning on higher education market and the specific of marketing mix. Thereby, educational product is more easily adapted to customer needs when it is designed in collaboration with existing and future students, their parents, with other universities in the field or even with graduates. Students themselves can contribute to the increase the quality of their education. Price may be a factor of choice when future student chooses to pursue a university course, especially in those situations where the price does not include only the payment of annual fees for education. Distribution takes into

  9. Diels-Alder reactions in confined spaces: the influence of catalyst structure and the nature of active sites for the retro-Diels-Alder reaction.

    Science.gov (United States)

    Cantín, Ángel; Gomez, M Victoria; de la Hoz, Antonio

    2016-01-01

    Diels-Alder cycloaddition between cyclopentadiene and p -benzoquinone has been studied in the confined space of a pure silica zeolite Beta and the impact on reaction rate due to the concentration effect within the pore and diffusion limitations are discussed. Introduction of Lewis or Brønsted acid sites on the walls of the zeolite strongly increases the reaction rate. However, contrary to what occurs with mesoporous molecular sieves (MCM-41), Beta zeolite does not catalyse the retro-Diels-Alder reaction, resulting in a highly selective catalyst for the cycloaddition reaction.

  10. Type of activity and order of experimental conditions affect noise annoyance by identifiable and unidentifiable transportation noise.

    Science.gov (United States)

    White, Kim; Bronkhorst, Adelbert W; Meeter, Martijn

    2018-04-01

    Previous studies have shown that identifiability of sound sources influence noise annoyance levels. The aim of the present experiment was to additionally study the effects of actively performing a task versus a less active pastime on noise annoyance. This was done by asking participants to perform a task (task condition) or read a magazine of their choice (no-task condition), while listening to identifiable and unidentifiable samples of transportation noise at varying sound exposure levels (55-85 ASEL). Annoyance was higher for identifiable samples (recordings) than for unidentifiable transformed samples (with equal spectral energy and envelope). Although there was no main effect of activity type on noise annoyance, for the transformed samples, an interaction was found between activity type and sound exposure levels: annoyance started lower in the no-task condition, but rose more steeply with ascending exposure levels than was the case during task performance (large effect). When assessing order effects, it was found that annoyance was higher when the task condition came first, especially for lower sound exposure levels (large effects). It is therefore concluded that the type of activity and the condition order do influence noise annoyance but in interaction with exposure levels, the type of noise and habituation.

  11. In Vitro Activity of Isavuconazole and Comparators against Clinical Isolates of the Mucorales Order.

    Science.gov (United States)

    Arendrup, Maiken Cavling; Jensen, Rasmus Hare; Meletiadis, Joseph

    2015-12-01

    The in vitro activity of isavuconazole against Mucorales isolates measured by EUCAST E.Def 9.2 and CLSI M38-A2 methodologies was investigated in comparison with those of amphotericin B, posaconazole, and voriconazole. Seventy-two isolates were included: 12 of Lichtheimia corymbifera, 5 of Lichtheimia ramosa, 5 of group I and 9 of group II of Mucor circinelloides, 9 of Rhizomucor pusillus, 26 of Rhizopus microsporus, and 6 of Rhizopus oryzae. Species identification was confirmed by internal transcribed spacer (ITS) sequencing. EUCAST MICs were read on day 1 (EUCAST-d1) and day 2 (EUCAST-d2), and CLSI MICs were read on day 2 (CLSI-d2). Isavuconazole MIC50s (range) (mg/liter) by EUCAST-d1, CLSI-d2, and EUCAST-d2 were 1 (0.125 to 16), 1 (0.125 to 2), and 4 (0.5 to >16), respectively, across all isolates. The similar values for comparator drugs were as follows: posaconazole, 0.25 (≤ 0.03 to >16), 0.25 (0.06 to >16), and 1 (0.06 to >16); amphotericin, 0.06 (≤ 0.03 to 0.5), 0.06 (≤ 0.03 to 0.25), and 0.125 (≤ 0.03 to 1); voriconazole, 16 (2 to >16), 8 (1 to >16), and >16 (8 to >16), respectively. Isavuconazole activity varied by species: Lichtheimia corymbifera, 1 (0.5 to 2), 1 (1 to 2), and 2 (1 to 4); Lichtheimia ramosa, 0.25 (0.125 to 0.5), 1 (0.5 to 2), and 2 (0.5 to 4); Rhizomucor pusillus, 0.5 (0.5 to 1), 1 (0.125 to 1), and 2 (1 to 2); Rhizopus microsporus, 1 (0.5 to 4), 0.5 (0.125 to 1), and 4 (1 to 8); and Rhizopus oryzae, 1 (0.5 to 4), 1 (0.125 to 2), and 4 (0.5 to 8), respectively, were more susceptible than Mucor circinelloides: group I, 8 (4 to 8), 4 (2 to 4), and 16 (2 to 16), respectively, and group II, 8 (1 to 16), 8 (1 to 8), and 16 (4 to >16), respectively. This was also observed for posaconazole. The essential agreement was best between EUCAST-d1 and CLSI-d2 (75% to 83%). Isavuconazole displayed in vitro activity against Mucorales isolates with the exception of Mucor circinelloides. The MICs were in general 1 to 3 steps higher than those for

  12. Solidification of highly active fission products by a thermite reaction. Pt. 1

    International Nuclear Information System (INIS)

    Rudolph, G.; Hild, W.

    1976-07-01

    To solidify high-level fission products a process was developed according to which a high-melting ceramic product is obtained as a solidification matrix in a thermite reaction. With a constant content of fission product oxides reaction mixtures consisting of 35 to 55 wt.% of manganese dioxide, 24 to 32 wt.% of aluminum shot and 17 to 36 wt.% of sand give suitable products. In the thermite reactiom some components contained in the reactic mixture volatilize partly by evaporation (alkali oxides, manganese oxide, and others) and partly by the formation of volatile oxides having lower valencies (silicon and aluminum oxide). The smoke generated can be easily collected in filters made of glass wool fibers. (orig./HR) [de

  13. Nuclear Energy Gradients for Internally Contracted Complete Active Space Second-Order Perturbation Theory: Multistate Extensions.

    Science.gov (United States)

    Vlaisavljevich, Bess; Shiozaki, Toru

    2016-08-09

    We report the development of the theory and computer program for analytical nuclear energy gradients for (extended) multistate complete active space perturbation theory (CASPT2) with full internal contraction. The vertical shifts are also considered in this work. This is an extension of the fully internally contracted CASPT2 nuclear gradient program recently developed for a state-specific variant by us [MacLeod and Shiozaki, J. Chem. Phys. 2015, 142, 051103]; in this extension, the so-called λ equation is solved to account for the variation of the multistate CASPT2 energies with respect to the change in the amplitudes obtained in the preceding state-specific CASPT2 calculations, and the Z vector equations are modified accordingly. The program is parallelized using the MPI3 remote memory access protocol that allows us to perform efficient one-sided communication. The optimized geometries of the ground and excited states of a copper corrole and benzophenone are presented as numerical examples. The code is publicly available under the GNU General Public License.

  14. LASSO-ligand activity by surface similarity order: a new tool for ligand based virtual screening.

    Science.gov (United States)

    Reid, Darryl; Sadjad, Bashir S; Zsoldos, Zsolt; Simon, Aniko

    2008-01-01

    Virtual Ligand Screening (VLS) has become an integral part of the drug discovery process for many pharmaceutical companies. Ligand similarity searches provide a very powerful method of screening large databases of ligands to identify possible hits. If these hits belong to new chemotypes the method is deemed even more successful. eHiTS LASSO uses a new interacting surface point types (ISPT) molecular descriptor that is generated from the 3D structure of the ligand, but unlike most 3D descriptors it is conformation independent. Combined with a neural network machine learning technique, LASSO screens molecular databases at an ultra fast speed of 1 million structures in under 1 min on a standard PC. The results obtained from eHiTS LASSO trained on relatively small training sets of just 2, 4 or 8 actives are presented using the diverse directory of useful decoys (DUD) dataset. It is shown that over a wide range of receptor families, eHiTS LASSO is consistently able to enrich screened databases and provides scaffold hopping ability.

  15. LASSO—ligand activity by surface similarity order: a new tool for ligand based virtual screening

    Science.gov (United States)

    Reid, Darryl; Sadjad, Bashir S.; Zsoldos, Zsolt; Simon, Aniko

    2008-06-01

    Virtual Ligand Screening (VLS) has become an integral part of the drug discovery process for many pharmaceutical companies. Ligand similarity searches provide a very powerful method of screening large databases of ligands to identify possible hits. If these hits belong to new chemotypes the method is deemed even more successful. eHiTS LASSO uses a new interacting surface point types (ISPT) molecular descriptor that is generated from the 3D structure of the ligand, but unlike most 3D descriptors it is conformation independent. Combined with a neural network machine learning technique, LASSO screens molecular databases at an ultra fast speed of 1 million structures in under 1 min on a standard PC. The results obtained from eHiTS LASSO trained on relatively small training sets of just 2, 4 or 8 actives are presented using the diverse directory of useful decoys (DUD) dataset. It is shown that over a wide range of receptor families, eHiTS LASSO is consistently able to enrich screened databases and provides scaffold hopping ability.

  16. Effects of slip-induced changes in ankle movement on muscle activity and ground reaction forces during running acceleration

    DEFF Research Database (Denmark)

    Ketabi, Shahin; Kersting, Uwe G.

    2013-01-01

    Ground contact in running is always linked to a minimum amount of slipping, e.g., during the early contact phase when horizontal forces are high compared to vertical forces. Studies have shown altered muscular activation when expecting slips [2-4]. It is not known what the mechanical effect of su...... of such slip episodes are on joint loading or performance. The aim of the present study was to examine the effect of changes in ankle movement on ankle joint loading, muscle activity, and ground reaction forces during linear acceleration....

  17. Interactions of nitrite with catalase: Enzyme activity and reaction kinetics studies.

    Science.gov (United States)

    Krych-Madej, Justyna; Gebicka, Lidia

    2017-06-01

    Catalase, a heme enzyme, which catalyzes decomposition of hydrogen peroxide to water and molecular oxygen, is one of the main enzymes of the antioxidant defense system of the cell. Nitrite, used as a food preservative has long been regarded as a harmful compound due to its ability to form carcinogenic nitrosamines. Recently, much evidence has been presented that nitrite plays a protective role as a nitric oxide donor under hypoxic conditions. In this work the effect of nitrite on the catalytic reactions of catalase was studied. Catalase was inhibited by nitrite, and this process was pH-dependent. IC 50 values varied from about 1μM at pH5.0 to about 150μM of nitrite at pH7.4. The presence of chloride significantly enhanced nitrite-induced catalase inhibition, in agreement with earlier observations. The kinetics of the reactions of nitrite with ferric catalase, its redox intermediate, Compound I, and catalase inactive form, Compound II, was also studied. Possible mechanisms of nitrite-induced catalase inhibition are analyzed and the biological consequences of the reactions of catalase with nitrite are discussed. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Direct Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Austern, N. [University of Pittsburgh, Pittsburgh, PA (United States)

    1963-01-15

    In order to give a unified presentation of one point of view, these lectures are devoted only to a detailed development of the standard theories of direct reactions, starting from basic principles. Discussion is given of the present status of the theories, of the techniques used for practical calculation, and of possible future developments. The direct interaction (DI) aspects of a reaction are those which involve only a few of the many degrees of freedom of a nucleus. In fact the minimum number of degrees of freedom which must be involved in a reaction are those required to describe the initial and final channels, and DI studies typically consider these degrees of freedom and no others. Because of this simplicity DI theories may be worked out in painstaking detail. DI processes concern only part of the wave function for a problem. The other part involves complicated excitations of many degrees of freedom, and gives the compound nucleus (CN) effects. While it is extremely interesting to learn how to separate DI and CN effects in an orderly manner, if they are both present in a reaction, no suitable method has yet been found. Instead, current work stresses the kinds of reactions and the kinds of final states in which DI effects dominate and in which CN effects may almost be forgotten. The DI cross-sections which are studied are often extremely large, comparable to elastic scattering cross-sections. (author)

  19. Toehold-mediated strand displacement reaction-dependent fluorescent strategy for sensitive detection of uracil-DNA glycosylase activity.

    Science.gov (United States)

    Wu, Yushu; Wang, Lei; Jiang, Wei

    2017-03-15

    Sensitive detection of uracil-DNA glycosylase (UDG) activity is beneficial for evaluating the repairing process of DNA lesions. Here, toehold-mediated strand displacement reaction (TSDR)-dependent fluorescent strategy was constructed for sensitive detection of UDG activity. A single-stranded DNA (ssDNA) probe with two uracil bases and a trigger sequence were designed. A hairpin probe with toehold domain was designed, and a reporter probe was also designed. Under the action of UDG, two uracil bases were removed from ssDNA probe, generating apurinic/apyrimidinic (AP) sites. Then, the AP sites could inhibit the TSDR between ssDNA probe and hairpin probe, leaving the trigger sequence in ssDNA probe still free. Subsequently, the trigger sequence was annealed with the reporter probe, initiating the polymerization and nicking amplification reaction. As a result, numerous G-quadruplex (G4) structures were formed, which could bind with N-methyl-mesoporphyrin IX (NMM) to generate enhanced fluorescent signal. In the absence of UDG, the ssDNA probe could hybridize with the toehold domain of the hairpin probe to initiate TSDR, blocking the trigger sequence, and then the subsequent amplification reaction would not occur. The proposed strategy was successfully implemented for detecting UDG activity with a detection limit of 2.7×10 -5 U/mL. Moreover, the strategy could distinguish UDG well from other interference enzymes. Furthermore, the strategy was also applied for detecting UDG activity in HeLa cells lysate with low effect of cellular components. These results indicated that the proposed strategy offered a promising tool for sensitive quantification of UDG activity in UDG-related function study and disease prognosis. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. ACTIVATION REACTION ON THE ELECTROENCEPHALOGRAM IN SUBSTANCE DEPENDENT PATIENTS: LINKS TO ADDICTION STUDIES AND PSYCHOLOGICAL FACTORS AND CHANGES IN NEUROFEEDBACK TRAINING

    Directory of Open Access Journals (Sweden)

    M. e Melnikov

    2014-01-01

    Full Text Available Depth of activation reaction (α-activity suppression during the eyes-opening task is considered to be an important quantitative characteristic of α-band brainwaves. Activation reaction was assessed from O1 and O2 leads in 31 male substance dependent subjects. In 7 cases it was measured twice: before and after α- or β-brainwave biofeedback training. The correlations were found between grade of α suppression in eyes-opening task and attitude towards disease and treatment, personality maturity, and level of pathological personality traits. Activation reaction was significantly improved by α-training and non-significantly diminished after β-1-training.

  1. Psychosocial versus physiological stress – meta-analyses on deactivations and activations of the neural correlates of stress reactions

    Science.gov (United States)

    Kogler, Lydia; Mueller, Veronika I.; Chang, Amy; Eickhoff, Simon B.; Fox, Peter T.; Gur, Ruben C.; Derntl, Birgit

    2015-01-01

    Stress is present in everyday life in various forms and situations. Two stressors frequently investigated are physiological and psychosocial stress. Besides similar subjective and hormonal responses, it has been suggested that they also share common neural substrates. The current study used activation-likelihood-estimation meta-analysis to test this assumption by integrating results of previous neuroimaging studies on stress processing. Reported results are cluster-level FWE corrected. The inferior frontal gyrus (IFG) and the anterior insula (AI) were the only regions that demonstrated overlapping activation for both stressors. Analysis of physiological stress showed consistent activation of cognitive and affective components of pain processing such as the insula, striatum, or the middle cingulate cortex. Contrarily, analysis across psychosocial stress revealed consistent activation of the right superior temporal gyrus and deactivation of the striatum. Notably, parts of the striatum appeared to be functionally specified: the dorsal striatum was activated in physiological stress, whereas the ventral striatum was deactivated in psychosocial stress. Additional functional connectivity and decoding analyses further characterized this functional heterogeneity and revealed higher associations of the dorsal striatum with motor regions and of the ventral striatum with reward processing. Based on our meta-analytic approach, activation of the IFG and the AI seems to indicate a global neural stress reaction. While physiological stress activates a motoric fight-or-flight reaction, during psychosocial stress attention is shifted towards emotion regulation and goal-directed behavior, and reward processing is reduced. Our results show the significance of differentiating physiological and psychosocial stress in neural engagement. Furthermore, the assessment of deactivations in addition to activations in stress research is highly recommended. PMID:26123376

  2. Spontaneous interfacial reaction between metallic copper and PBS to form cupric phosphate nanoflower and its enzyme hybrid with enhanced activity.

    Science.gov (United States)

    He, Guangli; Hu, Weihua; Li, Chang Ming

    2015-11-01

    We herein report the spontaneous interfacial reaction between copper foil with 0.01 M phosphate buffered saline (PBS) to form free-standing cupric phosphate (Cu3(PO4)2) nanoflowers at ambient temperature. The underlying chemistry was thoroughly investigated and it is found that the formation of nanoflower is synergistically caused by dissolved oxygen, chlorine ions and phosphate ions. Enzyme-Cu3(PO4)2 hybrid nanoflower was further prepared successfully by using an enzyme-dissolving PBS solution and the enzymes in the hybrid exhibit enhanced biological activity. This work provides a facile route for large-scale synthesis of hierarchical inorganic and functional protein-inorganic hybrid architectures via a simple one-step solution-immersion reaction without using either template or surfactant, thus offering great potential for biosensing application among others. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Twisted Amides: From Obscurity to Broadly Useful Transition-Metal-Catalyzed Reactions by N-C Amide Bond Activation.

    Science.gov (United States)

    Liu, Chengwei; Szostak, Michal

    2017-05-29

    The concept of using amide bond distortion to modulate amidic resonance has been known for more than 75 years. Two classic twisted amides (bridged lactams) ingeniously designed and synthesized by Kirby and Stoltz to feature fully perpendicular amide bonds, and as a consequence emanate amino-ketone-like reactivity, are now routinely recognized in all organic chemistry textbooks. However, only recently the use of amide bond twist (distortion) has advanced to the general organic chemistry mainstream enabling a host of highly attractive N-C amide bond cross-coupling reactions of broad synthetic relevance. In this Minireview, we discuss recent progress in this area and present a detailed overview of the prominent role of amide bond destabilization as a driving force in the development of transition-metal-catalyzed cross-coupling reactions by N-C bond activation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Remeasurement and compilation of excitation function of proton induced reactions on iron for activation techniques

    International Nuclear Information System (INIS)

    Takacs, S.; Vasvary, L.; Tarkanyi, F.

    1994-01-01

    Excitation functions of proton induced reactions on nat Fe(p, xn) 56 Co have been remeasured in the energy region up to 18 MeV using stacked foil technique and standard high resolution gamma-ray spectrometry at the Debrecen MGC-20E cyclotron. Compilation of the available data measured between 1959 and 1993 has been made. The corresponding excitation functions have been reviewed, critical comparison of all the available data was done to obtain the most accurate data set. The feasibility of the evaluated data set was checked by reproducing experimental calibration curves for TLA by calculation. (orig.)

  5. Investigation of Activation Cross-Sections of Alpha-Induced Nuclear Reactions on Natural Silver

    International Nuclear Information System (INIS)

    Shahid, Muhammad; Kim, Kwangsoo; Naik, Haladhara; Zaman, Muhammad; Kang, Sinchul; Huh, Changgi; Kim, Guinyun

    2015-01-01

    The purpose was to study the production route of some radioisotopes applicable in medicine and industry. The measured results were compared with literature data and theoretical values. The nat Ag(α,x) reaction has already been studied for different energy ranges. However, the literature data needed new data set to increase the reliability of the reported results. The current experimental work will be helpful to make the literature data more reliable and to modify the theoretical models. The literature data needed new data set to increase the reliability of the reported results. The current experimental work is helpful to make the literature data more reliable and to modify the theoretical models

  6. Enhancement in the Catalytic Activity of Pd/USY in the Heck Reaction Induced by H2 Bubbling

    Directory of Open Access Journals (Sweden)

    Miki Niwa

    2010-12-01

    Full Text Available Pd was loaded on ultra stable Y (USY zeolites prepared by steaming NH4-Y zeolite under different conditions. Heck reactions were carried out over the prepared Pd/USY. We found that H2 bubbling was effective in improving not only the catalytic activity of Pd/USY, but also that of other supported Pd catalysts and Pd(OAc2. Moreover, the catalytic activity of Pd/USY could be optimized by choosing appropriate steaming conditions for the preparation of the USY zeolites; Pd loaded on USY prepared at 873 K with 100% H2O gave the highest activity (TOF = 61,000 h−1, which was higher than that of Pd loaded on other kinds of supports. The prepared Pd/USY catalysts were applicable to the Heck reactions using various kinds of substrates including bromo- and chloro-substituted aromatic and heteroaromatic compounds. Characterization of the acid properties of the USY zeolites revealed that the strong acid site (OHstrong generated as a result of steaming had a profound effect on the catalytic activity of Pd.

  7. Enhancement in the catalytic activity of Pd/USY in the heck reaction induced by H2 bubbling.

    Science.gov (United States)

    Okumura, Kazu; Tomiyama, Takuya; Moriyama, Sayaka; Nakamichi, Ayaka; Niwa, Miki

    2010-12-24

    Pd was loaded on ultra stable Y (USY) zeolites prepared by steaming NH(4)-Y zeolite under different conditions. Heck reactions were carried out over the prepared Pd/USY. We found that H₂ bubbling was effective in improving not only the catalytic activity of Pd/USY, but also that of other supported Pd catalysts and Pd(OAc)₂. Moreover, the catalytic activity of Pd/USY could be optimized by choosing appropriate steaming conditions for the preparation of the USY zeolites; Pd loaded on USY prepared at 873 K with 100% H₂O gave the highest activity (TOF = 61,000 h⁻¹), which was higher than that of Pd loaded on other kinds of supports. The prepared Pd/USY catalysts were applicable to the Heck reactions using various kinds of substrates including bromo- and chloro-substituted aromatic and heteroaromatic compounds. Characterization of the acid properties of the USY zeolites revealed that the strong acid site (OH(strong)) generated as a result of steaming had a profound effect on the catalytic activity of Pd.

  8. Hydrotreating NiMo/sepiolite catalysts: influence of catalyst preparation on activity for HDS, hydrogenation and chain isomerization reactions

    International Nuclear Information System (INIS)

    Melo, F.V.; Sanz, E.; Corma, A.; Mifsud, A.

    1987-01-01

    A series of NiMo catalysts supported on a sepiolite: a) in its natural state, b) modified by acid leaching, and c) modified by cation exchange, have been prepared. The preparation variables studied were: Method of metal deposition, amount of active phase, sepiolite pretreatment, and temperature and time of sulfurization. The catalytic activity for HDS, hydrogenation, and cracking-isomerization has been studied by feeding a thiophene-cyclohexene-cyclohexane mixture and carrying out the reaction in the following conditions: 300 0 and 400 0 C reaction temperature, 20 Kg.cm -2 total pressure, and 3 to 1 molar ratio of H 2 to hydrocarbons. An optimium for HDS and hydrogenation activity was found for a 12% wt MoO 3 , and 5% wt NiO, prepared by simultaneous impregnation by the pore volume method at Ph = 5.0. The optimum conditions with these catalysts are 400 0 C and 3 hours of sulfurization. An increase in the acidity of the support produces a decrease of HDS and hydrogenation and an increase of the cracking-isomerization activities. A good correlation between HDS and the concentration of an XNiO.MoO 3 phase is found. The XNiO.MoO 3 phase is completely sulfurized to a modified MoS 2 , while NiMoO 4 and MoO 3 are only slightly sulfurized. 31 refs.; 7 figs.; 1 table

  9. Catalytic Activity of Urchin-like Ni nanoparticles Prepared by Solvothermal Method for Hydrogen Evolution Reaction in Alkaline Solution

    International Nuclear Information System (INIS)

    Abbas, Syed Asad; Iqbal, Muhammad Ibrahim; Kim, Seong-Hoon; Jung, Kwang-Deog

    2017-01-01

    Highlights: • Urchin-like Ni is prepared in solvothermal reaction. • Urchin-like Ni is formed via Ni(OH) 2 aggregates in ethanol and oleylamine. • Exchange current density of urchin-like Ni is 0.191 mA cm −2 . • Urchin-like Ni exceeds the catalytic performance of commercial Pt/C in HER. - Abstract: Ni nanoparticles with different morphologies were synthesized for hydrogen evolution reaction (HER) in alkaline solution. Here, Ni(acac) 2 was converted into Ni metal nanoparticles in solvothermal reactions with simple alcohols and oleylamine (OAm). The morphology of the resulting Ni nanoparticles was dependent mainly on the OAm/Ni molar ratio in alcohol solvent. Aggregates of spherical Ni nanoparticles (NiEt-OAm1) were observed at the OAm/Ni molar ratio of 1.0, whereas two echinoid Ni nanoparticles (NiEt-OAm4 and NiEt-OAm6) could be prepared in ethanol at the OAm/Ni molar ratios of 4.0 and 6.0. Ni(OH) 2 formed in ethanol during a reaction time of 5 h was then reduced into echinoid Ni nanoparticles after 8 h. Echinoid Ni nanoparticles were formed by atomic addition on the tops of the multipod Ni particles formed via Ni(OH) 2 /NiO aggregates. Webbed feet-like particles (NiIPA-OAm4) with plate edges were also observed in isopropanol under the same reaction conditions. The catalytic activities of the prepared Ni nanoparticles for the hydrogen evolution reaction were evaluated in alkaline solution. The NiEt-OAm4 with urchin-like morphology was much more active than the NiIPA-OAm4 with webbed feet-like morphology. The exchange current density of Ni catalysts was increased with increasing the OAm/Ni molar ratio. The NiEt-OAm6 exhibited an exchange current of 0.191 mA cm −2 and the NiEt-OAm4 exceeded electrocatalytic performance of a commercial Pt catalysts (40% Pt on Vulcan XC 72) in a stability test for 100 kiloseconds at −1.5 V (vs. Hg/HgO) in 1.0 M NaOH due to its high stability.

  10. Effect of reaction parameters on photoluminescence and photocatalytic activity of zinc sulfide nanosphere synthesized by hydrothermal route

    Energy Technology Data Exchange (ETDEWEB)

    Chanu, T. Inakhunbi; Samanta, Dhrubajyoti [Centre for Material Science and Nanotechnology, Sikkim Manipal Institute of Technology, Sikkim Manipal University, Sikkim 737136 (India); Tiwari, Archana [Department of Physics, Sikkim University, 737102 Sikkim (India); Chatterjee, Somenath, E-mail: somenath@gmail.com [Centre for Material Science and Nanotechnology, Sikkim Manipal Institute of Technology, Sikkim Manipal University, Sikkim 737136 (India); Electronics & Communication Engineering Department, Sikkim Manipal Institute of Technology, Sikkim Manipal University, Sikkim 737136 (India)

    2017-01-01

    Highlights: • ZnS nanosphere synthesis in hydrothermal method with biomolecule as capping ligand. • Effect of reaction parameters to tune the size of ZnS nanoparticles. • Obtain multiple defect emission, which arises from interstitials/vacancies. • 87% degradation of Rh-B in the presence of ZnS nanoparticles under solar radiation. - Abstract: Zinc Sulfide (ZnS) nanospheres have been synthesized using amino acid, L-Histidine as a capping agent by hydrothermal method. The as prepared ZnS have been characterised using X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), High Resolution Transmission Electron Microscopy (HRTEM), Photoluminescence (PL), Fourier Transform Infra-Red spectroscopy (FTIR), UV–vis absorption spectroscopy and X-ray Photo Electron Spectroscopy (XPS). Effect of reaction parameters on particle size has been investigated. The morphology and size of the ZnS can be tuned based on the reaction parameters. ZnS nanosphere with a particle size of 5 nm is obtained when the reaction parameters are kept at 120 °C for 3 h. The PL of ZnS shows multiple defect emissions arising from interstitials/vacancies. Particle size of ZnS nanoparticles plays an important role in determining the photo catalytic activity. A chronological study on synthesis of ZnS nanosphere and its photo catalytic activity under the sunlight are discussed here, which reveals the photo degradation of Rhodamine B (RhB) upto 87% as observed with ZnS nanosphere having a particle size of 5 nm.

  11. Synergistically enhanced activity of nitrogen-doped carbon dots/graphene composites for oxygen reduction reaction

    Science.gov (United States)

    Liu, Hui; Zhao, Qingshan; Liu, Jingyan; Ma, Xiao; Rao, Yuan; Shao, Xiaodong; Li, Zhongtao; Wu, Wenting; Ning, Hui; Wu, Mingbo

    2017-11-01

    With rapid dissociative adsorption of oxygen, nitrogen-doped carbon nanomaterials have been demonstrated to be efficient alternative catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we developed a mild hydrothermal strategy to construct nitrogen-doped carbon dots/graphene (NCDs-NG) composites towards ORR. Carbon dots (CDs) were derived from petroleum coke via acid oxidation while graphene oxide (GO) was obtained from graphite by modified Hummer's method. Graphene was employed as a conductive substrate to disperse CDs during hydrothermal reducing reaction while ammonia was utilized as N source to dope both graphene and CDs. The synergistic effects, i.e. CDs as pillars for graphene and catalytic sites for ORR, the high conductivity of graphene, the quick O2 adsorption on doped pyridinic nitrogen endow the NCDs-NG composites with enhanced ORR catalytic performance in alkaline electrolyte. The onset potential of -95 mV and kinetic current density of 12.7 mA cm-2 at -0.7 V (vs. Ag/AgCl) can be compared to those of the commercial 20 wt% Pt/C catalyst. The electron transfer number is about 3.9, revealing a four-electron pathway for ORR. The optimal NCDs-NG catalyst shows superior durability and methanol tolerance than 20 wt% Pt/C. This work demonstrates a feasible and effective strategy to prepare metal-free efficient ORR electrocatalysts for fuel cell applications.

  12. Catalytic activity of calcium-based mixed metal oxides nanocatalysts in transesterification reaction of palm oil

    Science.gov (United States)

    Hassan, Noraakinah; Ismail, Kamariah Noor; Hamid, Ku Halim Ku; Hadi, Abdul

    2017-12-01

    Nowadays, biodiesel has become the forefront development as an alternative diesel fuel derived from biological sources such as oils of plant and fats. Presently, the conventional transesterification of vegetable oil to biodiesel gives rise to some technological problem. In this sense, heterogeneous nanocatalysts of calcium-based mixed metal oxides were synthesized through sol-gel method. It was found that significant increase of biodiesel yield, 91.75 % was obtained catalyzed by CaO-NbO2 from palm oil compared to pure CaO of 53.99 % under transesterification conditions (methanol/oil ratio 10:1, reaction time 3 h, catalyst concentration 4 wt%, reaction temperature 60 °C, and mixing speed of 600 rpm). The phase structure and crystallinity as well as the texture properties of the prepared catalysts were characterized by X-ray Diffraction (XRD) and the textural properties were characterized by N2 adsorption-desorption analysis. Sol-gel method has been known as versatile method in controlling the structural and chemical properties of the catalyst. Calcium-based mixed oxide synthesized from sol-gel method was found to exist as smaller crystallite size with high surface area.

  13. Analytic study of the chain dark decomposition reaction of iodides - atomic iodine donors - in the active medium of a pulsed chemical oxygen-iodine laser: 1. Criteria for the development of the branching chain dark decomposition reaction of iodides

    International Nuclear Information System (INIS)

    Andreeva, Tamara L; Kuznetsova, S V; Maslov, Aleksandr I; Sorokin, Vadim N

    2009-01-01

    The scheme of chemical processes proceeding in the active medium of a pulsed chemical oxygen-iodine laser (COIL) is analysed. Based on the analysis performed, the complete system of differential equations corresponding to this scheme is replaced by a simplified system of equations describing in dimensionless variables the chain dark decomposition of iodides - atomic iodine donors, in the COIL active medium. The procedure solving this system is described, the basic parameters determining the development of the chain reaction are found and its specific time intervals are determined. The initial stage of the reaction is analysed and criteria for the development of the branching chain decomposition reaction of iodide in the COIL active medium are determined. (active media)

  14. Communication: Extended multi-state complete active space second-order perturbation theory: Energy and nuclear gradients

    Science.gov (United States)

    Shiozaki, Toru; Győrffy, Werner; Celani, Paolo; Werner, Hans-Joachim

    2011-08-01

    The extended multireference quasi-degenerate perturbation theory, proposed by Granovsky [J. Chem. Phys. 134, 214113 (2011)], is combined with internally contracted multi-state complete active space second-order perturbation theory (XMS-CASPT2). The first-order wavefunction is expanded in terms of the union of internally contracted basis functions generated from all the reference functions, which guarantees invariance of the theory with respect to unitary rotations of the reference functions. The method yields improved potentials in the vicinity of avoided crossings and conical intersections. The theory for computing nuclear energy gradients for MS-CASPT2 and XMS-CASPT2 is also presented and the first implementation of these gradient methods is reported. A number of illustrative applications of the new methods are presented.

  15. Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions

    Directory of Open Access Journals (Sweden)

    Paul P. Kelly

    2015-09-01

    Full Text Available Cytochrome P450 monooxygenases are useful biocatalysts for C–H activation, and there is a need to expand the range of these enzymes beyond what is naturally available. A panel of 93 variants of active self-sufficient P450cam[Tyr96Phe]-RhFRed fusion enzymes with a broad diversity in active site amino acids was developed by screening a large mutant library of 16,500 clones using a simple, highly sensitive colony-based colorimetric screen against indole. These mutants showed distinct fingerprints of activity not only when screened in oxidations of substituted indoles but also for unrelated oxidations such as benzylic hydroxylations.

  16. Active sources in the cutoff of centrifugal fans to reduce the blade tones at higher-order duct mode frequencies

    Science.gov (United States)

    Neise, W.; Koopmann, G. H.

    1991-01-01

    A previously developed (e.g., Neise and Koopmann, 1984; Koopmann et al., 1988) active noise control technique in which the unwanted acoustic signals from centrifugal fans are suppressed by placing two externally driven sources near the cutoff of the casing was applied to the frequency region where not only plane sound waves are propagational in the fan ducts but also higher-order acoustic modes. Using a specially designed fan noise testing facility, the performance of two fans (280-mm impeller diam and 508 mm diam) was monitored with static pressure taps mounted peripherally around the inlet nozzle. Experimental results show that the aerodynamically generated source pressure field around the cutoff is too complex to be successfully counterimaged by only two active sources introduced in this region. It is suggested that, for an efficient application of this noise control technique in the higher-order mode frequency regime, it is neccessary to use an active source involving larger number of individually driven loudspeakers.

  17. Spatially and size selective synthesis of Fe-based nanoparticles on ordered mesoporous supports as highly active and stable catalysts for ammonia decomposition.

    Science.gov (United States)

    Lu, An-Hui; Nitz, Joerg-Joachim; Comotti, Massimiliano; Weidenthaler, Claudia; Schlichte, Klaus; Lehmann, Christian W; Terasaki, Osamu; Schüth, Ferdi

    2010-10-13

    Uniform and highly dispersed γ-Fe(2)O(3) nanoparticles with a diameter of ∼6 nm supported on CMK-5 carbons and C/SBA-15 composites were prepared via simple impregnation and thermal treatment. The nanostructures of these materials were characterized by XRD, Mössbauer spectroscopy, XPS, SEM, TEM, and nitrogen sorption. Due to the confinement effect of the mesoporous ordered matrices, γ-Fe(2)O(3) nanoparticles were fully immobilized within the channels of the supports. Even at high Fe-loadings (up to about 12 wt %) on CMK-5 carbon no iron species were detected on the external surface of the carbon support by XPS analysis and electron microscopy. Fe(2)O(3)/CMK-5 showed the highest ammonia decomposition activity of all previously described Fe-based catalysts in this reaction. Complete ammonia decomposition was achieved at 700 °C and space velocities as high as 60,000 cm(3) g(cat)(-1) h(-1). At a space velocity of 7500 cm(3) g(cat)(-1) h(-1), complete ammonia conversion was maintained at 600 °C for 20 h. After the reaction, the immobilized γ-Fe(2)O(3) nanoparticles were found to be converted to much smaller nanoparticles (γ-Fe(2)O(3) and a small fraction of nitride), which were still embedded within the carbon matrix. The Fe(2)O(3)/CMK-5 catalyst is much more active than the benchmark NiO/Al(2)O(3) catalyst at high space velocity, due to its highly developed mesoporosity. γ-Fe(2)O(3) nanoparticles supported on carbon-silica composites are structurally much more stable over extended periods of time but less active than those supported on carbon. TEM observation reveals that iron-based nanoparticles penetrate through the carbon layer and then are anchored on the silica walls, thus preventing them from moving and sintering. In this way, the stability of the carbon-silica catalyst is improved. Comparison with the silica supported iron oxide catalyst reveals that the presence of a thin layer of carbon is essential for increased catalytic activity.

  18. Higher-Order Sensory Cortex Drives Basolateral Amygdala Activity during the Recall of Remote, but Not Recently Learned Fearful Memories.

    Science.gov (United States)

    Cambiaghi, Marco; Grosso, Anna; Likhtik, Ekaterina; Mazziotti, Raffaele; Concina, Giulia; Renna, Annamaria; Sacco, Tiziana; Gordon, Joshua A; Sacchetti, Benedetto

    2016-02-03

    Negative experiences are quickly learned and long remembered. Key unresolved issues in the field of emotional memory include identifying the loci and dynamics of memory storage and retrieval. The present study examined neural activity in the higher-order auditory cortex Te2 and basolateral amygdala (BLA) and their crosstalk during the recall of recent and remote fear memories. To this end, we obtained local field potentials and multiunit activity recordings in Te2 and BLA of rats that underwent recall at 24 h and 30 d after the association of an acoustic conditioned (CS, tone) and an aversive unconditioned stimulus (US, electric shock). Here we show that, during the recall of remote auditory threat memories in rats, the activity of the Te2 and BLA is highly synchronized in the theta frequency range. This functional connectivity stems from memory consolidation processes because it is present during remote, but not recent, memory retrieval. Moreover, the observed increase in synchrony is cue and region specific. A preponderant Te2-to-BLA directionality characterizes this dialogue, and the percentage of time Te2 theta leads the BLA during remote memory recall correlates with a faster latency to freeze to the auditory conditioned stimulus. The blockade of this information transfer via Te2 inhibition with muscimol prevents any retrieval-evoked neuronal activity in the BLA and animals are unable to retrieve remote memories. We conclude that memories stored in higher-order sensory cortices drive BLA activity when distinguishing between learned threatening and neutral stimuli. How and where in the brain do we store the affective/motivational significance of sensory stimuli acquired through life experiences? Scientists have long investigated how "limbic" structures, such as the amygdala, process affective stimuli. Here we show that retrieval of well-established threat memories requires the functional interplay between higher-order components of the auditory cortex and the

  19. Deactivation of solid catalysts in liquid media: the case of leaching of active sites in biomass conversion reactions

    DEFF Research Database (Denmark)

    Sádaba, Irantzu; Lopez Granados, Manuel; Riisager, Anders

    2015-01-01

    This review is aimed to be a brief tutorial covering the deactivation of solid catalysts in the liquid phase, with specific focus on leaching, which can be especially helpful to researchers not familiarized with catalytic processes in the liquid phase. Leaching refers to the loss of active species....... However, as a consequence of the development of new processes for biorefineries, an increasing number of reactions deal with liquid media, and thus, the stability and reusability of a solid catalyst in this situation represent a huge challenge that requires specific attention. Leaching of active phases...... is particularly problematic because of its irreversibility and it can be one of the main causes of catalyst deactivation in liquid media, threatening the sustainability of the process. This tutorial review presents a survey of the main aspects concerning the deactivation due to leaching of active species from...

  20. Pt monolayer shell on hollow Pd core electrocatalysts: Scale up synthesis, structure, and activity for the oxygen reduction reaction

    Directory of Open Access Journals (Sweden)

    Vukmirovic Miomir B.

    2013-01-01

    Full Text Available We report on synthesis, characterization and the oxygen reduction reaction (ORR kinetics of Pt monolayer shell on Pd(hollow, or Pd-Au(hollow core electrocatalysts. Comparison between the ORR catalytic activity of the electrocatalysts with hollow cores and those of Pt solid and Pt hollow nanoparticles has been obtained using the rotating disk electrode technique. Hollow nanoparticles were made using Ni or Cu nanoparticles as sacrificial templates. The Pt ORR specific and mass activities of the electrocatalysts with hollow cores were found considerably higher than those of the electrocatalysts with the solid cores. We attribute this enhanced Pt activity to the smooth surface morphology and hollow-induced lattice contraction, in addition to the mass-saving geometry of hollow particles.

  1. Antioxidant activity of the melanoidin fractions formed from DGlucose and D-Fructose with L-Asparagine in the Maillard reaction

    Directory of Open Access Journals (Sweden)

    A.P Echavarría

    2013-03-01

    Full Text Available Melanoidins formed at the last stage of the Maillard reaction have been shown to possess certain functional properties, such as antioxidant activity. In order to gain more insight into these functional properties, soluble model systems melanoidins from L‑Asparagine with D‑glucose or D‑fructose fractionating by ultrafiltration were analyzed. The fractionating/concentration sequence of the melanoidin fraction (1-300 kDa enabled five fractions to be produced.Additionally, the absorption of melanoidins was measured at different wavelengths (280, 325, 405 and browning at 420 nm. The fractionation effect of melanoidin systems on the color intensity, UV-absorbance scan wavelengths (nm, CIE, L*, a*, b* parameters and antioxidant activity were measured. For this purpose, antioxidant activity was evaluated through the free radical scavenging activity, including 1,1-diphenyl-2-picryl-hydrazil (DPPH and 2,20-azinobis (3-ethylbenothiazoline-6-sulfonic acid, diammonium salt (ABTS. The results showed that the absorption of the melanoidins formed from Glucose/L-Asn was higher than for those derived from Fructose/L-Asn. On the other hand, their antioxidant power was lower than that for melanoidins formed from Fructose/L-Asn systems.

  2. The Synthesis and Electrocatalytic Activities of Molybdenum Sulfide for Hydrogen Evolution Reaction

    KAUST Repository

    Li, Zhengxing

    2014-01-01

    of the Pt-group metals for HER. Plenty of researches have been conducted for improving the HER activities of MoS2 by optimizing its synthesis method. However, it remains challenging to prepare MoS2 catalysts with high and controllable activity, and more

  3. Asymmetric Benzylic Allylic Alkylation Reaction of 3-Furfural Derivatives by Dearomatizative Dienamine Activation.

    Science.gov (United States)

    He, Xiao-Long; Zhao, Hui-Ru; Duan, Chuan-Qi; Han, Xu; Du, Wei; Chen, Ying-Chun

    2018-04-20

    The dearomatizative dienamine-type ortho-quinodimethane species are smoothly generated between 2-alkyl-3-furfurals and chiral secondary amine catalysts, which undergo asymmetric benzylic allylic alkylation reactions with 2-nitroallylic acetates efficiently. A spectrum of densely functionalized 3-furfural derivatives are delivered in moderate to high yields with good to excellent diastereo- and enantioselectivity (up to 98 % yield, >19:1 d.r., >99 % ee). The latent transformations allow the facile production of some enantioenriched architectures, such as 1,1,2,2-tetraarylethanes and triarylmethanes, which are not easily available from other protocols. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Morphological transformation during activation and reaction of an iron Fischer-Tropsch catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, N.B.; Kohler, S.; Harrington, M. [Sandia National Lab., Albuquerque, NM (United States)] [and others

    1995-12-31

    The purpose of this project is to support the development of slurry-phase bubble column processes being studied at the La Porte Alternative Fuel Development Unit. This paper describes the aspects of Sandia`s recent work regarding the advancement and understanding of the iron catalyst used in the slurry phase process. A number of techniques were used to understand the chemical and physical effects of pretreatment and reaction on the attrition and carbon deposition characteristics of iron catalysts. Unless otherwise stated, the data discussed was derived form experiments carried out on the catalyst chosen for the summer 1994 Fischer-Tropsch run at LaPorte, UCI 1185-78-370, (an L 3950 type) that is 88% Fe{sub 2}O{sub 3}, 11% CuO, and 0.052%K{sub 2}O.

  5. Second Order Cone Programming (SOCP) Relaxation Based Optimal Power Flow with Hybrid VSC-HVDC Transmission and Active Distribution Networks

    DEFF Research Database (Denmark)

    Ding, Tao; Li, Cheng; Yang, Yongheng

    2017-01-01

    The detailed topology of renewable resource bases may have the impact on the optimal power flow of the VSC-HVDC transmission network. To address this issue, this paper develops an optimal power flow with the hybrid VSC-HVDC transmission and active distribution networks to optimally schedule...... the generation output and voltage regulation of both networks, which leads to a non-convex programming model. Furthermore, the non-convex power flow equations are based on the Second Order Cone Programming (SOCP) relaxation approach. Thus, the proposed model can be relaxed to a SOCP that can be tractably solved...

  6. Comparison Between Pre-Exhaustion and Traditional Exercise Order on Muscle Activation and Performance in Trained Men

    Science.gov (United States)

    Soares, Enrico Gori; Brown, Lee E.; Gomes, Willy Andrade; Corrêa, Daniel Alves; Serpa, Érica Paes; da Silva, Josinaldo Jarbas; Junior, Guanis de Barros Vilela; Fioravanti, Gustavo zorzi; Aoki, Marcelo Saldanha; Lopes, Charles Ricardo; Marchetti, Paulo Henrique

    2016-01-01

    The purpose of this study was to measure the acute effects of pre-exhaustion vs. traditional exercise order on neuromuscular performance and sEMG in trained men. Fourteen young, healthy, resistance trained men (age: 25.5 ± 4.0 years, height: 174.9 ± 4.1 cm, and total body mass: 80.0 ± 11.1 kg) took part of this study. All tests were randomized and counterbalanced for all subjects and experimental conditions. Volunteers attended one session in the laboratory. First, they performed ten repetition maximum (10RM) tests for each exercise (bench press and triceps pushdown) separately. Secondly, they performed all three conditions at 10RM: pre-test (bench press and triceps pushdown, separately), pre-exhaustion (triceps pushdown+bench press, PE) and traditional (bench press+triceps pushdown, TR), and rested 30 minutes between conditions. Results showed that pre-test was significantly greater than PE (p = 0.031) but not different than TR, for total volume load lifted. There was a significant difference between the pre-test and the time-course of lactate measures (p = 0.07). For bench press muscle activity of the pectoralis major, the last repetition was significantly greater than the first repetition (pre-test: p = 0.006, PE: p = 0.016, and TR: p = 0.005). Also, for muscle activity of the triceps brachii, the last repetition was significantly greater than the first repetition (pre-test: p = 0.001, PE: p = 0.005, and TR: p = 0.006). For triceps pushdown, muscle activity of the triceps brachii, the last repetition was significantly greater than the first repetition (pre-test: p = 0.006, PE: p = 0.016, and TR: p = 0.005). For RPE, there were no significant differences between PE and TR (p = 0.15). Our results suggest that exercise order decreases repetitions performed, however, neuromuscular fatigue, lactate, and RPE are not impacted. The lack of difference in total volume load lifted between PE and TR might explain, at least in part, the similar metabolic and perceptual

  7. Measurements of activation reaction rates in transverse shielding concrete exposed to the secondary particle field produced by intermediate energy heavy ions on an iron target

    International Nuclear Information System (INIS)

    Ogawa, T.; Morev, M.N.; Iimoto, T.; Kosako, T.

    2012-01-01

    Reaction rate distributions were measured inside a 60-cm thick concrete pile placed at the lateral position of a thick (stopping length) iron target that was bombarded with heavy ions, 400 MeV/u C and 800 MeV/u Si. Foils of aluminum and gold, as well as gold, tungsten and manganese covered with cadmium were inserted at various locations in the concrete pile to serve as activation detectors. Features of reaction rate distribution, such as the shape of the reaction rate profile, contribution of the neutrons from intra-nuclear cascade and that from evaporation to the activation reactions are determined by the analysis of measured reaction rates. The measured reaction rates were compared with those calculated with radiation transport simulation codes, FLUKA and PHITS, to verify their capability to predict induced activity. The simulated reaction rates agree with the experimental results within a factor of three in general. However, systematic discrepancies between simulated reaction rates and measured reaction rates attributed to the neutron source terms are observed.

  8. Neutronics and activation of the preliminary reaction chamber of HiPER reactor based in a SCLL blanket

    Energy Technology Data Exchange (ETDEWEB)

    Juárez, Rafael, E-mail: rafael.juarez@upm.es [Instituto de Fusión Nuclear, UPM, Madrid (Spain); Escuela Técnica Superior de Ingenieros Industriales, UNED, Madrid (Spain); Sanz, Javier; Lopez-Revelles, A.J. [Escuela Técnica Superior de Ingenieros Industriales, UNED, Madrid (Spain); Perlado, José Manuel [Instituto de Fusión Nuclear, UPM, Madrid (Spain)

    2013-10-15

    Highlights: • Neutronic study of a proposal of a reaction chamber for HiPER reactor. • Two options for the blanket size, thin and thick, are studied and compared. • The thin blanket performs better than the thick blanket. • The proposed Vacuum Vessel is unviable as lifetime component in both cases. • Likely solutions for the Vacuum Vessel lifetime extension are explored. -- Abstract: The HiPER reactor design is exploring different reaction chambers. In this study, we tackle the neutronics and activation studies of a preliminary reaction chamber based in the following technologies: unprotected dry wall for the First Wall, self-cooled lead lithium blanket, and independent low activation steel Vacuum Vessel. The most critical free parameter in this stage is the blanket thickness, as a function of the {sup 6}Li enrichment. After a parametric study, we select for study both a “thin” and “thick” blanket, with “high” and “low” {sup 6}Li enrichment respectively, to reach a TBR = 1.1. To help to make a choice, we compute, for both blanket options, in addition to the TBR, the energy amplification factor, the tritium partial pressure, the {sup 203}Hg and {sup 210}Po total activity in the LiPb loop, and the Vacuum Vessel thickness required to guarantee the reweldability during its lifetime. The thin blanket shows a superior performance in the safety related issues and structural viability, but it operates at higher {sup 6}Li enrichment. It is selected for further improvements. The Vacuum Vessel shows to be unviable in both cases, with the thickness varying between 39 and 52 cm. Further chamber modifications, such as the introduction of a neutron reflector, are required to exploit the benefits of the thin blanket with a reasonable Vacuum Vessel.

  9. Influence of Micropore and Mesoporous in Activated Carbon Air-cathode Catalysts on Oxygen Reduction Reaction in Microbial Fuel Cells

    International Nuclear Information System (INIS)

    Liu, Yi; Li, Kexun; Ge, Baochao; Pu, Liangtao; Liu, Ziqi

    2016-01-01

    In this study, carbon samples with different micropore and mesoporous structures are prepared as air-cathode catalyst layer to explore the role of pore structure on oxygen reduction reaction. The results of linear sweep voltammetry and power density show that the commercially-produced activated carbon (CAC) has the best electrochemical performance, and carbon samples with only micropore or mesoporous show lower performance than CAC. Nitrogen adsorption-desorption isotherms analysis confirm that CAC has highest surface area (1616 m 2 g −1 ) and a certain amount of micropore and mesoporous. According to Tafel plot and rotating disk electrode, CAC behaves the highest kinetic activity and electron transfer number, leading to the improvement of oxygen reduction reaction. The air permeability test proves that mesoporous structure enhance oxygen permeation. Carbon materials are also analyzed by In situ Fourier Transform Infrared Spectroscopy and H 2 temperature programmed reduction, which indicate that micropore provide active sites for catalysis. In a word, micropore and mesoporous together would improve the electrochemical performance of carbon materials.

  10. Ex Vivo Antioxidant Activity of Selected Medicinal Plants against Fenton Reaction-Mediated Oxidation of Biological Lipid Substrates

    Directory of Open Access Journals (Sweden)

    Namratha Pai Kotebagilu

    2015-01-01

    Full Text Available Free radical-mediated oxidation is often linked to various degenerative diseases. Biological substrates with lipids as major components are susceptible to oxygen-derived lipid peroxidation due to their composition. Lipid peroxide products act as biomarkers in evaluating the antioxidant potential of various plants and functional foods. The study focused on evaluation of the antioxidant potential of two extracts (methanol and 80% methanol of four medicinal plants, Andrographis paniculata, Costus speciosus, Canthium parviflorum, and Abrus precatorius, against Fenton reaction-mediated oxidation of three biological lipid substrates; cholesterol, low-density lipoprotein, and brain homogenate. The antioxidant activity of the extracts was measured by thiobarbituric acid reactive substances method. Also, the correlation between the polyphenol, flavonoid content, and the antioxidant activity in biological substrates was analyzed. Results indicated highest antioxidant potential by 80% methanol extract of Canthium parviflorum (97.55%, methanol extract of Andrographis paniculata (72.15%, and methanol extract of Canthium parviflorum (49.55% in cholesterol, low-density lipoprotein, and brain, respectively. The polyphenol and flavonoid contents of methanol extract of Andrographis paniculata in cholesterol (r=0.816 and low-density lipoprotein (r=0.948 and Costus speciosus in brain (r=0.977, polyphenols, and r=0.949, flavonoids correlated well with the antioxidant activity. The findings prove the antioxidant potential of the selected medicinal plants against Fenton reaction in biological lipid substrates.

  11. Highly active and non-corrosive catalytic systems for the coupling reactions of ethylene oxide and CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Shuyao; Jin, So Jeong; Kim, Young Jin; Lee, Je Seung; Kim, Hoon Sik [Dept. of Chemistry and Research Institute of Basic Sciences, Kyung Hee University, Seoul (Korea, Republic of); Hong, Jongki; Lee, Won Woong [College of Pharmacy, Kyung Hee University, Seoul (Korea, Republic of); Ryu, Jung Bok [R and D Center, Chuncheon (Korea, Republic of)

    2017-02-15

    Lithium halide-based molten salts (LiX-[BMIm]Br) synthesized from the reactions of lithium halides (LiX, X = Cl or Br) with 1-butyl-3-methylimidazolium bromide ([BMIm]Br), and their catalytic performances and corrosivities were tested for the coupling reactions of ethylene oxide with carbon dioxide to produce ethylene carbonate. The activity of a molten salt was influenced with the change of halide ion. At a fixed molar amount of LiX, the activity of LiX-[BMIm]Br increased with increasing molar ratio of LiX/[BMIm]Br up to 1–1.25, and then decreased thereafter. Fast atom bombardment mass spectral analysis of LiBr-[BMIm]Br, obtained by dissolving LiBr in [BMIm]Br in a 1:1 molar ratio, implies that [Li{sub a} X{sub a+1}]{sup −} are active species for the carboxylation of ethylene oxide with LiX-[BMIm]Br. The corrosion test toward carbon steel coupons demonstrates that all the Cl-containing molten salts are corrosive, whereas the salts without containing Cl{sup −} are non-corrosive under the carboxylation condition.

  12. Measurement of activation reaction rate distributions in a lead assembly bombarded with 500-MeV protons

    CERN Document Server

    Takada, H; Sasa, T; Tsujimoto, K; Yasuda, H

    2000-01-01

    Reaction rate distributions of various activation detectors such as the /sup nat/Ni(n, x)/sup 58/Co, /sup 197/Au(n,2n)/sup 196/Au, and /sup 197/Au(n,4n)/sup 194/Au reactions were measured to study the production and the transport of spallation neutrons in a lead assembly bombarded with protons of 500 MeV. The measured data were analyzed with the nucleon-meson transport code NMTC/JAERI combined with the MCNP4A code using the nuclide production cross sections based on the JENDL Dosimetry File and those calculated with the ALICE-F code. It was found that the NMTC/JAERI-MCNP4A calculations agreed well with the experiments for the low-energy-threshold reaction of /sup nat/Ni(n, x)/sup 58/Co. With the increase of threshold energy, however, the calculation underestimated the experiments, especially above 20 MeV. The reason for the disagreement can be attributed to the underestimation of the neutron yield in the tens of mega-electron-volt regions by the NMTC/JAERI code. (32 refs).

  13. Characteristic antioxidant activity and comprehensive flavor compound profile of scallop (Chlamys farreri) mantle hydrolysates-ribose Maillard reaction products.

    Science.gov (United States)

    Han, Jia-Run; Yan, Jia-Nan; Sun, Shi-Guang; Tang, Yue; Shang, Wen-Hui; Li, Ao-Ting; Guo, Xiao-Kun; Du, Yi-Nan; Wu, Hai-Tao; Zhu, Bei-Wei; Xiong, Youling L

    2018-09-30

    The objective of the present study was to improve the utilization of scallop (Chlamys farreri) byproducts by using Maillard reaction. Scallop mantle hydrolysates (SMHs) were prepared using neutrase then reacted with ribose. Thirty-four peptides were identified from SMHs by UPLC-Q-TOF-MS, and the abundance of Asp and Lys suggested the strong Maillard reactivity. The formation of Schiff's base as well as modification of amide I, II and III bands in Maillard reaction products (MRPs) was confirmed by ultraviolet-visible, fluorescence, and Fourier transform infrared spectroscopy. Thirty volatile compounds were produced by the reaction of SMHs with ribose. Moreover, MRPs with enhanced radical scavenging and anti-linoleic acid peroxidation activities over SMHs promoted the survival and reduced the DNA damage of HepG2 cells treated with hydrogen peroxide. These results suggest that SMHs-ribose MRPs can be potentially used as food antioxidant for suppressing of lipid oxidation or protecting of cell from oxidative damage. Copyright © 2018 Elsevier Ltd. All rights reserved.

  14. Operando investigation of Au-MnOx thin films with improved activity for the oxygen evolution reaction

    DEFF Research Database (Denmark)

    Frydendal, Rasmus; Seitz, Linsey C.; Sokaras, Dimosthenis

    2017-01-01

    The electrochemical splitting of water holds great potential as a method for producing clean fuels by storing electricity from intermittent energy sources. The efficiency of such a process would be greatly facilitated by incorporating more active catalysts based on abundant materials for the oxygen...... improvement over pure MnOx. These films are characterized with operando X-ray Absorption Spectroscopy, which reveal that Mn assumes a higher oxidation state under reaction conditions when Au is present. The magnitude of the enhancement is correlated to the size of the Au domains, where larger domains...

  15. All-oxide Raman-active traps for light and matter: probing redox homeostasis model reactions in aqueous environment.

    Science.gov (United States)

    Alessandri, Ivano; Depero, L E

    2014-04-09

    Core-shell colloidal crystals can act as very efficient traps for light and analytes. Here it is shown that Raman-active probes can be achieved using SiO2-TiO2 core-shell beads. These systems are successfully tested in monitoring of glutathione redox cycle at physiological concentration in aqueous environment, without need of any interfering enhancers. These materials represent a promising alternative to conventional, metal-based SERS probes for investigating chemical and biochemical reactions under real working conditions. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Calculation and evaluation of the activation cross sections for 187Re(n,2n)186m,gRe reactions

    International Nuclear Information System (INIS)

    Huang Xiaolong; Lu Hanlin; Zhou Chunmei

    1998-01-01

    The activation cross sections for 187 Re(n,2n) 186m,g Re reactions are calculated using UNF code. The calculations are in good agreement with the re-evaluated measured data. Finally the excitation function for 187 Re(n,2n) 186m,g Re reactions are evaluated and recommended based on present calculations and evaluated decay data

  17. Activation-energy for the reaction h+oh--]eaq- - kinetic determination of the enthalpy and entropy of solvation of the hydrated electron

    DEFF Research Database (Denmark)

    Hickle, B.; Sehested, Knud

    1985-01-01

    The reaction between atomic hydrogen and hydroxide ion in aqueous solutions H + OH- - eaq- + H20 has been studied by pulse radiolysis. The rate constant was measured at pH 11.7 and 12 by following the growth of the hydrated electron absorption at 600 nm. The activation energy of the reaction has...

  18. Synthesis, reactions, and antiarrhythmic activities of some novel pyrimidines and pyridines fused with thiophene moiety

    OpenAIRE

    AMR, Abdel-Galil El-Sayed; ABDEL-HAFEZ, Naglaa Abdel-Samei

    2009-01-01

    We report herein the synthesis and antiarrhythmic activities of some newly synthesized heterocyclic theino[2,3-c]pyrimidine and theino[2,3-c]pyridine derivatives fused with thiophene moiety. Initially the acute toxicity of the compounds was assayed via the determination of their LD50. The antiarrhythmic activities for the compounds were determined and all the tested compounds were found more potent than Procaine amide\\textregistered and Lidocaine\\textregistered as positive antiarrhyth...

  19. Synthesis, reactions, and antiarrhythmic activities of some novel pyrimidines and pyridines fused with thiophene moiety

    OpenAIRE

    AMR, Abdel-Galil El-Sayed; ABDEL-HAFEZ, Naglaa Abdel-Samei; MOHAMED, Salwa Fahem; ABDALLA, Mohamed Mostafa

    2014-01-01

    We report herein the synthesis and antiarrhythmic activities of some newly synthesized heterocyclic theino[2,3-c]pyrimidine and theino[2,3-c]pyridine derivatives fused with thiophene moiety. Initially the acute toxicity of the compounds was assayed via the determination of their LD50. The antiarrhythmic activities for the compounds were determined and all the tested compounds were found more potent than Procaine amide\\textregistered and Lidocaine\\textregistered as positive antiarrhyth...

  20. Alkali – activated binders: a review part 1. Historical background, terminology, reaction mechanisms and hydration products

    OpenAIRE

    Torgal, Fernando Pacheco; Gomes, J. P. Castro; Jalali, Said

    2008-01-01

    The disintegration of concrete structures made of ordinary Portland cement (OPC) is a worrying topic of increasing significance. The development of new binders with longer durability is therefore needed. Alkali-activated binders have emerged as an alternative to OPC binders, which seems to have superior durability and environmental impact. This paper reviews current knowledge about alkali-activated binders. The subjects of Part 1 in this paper are historical background, terminology a...

  1. Media Outlet and Consumer Reactions to Promotional Activities of the Choose Health LA Restaurants Program in Los Angeles County.

    Science.gov (United States)

    Gase, Lauren N; Montes, Christine; Robles, Brenda; Tyree, Rachel; Kuo, Tony

    2016-01-01

    This study sought to assess promotional activities undertaken to raise public awareness of the Choose Health LA Restaurants program in Los Angeles County, an environmental change strategy that recognizes restaurants for offering reduced-size and healthier menu options. We used multiple methods to assess public awareness of and reactions to the promotional activities, including an assessment of the reach of core promotional activities, a content analysis of earned media, and an Internet panel survey. The study was conducted in Los Angeles County, home to more than 10 million residents. An online survey firm recruited participants for an Internet panel survey; to facilitate generalization of results to the county's population, statistical weights were applied to analyses of the survey data. Promotional activities to raise awareness of the program included community engagement, in-store promotion, and a media campaign. Outcomes included media impressions, the number of people who reported seeing the Choose Health LA Restaurants logo, and a description of the themes present in earned media. Collectively, paid media outlets reported 335 587 229 total impressions. The Internet panel survey showed that 12% of people reported seeing the program logo. Common themes in earned media included the Choose Health LA Restaurants program aims to provide restaurant patrons with more choices, represents a new opportunity for restaurants and public health to work together, will benefit participating restaurants, and will positively impact health. Promotional activities for the Choose Health LA Restaurants program achieved modest reach and positive reactions from media outlets and consumers. The program strategy and lessons learned can help inform present and future efforts to combine environmental and individually focused strategies that target key influences of consumer food selection.

  2. Interesterification reaction activity, fatty acid composition and selectivity ratio of soybean oil

    Directory of Open Access Journals (Sweden)

    El-Shattory, Y.

    1998-12-01

    Full Text Available The interesterification reaction was carried out by adding oleic acid to soybean oil by ratio 1:2 w/w under different conditions of temperature, stirring and catalyst percentages. Assessment of the interesterification of oils was reported by determination of saponification value, iodine value and fatty acids composition. This study showed that linolenic acid which is responsible for flavour instability of soybean oil and consider as primary factor contributing to deterioration of this oil could be reduced to less than or equals 3%.

    Se han llevado a cabo reacciones de interesterificación mediante la adición de ácido oleico a aceite de soja en la relación 1:2 w/w bajo diferentes condiciones de temperatura, agitación y porcentaje de catalizador. La evaluación de la interesterificación de los aceites se realizó por determinación del índice de saponificación, el índice de iodo y la composición en ácidos grasos. Este estudio mostró que el ácido linolénico, que es responsable de la inestabilidad del flavor del aceite de soja y considerado como factor primario que contribuye a la deterioración de este aceite, podría ser reducido a cantidades menores o iguales al 3%.

  3. The role of reaction pathways and support interactions in the development of high activity hydrotreating catalysts

    DEFF Research Database (Denmark)

    Topsøe, Henrik; Hinnemann, Berit; Nørskov, Jens Kehlet

    2005-01-01

    structures may be present as single sulfide sheets. Thus, stacking is not an essential feature of Type II catalysts. The article illustrates how the new scientific insight has aided the introduction of the new high activity BRIM (TM) type catalysts for FCC pre-treatment and production of ultra low sulfur...... exhibiting a metallic character are observed to be involved in adsorption, hydrogenation and C-S bond cleavage. The insight is seen to provide a new framework for understanding the DDS and HYD pathways and the role of steric hindrance and poisons. Density functional theory (DFT) calculations have illustrated...... how support interactions may influence the activity of sulfided catalysts. The brim sites and the tendency to form vacancies are seen to differ in types I and II Co-Mo-S. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) studies show that the high activity Type II...

  4. 125I-Fibrin deposition in contact sensitivity reactions in the mouse. Sensitivity of the assay for quantitating reactions after active or passive sensitization

    International Nuclear Information System (INIS)

    Mekori, Y.A.; Dvorak, H.F.; Galli, S.J.

    1986-01-01

    The clotting associated with delayed hypersensitivity (DH) responses in the mouse by sensitizing the animals to the contactant oxazolone (Ox), and then administering 125 I-guinea pig fibrinogen i.v. 10 to 30 min before antigen challenge 5 days later. Early (4 to 8 hr) contact sensitivity (CS) responses in immunized mice were barely detectable by three conventional measures of CS, but the total 125 I-cpm in ears challenged with hapten was 3.6 to 4.5 x that in control ears challenged with vehicle alone; moreover, the amount of urea-insoluble cpm (cross-linked 125 I-fibrin-associated cpm) in the reactions to Ox was 6.5-fold to 8.2-fold that present in the control reactions. In 24 hr reactions that were near peak intensity by measurements of ear swelling, ear weight ratios, and ratios of 125 I-5-iodo-2-deoxyuridine-labeled leukocyte infiltration, the cpm in antigen-challenged ears exceeded that in control ears by 13-fold to 53-fold. In addition, antigen-challenged ears contained 27 to 300 x the urea-insoluble cpm present in control ears. 125 I-Fibrin deposition was not a specific characteristic of CS reactions, because a small amount of urea-insoluble reactivity was also detected in some reactions to Ox in native mice. Nevertheless, the assay was exquisitely sensitive and readily detected quantitative differences between the immunologically specific and nonspecific reactions at very early intervals after challenge or with suboptimal doses of antigen

  5. Effects of some inhibitors of protein synthesis on the chloroplast fine structure, CO2 fixation and the Hill reaction activity

    Directory of Open Access Journals (Sweden)

    S. Więckowski

    2015-01-01

    Full Text Available A comparative study concerning the effects of chloramphenicol (100 μg ml-1, actidione (10 μg ml-1, 5-bromouracil (190 μg ml-1, actinomycin D (30 μg ml-1 and DL-ethionine (800 μg ml-1 on the chloroplast fine structure, 14CO2 incorporation and the Hill reaction activity was the subject of the experiments presented in this paper. The experiments were conducted on bean seedlings under the conditions when chlorophyll accumulation was inhibited only partially. The results obtained indicate that chloromphenicol is responsible for the reduction of the number of grana per section of plastid and for the formation of numerous vesicles in the stroma. In the presence of actidione, actinomycin D or DL-ethionine the lamellae are poorly differentiated into .stroma and granum regions and there occur disturbances in the typical orientation of lamellae within chloroplasts. Only in the presence of 5-bromouracil the development of chloroplast structure resemble that in control plants. A comparison of the results obtained with those published earlier (Więckowski et al., 1974; Ficek and Więckowski, 1974 shows that such processes as assimilatory pigment accumulation, the rate of CO2 fixation, the Hill reaction activity, and the development of lamellar system are suppressed in a different extent by the inhibitors used.

  6. Boosting Chemical Stability, Catalytic Activity, and Enantioselectivity of Metal-Organic Frameworks for Batch and Flow Reactions.

    Science.gov (United States)

    Chen, Xu; Jiang, Hong; Hou, Bang; Gong, Wei; Liu, Yan; Cui, Yong

    2017-09-27

    A key challenge in heterogeneous catalysis is the design and synthesis of heterogeneous catalysts featuring high catalytic activity, selectivity, and recyclability. Here we demonstrate that high-performance heterogeneous asymmetric catalysts can be engineered from a metal-organic framework (MOF) platform by using a ligand design strategy. Three porous chiral MOFs with the framework formula [Mn 2 L(H 2 O) 2 ] are prepared from enantiopure phosphono-carboxylate ligands of 1,1'-biphenol that are functionalized with 3,5-bis(trifluoromethyl)-, bismethyl-, and bisfluoro-phenyl substituents at the 3,3'-position. For the first time, we show that not only chemical stability but also catalytic activity and stereoselectivity of the MOFs can be tuned by modifying the ligand structures. Particularly, the MOF incorporated with -CF 3 groups on the pore walls exhibits enhanced tolerance to water, weak acid, and base compared with the MOFs with -F and -Me groups. Under both batch and flow reaction systems, the CF 3 -containing MOF demonstrated excellent reactivity, selectivity, and recyclability, affording high yields and enantioselectivities for alkylations of indoles and pyrrole with a range of ketoesters or nitroalkenes. In contrast, the corresponding homogeneous catalysts gave low enantioselectivity in catalyzing the tested reactions.

  7. Measurement method of activation cross-sections of reactions producing short-lived nuclei with 14 MeV neutrons

    CERN Document Server

    Kawade, K; Kasugai, Y; Shibata, M; Iida, T; Takahashi, A; Fukahori, T

    2003-01-01

    We describe a method for obtaining reliable activation cross-sections in the neutron energy range between 13.4 and 14.9 MeV for the reactions producing short-lived nuclei with half-lives between 0.5 and 30 min. We noted neutron irradiation fields and measured induced activities, including (1) the contribution of scattered low-energy neutrons, (2) the fluctuation of the neutron fluence rate during the irradiation, (3) the true coincidence sum effect, (4) the random coincidence sum effect, (5) the deviation in the measuring position due to finite sample thickness, (6) the self-absorption of the gamma-ray in the sample material and (7) the interference reactions producing the same radionuclides or the ones emitting the gamma-ray with the same energy of interest. The cross-sections can be obtained within a total error of 3.6%, when good counting statistics are achieved, including an error of 3.0% for the standard cross-section of sup 2 sup 7 Al (n, alpha) sup 2 sup 4 Na. We propose here simple methods for measuri...

  8. Effects of Maillard reaction products in a glucose-glycine alcoholic solution on antioxidative and antimutagenic activities.

    Science.gov (United States)

    Ko, Chih-Yuan; Chen, Xiao-Yu; Chang, Wen-Chang; Zeng, Yi-Ming; Lin, Ru-Hai; Zhang, Xiao-Bin; Wu, James Swi-Bea; Shen, Szu-Chuan

    2018-04-12

    Marinating meat with alcohol, such as wine and beer, is a common culinary practice in cultures worldwide. This study we use a model marination solution comprising 0.2 M glucose-0.2 M glycine buffered to pH 4.3 containing either 0% or 50% ethanol and mimicked the cooking process by heating for 12 h. Antioxidative and antimutagenic characteristics of Maillard reaction products (MRPs) were investigated. Reducing power, antioxidant activity (Fe 2+ chelating ability) and free radical neutralization ability generated from DPPH and ABTS were determined. Ames testing was performed. Results indicate that MRPs from aqueous and alcoholic solution exhibit four antioxidative assays in a dose-dependent manner from 0.16 to 10.00 mg mL -1 . However, MRPs from the alcoholic model was superior. In Ames testing, MRPs from both models are neither toxic nor mutagenic at the test concentrations of 0.63-10.00 mg plate -1 . However, MRPs from the alcoholic model exhibited a higher inhibitory effect on the direct-acting mutagen 4-NQNO compared to the aqueous model. This result is consistent with the observation that MRPs with higher antioxidative capacity exhibit superior antimutagenic activity, suggesting that there are more different products in the alcoholic model. Our results add to the current knowledge about the antioxidative and antimutagenic properties of Maillard reaction products arising when food is cooked in the presence of ethanol. This article is protected by copyright. All rights reserved.

  9. Catalytic activity in reactions of isotopic exchange of carbon monoxide and adsorption properties of catalysts on zinc oxide base

    International Nuclear Information System (INIS)

    Mikheeva, T.M.; Kasatkina, L.A.; Volynkina, A.Ya.

    1987-01-01

    Activity of different zinc oxide samples in reaction of CO homomolecular isotopic exchnge (HMIE) ( 13 C 18 O+ 12 C 16 O= 13 C 16 O+ 12 C 18 O), CO adsorption on ZnO and isotopic exchange between adsorbed and gaseous CO are investigated. The most active is ZnO sample prepared from ZnCO 3 . Quantitative ratio between different with respect to surface strength molecules of adsorbed CO are experimentally determined. It is shown that by increase of ZnO time contact with CO the quantity of adsorbed CO(N σ/0 ), capable of fast exchange with a gaseous phase, is reduced and the quantity of slowly exchanged adsorbed CO is increased. Correlation between decrease of N σ/0 and decrease of CO HMIE with the catalyst holding time in CO medium is stated

  10. New Insight into the Hydrogen Evolution Reaction under Buffered Near-Neutral pH Conditions: Enthalpy and Entropy of Activation

    KAUST Repository

    Shinagawa, Tatsuya; Takanabe, Kazuhiro

    2016-01-01

    performance was summarized with respect to the binding energy of the reaction intermediate species, a classic volcano-shaped relationship was obtained. Interestingly, the temperature sensitivity analysis disclosed that smaller activation energies did

  11. Antioxidant activity of the melanoidin fractions formed from D-Glucose and D-Fructose with L-Asparagine in the Maillard reaction

    Directory of Open Access Journals (Sweden)

    A.P Echavarría

    2013-01-01

    Full Text Available Melanoidins formed at the last stage of the Maillard reaction have been shown to possess certain functional properties, such as antioxidant activity. In order to gain more insight into these functional properties, soluble model systems melanoidins from L - Asparagine with D - glucose or D - fructose fractionating by ultrafiltration were analyzed. The fractionating/concentration sequence of the melanoidin fraction (1 - 300 kDa enabled five fractions to be produced. Additionally, the absorption of melanoidins was measured at different wavelengths (280, 325, 405 and browning at 420 nm. The fractionati on effect of melanoidin systems on the color intensity, UV - absorbance scan wavelengths (nm, CIE, L*, a*, b* parameters and antioxidant activity were measured. For this purpose, antioxidant activity was evaluated through the free radical scavenging activit y, including 1,1 - diphenyl - 2 - picryl - hydrazil (DPPH and 2,20 - azinobis (3 - ethylbenothiazoline - 6 - sulfonic acid, diammonium salt (ABTS. The results showed that the absorption of the melanoidins formed from Glucose/L - Asn was higher than for those derived from Fructose/L - Asn. On the other hand, their antioxidant power was lower than that for melanoidins formed from Fructose/L - Asn systems.

  12. Electrochemical probing into the active sites of graphitic-layer encapsulated iron oxygen reduction reaction electrocatalysts

    DEFF Research Database (Denmark)

    Zhong, Lijie; Jensen, Jens Oluf; Cleemann, Lars Nilausen

    2018-01-01

    is still unclear compared with the well-recognized surface coordinated FeNx/C structure. Using the strong complexing effect of the iron component with anions, cyanide (CN−) in alkaline and thiocyanate (SCN−) in acidic media, the metal containing active sites are electrochemically probed. Three...

  13. A Catalytically Active Membrane Reactor for Fast, Highly Exothermic, Heterogeneous Gas Reactions. A Pilot Plant Study

    NARCIS (Netherlands)

    Veldsink, Jan W.; Versteeg, Geert F.; Swaaij, Wim P.M. van

    1995-01-01

    Membrane reactors have been frequently studied because of their ability to combine chemical activity and separation properties into one device. Due to their thermal stability and mechanical strength, ceramic membranes are preferred over polymeric ones, but small transmembrane fluxes obstruct a

  14. Reactions to Humorous Sexual Stimuli as a Function of Sexual Activeness and Satisfaction.

    Science.gov (United States)

    Prerost, Frank J.

    1984-01-01

    Assessed male (N=60) and female (N=60) responses to pictorial humorous sexual material in relationship to degree of sexual expression and personal satisfaction with sexual behavior. Results showed persons with active and satisfying sexual expression enjoyed sexually explicit cartoons and showed less preference for aggressive themes. (LLL)

  15. Catalytic activity of metall-like carbides in carbon oxide oxidation reaction

    International Nuclear Information System (INIS)

    Kharlamov, A.I.; Kosolapova, T.Ya.; Rafal, A.N.; Kirillova, N.V.

    1980-01-01

    Kinetics of carbon oxide oxidation upon carbides of hafnium, niobium, tantalum, molybdenum, zirconium and chromium is studied. Probable mechanism of the catalysts action is suggested. The established character of the change of the carbide catalytic activity is explained by the change of d-electron contribution to the metal-metal interaction

  16. Adaptive and innate immune reactions regulating mast cell activation: from receptor-mediated signaling to responses

    DEFF Research Database (Denmark)

    Tkaczyk, Christine; Jensen, Bettina M; Iwaki, Shoko

    2006-01-01

    differentially activate multiple signaling pathways within the mast cells required for the generation and/or release of inflammatory mediators. Thus, the composition of the suite of mediators released and the physiologic ramifications of these responses are dependent on the stimuli and the microenvironment...

  17. Quantification of the histochemical reaction for alkaline phosphatase activity using the indoxyl-tetranitro BT method

    NARCIS (Netherlands)

    van Noorden, C. J.; Jonges, G. N.

    1987-01-01

    The indoxyl-tetranitro BT method for the demonstration of alkaline phosphatase activity has been optimized and its validity for quantitative histochemistry tested. The study has been performed with model films of polyacrylamide gel incorporating homogenate of rat liver and with cryostat sections

  18. Boosting the Performance of the Nickel Anode in the Oxygen Evolution Reaction by Simple Electrochemical Activation

    KAUST Repository

    Shinagawa, Tatsuya; Ng, Marcus Tze-Kiat; Takanabe, Kazuhiro

    2017-01-01

    The development of cost-effective and active water-splitting electrocatalysts that work at mild pH is an essential step towards the realization of sustainable energy and material circulation in our society. Its success requires a drastic improvement

  19. Nuclear chemistry research of high-energy nuclear reactions at Carnegie-Mellon University, 1961--1977. Summary report. [Summaries of research activities at Carnegie-Mellon University

    Energy Technology Data Exchange (ETDEWEB)

    Caretto, A.A. Jr.

    1977-11-01

    The activities and the results of research in the study of high energy nuclear reactions carried out at Carnegie Institute of Technology from 1957 to 1967 and at Carnegie-Mellon University from 1967 to 1977 are summarized. A complete list of all publications, doctoral dissertations, and reports resulting from the research of this project is also included. A major part of the report is a review of the research activities and results. The objective of the research of this project was the study of reactions initiated by projectiles of energy above about 100 MeV. The main effort was the investigation of simple nuclear reactions with the objective to deduce reaction mechanisms. These reactions were also used as probes to determine the nuclear structure of the target. In addition, a number of studies of spallation reactions were undertaken which included the determination of excitation functions and recoil properties. Recent research activities which have involved the study of pion induced reactions as well as reactions initiated by heavy ions is also discussed.

  20. Infusion Reactions Associated with the Medical Application of Monoclonal Antibodies: The Role of Complement Activation and Possibility of Inhibition by Factor H

    OpenAIRE

    Tamás Fülöp; Tamás Mészáros; Gergely Tibor Kozma; János Szebeni; Mihály Józsi

    2018-01-01

    Human application of monoclonal antibodies (mAbs), enzymes, as well as contrast media and many other particulate drugs and agents referred to as “nanomedicines”, can initiate pseudoallergic hypersensitivity reactions, also known as infusion reactions. These may in part be mediated by the activation of the complement system, a major humoral defense system of innate immunity. In this review, we provide a brief outline of complement activation-related pseudoallergy (CARPA) in general, and then f...

  1. Precise 238U(n,2n)237U reaction cross-section measurements using the activation facility at TUNL

    Science.gov (United States)

    Krishichayan, Fnu; Bhike, M.; Tornow, W.

    2014-09-01

    Accurate neutron-induced 238U(n,2n)237U reaction data are required for many practical applications, especially in the field of nuclear energy, including advanced heavy water reactors, where 238U is used as the breeding material to regenerate the fissile material 239Pu. Precise (n,2n) cross-section measurements of 238U are underway at TUNL with mono-energetic neutrons in the 8.0 to 14.0 MeV energy range in steps of 0.25 MeV using the activation technique. After activation of the 0.5 inch diameter and 442 mg 238U foil, the activity of the 208 keV characteristic γ-line is tracked for 6 weeks with a high efficient HPGe clover detector to determine the initial activity needed for the cross-section determination. Results of the cross-section measurements, determined relative to 27Al and 197Au neutron activation monitor foils, and the comparison with theoretical models will be presented during the meeting.

  2. Evaluation and Enhancement of the Oxygen Reduction Reaction Activity on Hafnium Oxide Nanoparticles Assisted by L(+)-lysine

    International Nuclear Information System (INIS)

    Chisaka, Mitsuharu; Itagaki, Noriaki

    2016-01-01

    Evaluation of the oxygen reduction reaction (ORR) on oxide compounds is difficult owing to the insulating nature of oxides. In this study, various amounts of L(+)-lysine were added to the precursor dispersion for the hydrothermal synthesis of hafnium oxide nanoparticles on reduced graphene oxide sheets (HfO_x–rGO) to coat the HfO_x catalysts with layers of carbon, thereby increasing the conductivity and number of active sites. When the mass ratio of L(+)-lysine to GO, R, was above 26, carbon layers were formed and the amount monotonically increased with increasing R, as noted by cyclic voltammogrametry. X-ray photoelectron spectroscopy and rotating disk electrode analyses revealed that pyrolysis produced ORR-active oxygen defects, whose formation was proposed to involve carbothermal reduction. When 53 ≤ R ≤ 210, HfO_x–rGO contained a similar amount of oxygen defects and ORR activity, as represented by an onset potential of 0.9 V versus the reversible hydrogen electrode in 0.1 mol dm"−"3 H_2SO_4. However, the number of active sites depended on R due to the amount of L(+)-lysine-derived carbon layers that increased both the number of active sites and resistivity towards oxygen diffusion.

  3. Electro-activation of sweet defatted whey: Impact on the induced Maillard reaction products and bioactive peptides.

    Science.gov (United States)

    Kareb, Ourdia; Gomaa, Ahmed; Champagne, Claude P; Jean, Julie; Aïder, Mohammed

    2017-04-15

    Electro-activation was used to add value to sweet defatted whey. This study aimed to investigate and to characterize the bioactive compounds formed under different electro-activation conditions by molecular and proteomic approaches. The effects of electric current intensity (400, 500 or 600mA) and whey concentration (7, 14 or 21% (w/v)) as a function of the electro-activation time (0, 15, 30 or 45min) were evaluated. The targeted dependent variables were the formation of Maillard reaction products (MRPs), protein hydrolysates and glycated compounds. It was shown that the MRPs derived from electro-activated whey at a concentration of 14% had the highest potential of biological activity. SDS-PAGE analyses indicated the formation of hydrolysates and glycated compounds with different molecular weight distributions. FTIR indicated the predominance of intermediate MRPs, such as the Schiff base compounds. LC-MS/MS and proteomics analysis showed the production of multi-functional bioactive peptides due to the hydrolysis of whey proteins. Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.

  4. Female PFP patients present alterations in eccentric muscle activity but not the temporal order of activation of the vastus lateralis muscle during the single leg triple hop test.

    Science.gov (United States)

    Kalytczak, Marcelo Martins; Lucareli, Paulo Roberto Garcia; Dos Reis, Amir Curcio; Bley, André Serra; Biasotto-Gonzalez, Daniela Aparecida; Correa, João Carlos Ferrari; Politti, Fabiano

    2018-04-07

    This study aimed to compare the concentric and eccentric activity and the temporal order of peak activity of the hip and knee muscles between women with patellofemoral pain (PFP) and healthy women during the single leg triple hop test (SLTHT). Electromyographic (EMG) and Kinematic data were collected from 14 healthy women (CG) and 14 women diagnosed with PFP (PFG) during a single session of the single leg triple hop test. Integral surface electromyography (iEMG) data of the hip and knee muscles in eccentric and concentric phases and the length of time that each muscle needed to reach the maximal peak of muscle activity were calculated. The iEMG in the eccentric phase was significantly higher (p < 0.05) than the concentric phase, for the gluteus maximus and gluteus medius muscles (CG and PFG) and for the vastus lateralis muscle (PFG). The vastus lateralis muscle was the first muscle to reach the highest peak of activity in the PFG, and the third to reach this peak in the CG. In the present study, the activity of the vastus lateralis muscle during the eccentric phase of the jump was greater than concentric phase, as a temporal anticipation of its peak in activity among women with PFP. Copyright © 2018 Elsevier B.V. All rights reserved.

  5. Activity and Stability of RuOx Based Electrocatalysts for the Oxygen Evolution Reaction

    DEFF Research Database (Denmark)

    Paoli, Elisa Antares

    . By coupling Electrochemical Quartz Crystal Microbalance (EQCM) measurements with Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) analyses of the electrolyte, we emphasize the importance of monitoring the mass loss. Finally, the thesis focuses on improving the stability of ruthenium dioxide under OER...... results show that an improvement of stability can be obtained, slightly decreasing the activity as well. Unfortunately, a drastic enhancement, as hoped, was not detected. Instead the results serve as a starting point from which the strategy and method for stability improvements can be further developed....... activity on oxides and studies on well-defined surfaces are required. Notably, industrial applications demand maximized surface-to-bulk ratio, hence fabrication of catalysts in nanoparticulate form. In this perspective, this project aimed at investigating well-defined mass-selected ruthenium and ruthenium...

  6. Improvement of Evaluated Nuclear Data Files with Emphasis on Activation and Dosimetry Reactions

    International Nuclear Information System (INIS)

    Trkov, A.

    2013-01-01

    Researchers from the Jozef Stefan Institute are actively involved in the development of the fusion technology through the Slovenian Fusion Association. Neutronics calculations are one of the key areas of expertise and FENDL library is the reference library for the ITER device. The quality of the nuclear data library is therefore of great concern, which drives the motivation for participation in the CRP. Specific contributions to the CRP are briefly described

  7. Enhanced Bacterial α(2,6-Sialyltransferase Reaction through an Inhibition of Its Inherent Sialidase Activity by Dephosphorylation of Cytidine-5'-Monophosphate.

    Directory of Open Access Journals (Sweden)

    Ji-Yeon Kang

    Full Text Available Bacterial α(2,6-sialyltransferases (STs from Photobacterium damsela, Photobacterium sp. JT-ISH-224, and P. leiognathi JT-SHIZ-145 were recombinantly expressed in Escherichia coli and their ST activities were compared directly using a galactosylated bi-antennary N-glycan as an acceptor substrate. In all ST reactions, there was an increase of sialylated glycans at shorter reaction times and later a decrease in prolonged reactions, which is related with the inherent sialidase activities of bacterial STs. These sialidase activities are greatly increased by free cytidine monophosphate (CMP generated from a donor substrate CMP-N-acetylneuraminic acid (CMP-Neu5Ac during the ST reactions. The decrease of sialylated glycans in prolonged ST reaction was prevented through an inhibition of sialidase activity by simple treatment of alkaline phosphatase (AP, which dephosphorylates CMP to cytidine. Through supplemental additions of AP and CMP-Neu5Ac to the reaction using the recombinant α(2,6-ST from P. leiognathi JT-SHIZ-145 (P145-ST, the content of bi-sialylated N-glycan increased up to ~98% without any decrease in prolonged reactions. This optimized P145-ST reaction was applied successfully for α(2,6-sialylation of asialofetuin, and this resulted in a large increase in the populations of multi-sialylated N-glycans compared with the reaction without addition of AP and CMP-Neu5Ac. These results suggest that the optimized reaction using the recombinant P145-ST readily expressed from E. coli has a promise for economic glycan synthesis and glyco-conjugate remodeling.

  8. Reduced-order model based active disturbance rejection control of hydraulic servo system with singular value perturbation theory.

    Science.gov (United States)

    Wang, Chengwen; Quan, Long; Zhang, Shijie; Meng, Hongjun; Lan, Yuan

    2017-03-01

    Hydraulic servomechanism is the typical mechanical/hydraulic double-dynamics coupling system with the high stiffness control and mismatched uncertainties input problems, which hinder direct applications of many advanced control approaches in the hydraulic servo fields. In this paper, by introducing the singular value perturbation theory, the original double-dynamics coupling model of the hydraulic servomechanism was reduced to a integral chain system. So that, the popular ADRC (active disturbance rejection control) technology could be directly applied to the reduced system. In addition, the high stiffness control and mismatched uncertainties input problems are avoided. The validity of the simplified model is analyzed and proven theoretically. The standard linear ADRC algorithm is then developed based on the obtained reduced-order model. Extensive comparative co-simulations and experiments are carried out to illustrate the effectiveness of the proposed method. Copyright © 2017 ISA. Published by Elsevier Ltd. All rights reserved.

  9. Enhanced photo-catalytic activity of ordered mesoporous indium oxide nanocrystals in the conversion of CO2 into methanol.

    Science.gov (United States)

    Gondal, M A; Dastageer, M A; Oloore, L E; Baig, U; Rashid, S G

    2017-07-03

    Ordered mesoporous indium oxide nanocrystal (m-In 2 O 3 ) was synthesized by nanocasting technique, in which highly ordered mesoporous silca (SBA-15) was used as structural matrix. X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halanda (BJH) studies were carried out on m-In 2 O 3 and the results revealed that this material has a highly ordered mesoporous surface with reduced grain size, increased surface area and surface volume compared to the non porous indium oxide. The diffuse reluctance spectrum exhibited substantially improved light absorption efficiency in m-In 2 O 3 compared to normal indium oxide, however, no considerable change in the band gap energies of these materials was observed. When m-In 2 O 3 was used as a photo-catalyst in the photo-catalytic process of converting carbon dioxide (CO 2 ) into methanol under the pulsed laser radiation of 266-nm wavelengths, an enhanced photo-catalytic activity with the quantum efficiency of 4.5% and conversion efficiency of 46.3% were observed. It was found that the methanol production yield in this chemical process is as high as 485 µlg -1 h -1 after 150 min of irradiation, which is substantially higher than the yields reported in the literature. It is quite clear from the results that the introduction of mesoporosity in indium oxide, and the consequent enhancement of positive attributes required for a photo-catalyst, transformed photo-catalytically weak indium oxide into an effective photo-catalyst for the conversion of CO 2 into methanol.

  10. A neural model for temporal order judgments and their active recalibration: a common mechanism for space and time?

    Directory of Open Access Journals (Sweden)

    Mingbo eCai

    2012-11-01

    Full Text Available When observers experience a constant delay between their motor actions and sensory feedback, their perception of the temporal order between actions and sensations adapt (Stetson et al., 2006a. We present here a novel neural model that can explain temporal order judgments (TOJs and their recalibration. Our model employs three ubiquitous features of neural systems: 1 information pooling, 2 opponent processing, and 3 synaptic scaling. Specifically, the model proposes that different populations of neurons encode different delays between motor-sensory events, the outputs of these populations feed into rivaling neural populations (encoding before and after, and the activity difference between these populations determines the perceptual judgment. As a consequence of synaptic scaling of input weights, motor acts which are consistently followed by delayed sensory feedback will cause the network to recalibrate its point of subjective simultaneity. The structure of our model raises the possibility that recalibration of TOJs is a temporal analogue to the motion aftereffect. In other words, identical neural mechanisms may be used to make perceptual determinations about both space and time. Our model captures behavioral recalibration results for different numbers of adapting trials and different adapting delays. In line with predictions of the model, we additionally demonstrate that temporal recalibration can last through time, in analogy to storage of the motion aftereffect.

  11. Chemical characteristics and enhanced hepatoprotective activities of Maillard reaction products derived from milk protein-sugar system.

    Science.gov (United States)

    Oh, Nam Su; Young Lee, Ji; Lee, Hyun Ah; Joung, Jae Yeon; Shin, Yong Kook; Kim, Sae Hun; Kim, Younghoon; Lee, Kwang Won

    2016-02-01

    The objective of this study was to investigate the characteristics, antioxidative properties, and hepatoprotective effects of Maillard reaction products (MRP) from milk protein reacted with sugars. The MRP were obtained from milk protein, whey protein concentrates and sodium caseinate, using 2 types of sugars, lactose and glucose, by heating the mixture at 55°C for 7d in a sodium phosphate buffer (pH 7.4). Changes in the chemical modification of the milk protein were monitored by measuring the protein-bound carbonyls and PAGE protein profiles. The results showed that the amount of protein-bound carbonyls increased after Maillard reaction (MR). In addition, sodium dodecyl sulfate-PAGE analysis indicated a formation of high-molecular weight complexes through MR. The modification sites induced by MR of milk protein were monitored by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis of tryptic-digested gel spots of MRP. As a result, modification and their localization in AA sequence of MRP was identified. Also, the MRP showed higher antioxidant activities than the intact milk protein, and they reduced intracellular reactive oxygen species production and inhibited the depletion of the reduced glutathione concentrations in the HepG2 cells. In particular, glucose-sodium caseinate MRP showed the highest biological activities among all MRP. Therefore, these results suggest that the MRP from milk protein reacting with sugars possess effective antioxidant activity and have a protective ability against oxidative damage. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  12. Effect of reaction environments on the reactivity of PCB (2-chlorobiphenyl) over activated carbon impregnated with palladized iron

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Hyeok [Department of Civil Engineering, University of Texas at Arlington, 416 Yates Drive, Arlington, TX 76019-0308 (United States); Al-Abed, Souhail R., E-mail: al-abed.souhail@epa.gov [National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 West Martin Luther King Drive, Cincinnati, OH 45268 (United States)

    2010-07-15

    Reactive activated carbon (RAC) impregnated with palladized iron nanoparticles has been developed to treat polychlorinated biphenyls (PCBs). In this study, we evaluated the effects of various reaction environments on the adsorption-mediated dechlorination of 2-chlorobiphenyl (2-ClBP) in the RAC system. The results were discussed in close connection to the implementation issue of the RAC system for the remediation of contaminated sites with PCBs. Adsorption event of 2-ClBP onto RAC limited the overall performance under condition with a 2-ClBP/RAC mass ratio of less than 1.0 x 10{sup -4} above which dechlorination of 2-ClBP adsorbed to RAC was the reaction rate-determining step. Acidic and basic conditions were harmful to 2-ClBP adsorption and iron stability while neutral pH showed the highest adsorption-promoted dechlorination of 2-ClBP and negligible metal leaching. Coexisting natural organic matter (NOM) slightly inhibited 2-ClBP adsorption onto RAC due to the partial partitioning of 2-ClBP into NOM in the liquid phase while the 2-ClBP absorbed into NOM, which also tended to adsorb onto RAC, was less available for the dechlorination reaction. Common anions slowed down 2-ClBP adsorption but adsorbed 2-ClBP was almost simultaneously dechlorinated. Some exceptions included strong inhibitory effect of carbonate species on 2-ClBP adsorption and severe detrimental effect of sulfite on 2-ClBP dechlorination. Results on treatment of 2-ClBP spiked to actual sediment supernatants implied site-specific reactivity of RAC.

  13. Pt skin coated hollow Ag-Pt bimetallic nanoparticles with high catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Fu, Tao; Huang, Jianxing; Lai, Shaobo; Zhang, Size; Fang, Jun; Zhao, Jinbao

    2017-10-01

    The catalytic activity and stability of electrocatalyst is critical for the commercialization of fuel cells, and recent reports reveal the great potential of the hollow structures with Pt skin coat for developing high-powered electrocatalysts due to their highly efficient utilization of the Pt atoms. Here, we provide a novel strategy to prepare the Pt skin coated hollow Ag-Pt structure (Ag-Pt@Pt) of ∼8 nm size at room temperature. As loaded on the graphene, the Ag-Pt@Pt exhibits a remarkable mass activity of 0.864 A/mgPt (at 0.9 V, vs. reversible hydrogen electrode (RHE)) towards oxygen reduction reaction (ORR), which is 5.30 times of the commercial Pt/C catalyst, and the Ag-Pt@Pt also shows a better stability during the ORR catalytic process. The mechanism of this significant enhancement can be attributed to the higher Pt utilization and the unique Pt on Ag-Pt surface structure, which is confirmed by the density functional theory (DFT) calculations and other characterization methods. In conclusion, this original work offers a low-cost and environment-friendly method to prepare a high active electrocatalyst with cheaper price, and this work also discloses the correlation between surface structures and ORR catalytic activity for the hollow structures with Pt skin coat, which can be instructive for designing novel advanced electrocatalysts for fuel cells.

  14. Incorporation of tantalum ions enhances the electrocatalytic activity of hexagonal WO3 nanowires for hydrogen evolution reaction

    International Nuclear Information System (INIS)

    Xie, Xiang; Mu, Wanjun; Li, Xingliang; Wei, Hongyuan; Jian, Yuan; Yu, Qianhong; Zhang, Rui; Lv, Kai; Tang, Hui; Luo, Shunzhong

    2014-01-01

    WO 3 has been identified as a promising candidate electrocatalyst for hydrogen evolution reaction (HER), because it can form a tungsten bronze (HxWO 3 ) which is highly electron and proton conducting. In this paper, we report that the electrocatalytic activity of WO 3 for HER can be enhanced by incorporation of tantalum ions (Ta 5+ ) into the lattice of WO 3 . The most active performance is achieved with the molar ratio of Ta/W being 0.01, which is two times more active than that of undoped WO 3 at an overpotential of -0.52 V. It is shown that incorporation of proper Ta 5+ into WO 3 can induce moderate defects and oxygen vacancies, as well as intercalate a higher amount of protons, which enhance the electron transfer and short the protons diffusion paths. These changes correlated positively with the enhanced catalytic HER activity. This study demonstrates, for the first time, that metal ions-doped WO 3 nanowires are promising electrocatalysts for HER

  15. Activities of some enzymes of lignin formation in reaction wood of Thuja orientalis, Metasequoia glyptostroboides and Robinia pseudoacacia.

    Science.gov (United States)

    Kutsuki, H; Higuchi, T

    1981-07-01

    The activities of the following five enzymes which are involved in the formation of lignin have been compared in reaction wood and in opposite wood: phenylalanine ammonia lyase (EC 4.3.1.5), caffeate 3-O-methyltransferase (EC 2.1.1.-), p-hydroxycinnamate: CoA ligase (EC 6.2.1.12), cinnamyl alcohol dehydrogenase (EC 1.1.1.-) and peroxidase (EC 1.11.1.7). The activities of the four first-named enzymes in the compression wood of Thuja orientalis L. and Metasequoia glyptostroboides Hu et Cheng were 2.8±1.4-fold and 2.6±1.5-fold higher than those in opposite wood, respectively, whereas peroxidase had the same level of activity in either type of wood. On the other hand, no differences were observed in the activities of the five enzymes between tension and opposite woods of Robinia pseudoacacia L. These findings are well in accord with the chemical structure of lignin in the compression and tension woods of the three species studied: high content of lignin rich in condensed units in compression wood, and little difference in lignin between tension and opposite woods.

  16. Carbon Supported Engineering NiCo2O4 Hybrid Nanofibers with Enhanced Electrocatalytic Activity for Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Diab Hassan

    2016-09-01

    Full Text Available The design of cheap and efficient oxygen reduction reaction (ORR electrocatalysts is of a significant importance in sustainable and renewable energy technologies. Therefore, ORR catalysts with superb electrocatalytic activity and durability are becoming a necessity but still remain challenging. Herein, we report C/NiCo2O4 nanocomposite fibers fabricated by a straightforward electrospinning technique followed by a simple sintering process as a promising ORR electrocatalyst in alkaline condition. The mixed-valence oxide can offer numerous accessible active sites. In addition, the as-obtained C/NiCo2O4 hybrid reveals significantly remarkable electrocatalytic performance with a highly positive onset potential of 0.65 V, which is only 50 mV lower than that of commercially available Pt/C catalysts. The analyses indicate that C/NiCo2O4 catalyst can catalyze O2-molecules via direct four electron pathway in a similar behavior as commercial Pt/C catalysts dose. Compared to single NiCo2O4 and carbon free NiCo2O4, the C/NiCo2O4 hybrid displays higher ORR current and more positive half-wave potential. The incorporated carbon matrices are beneficial for fast electron transfer and can significantly impose an outstanding contribution to the electrocatalytic activity. Results indicate that the synthetic strategy hold a potential as efficient route to fabricate highly active nanostructures for practical use in energy technologies.

  17. Green synthesis of silver nanoparticles using Prosopis juliflora bark extract: reaction optimization, antimicrobial and catalytic activities.

    Science.gov (United States)

    Arya, Geeta; Kumari, R Mankamna; Gupta, Nidhi; Kumar, Ajeet; Chandra, Ramesh; Nimesh, Surendra

    2017-07-18

    In the present study, silver nanoparticles (PJB-AgNPs) have been biosynthesized employing Prosopis juliflora bark extract. The biosynthesis of silver nanoparticles was monitored on UV-vis spectrophotometer. The size, charge and polydispersity index (PDI) of PJB-AgNPs were determined using dynamic light scattering (DLS). Different parameters dictating the size of PJB-AgNPs were explored. Nanoparticles biosynthesis optimization studies suggested efficient synthesis of highly dispersed PJB-AgNPs at 25 °C when 9.5 ml of 1 mM AgNO 3 was reduced with 0.5 ml of bark extract for 40 min. Characterization of PJB-AgNPs by SEM showed spherical-shaped nanoparticles with a size range ∼10-50 nm along with a hydrodynamic diameter of ∼55 nm as evaluated by DLS. Further, characterizations were done by FTIR and EDS to evaluate the functional groups and purity of PJB-AgNPs. The antibacterial potential of PJB-AgNPs was tested against E. coli and P. aeruginosa. The PJB-AgNPs remarkably exhibited anticancer activity against A549 cell line as evidenced by Alamar blue assay. The dye degradation activity was also evaluated against 4-nitrophenol that has carcinogenic effect. The results thus obtained suggest application of PJB-AgNPs as antimicrobial, anticancer and catalytic agents.

  18. The role of chemokines and chemokine receptors in eosinophil activation during inflammatory allergic reactions

    Directory of Open Access Journals (Sweden)

    Oliveira S.H.P.

    2003-01-01

    Full Text Available Chemokines are important chemotactic cytokines that play a fundamental role in the trafficking of leukocytes to sites of inflammation. They are also potent cell-activating factors, inducing cytokine and histamine release and free radical production, a fact that makes them particularly important in the pathogenesis of allergic inflammation. The action of chemokines is regulated at the level of agonist production and processing as well as at the level of receptor expression and coupling. Therefore, an analysis of the ligands must necessarily consider receptors. Eosinophils are target cells involved in the allergic inflammatory response since they are able to release a wide variety of mediators including CC and CXC chemokines and express their receptors. These mediators could damage the airway epithelial cells and might be important to stimulate other cells inducing an amplification of the allergic response. This review focuses on recently emerging data pertaining to the importance of chemokines and chemokine receptors in promoting eosinophil activation and migration during the allergic inflammatory process. The analysis of the function of eosinophils and their chemokine receptors during allergic inflammation might be a good approach to understanding the determinants of asthma severity and to developing novel therapies.

  19. Activation cross sections of deuteron induced reactions on niobium in the 30–50 MeV energy range

    International Nuclear Information System (INIS)

    Ditrói, F.; Tárkányi, F.; Takács, S.; Hermanne, A.; Ignatyuk, A.V.

    2016-01-01

    Highlights: • Deuteron induced nuclear reactions on natural niobium up to 50 MeV. • Stacked foil irradiation technique. • Comparison of results with the ALICE-D, EMPIRE-D and TENDL-2015 calculations. • Application of radioisotopes in medicine and industry. - Abstract: Activation cross-sections of deuterons induced reactions on Nb targets were determined with the aim of different applications and comparison with theoretical models. We present the experimental excitation functions of "9"3Nb(d,x)"9"3"m","9"0Mo, "9"2"m","9"1"m","9"0Nb, "8"9","8"8Zr and "8"8","8"7"m","8"7"gY in the energy range of 30–50 MeV. The results were compared with earlier measurements and with the cross-sections calculated by means of the theoretical model codes ALICE-D, EMPIRE-D and TALYS (on-line TENDL-2014 and TENDL-2015 libraries). Possible applications of the radioisotopes are discussed in detail.

  20. Effect of interfering reactions on the determination of iodine-129 concentrations in the enviroment by activation analysis

    International Nuclear Information System (INIS)

    Filistovich, V.; Nedvetskajte, T.

    1985-01-01

    The influence of the interfering reactions sup(235)U(n, f) sup(129)In(n, γ)sup(130)I, sup(128)Te(n, γ)sup(129)Te, sup(129)Te(Tsub(1/2)sup(βsup(-))=69.6 min) sup(129)I(n, γ)sup(130)I and sup(127)I(3n, γ)sup(130)I on the measurements by the activation analysis method of the background sup(129)I concentrations in the environment has been investigated. The calculations have shown that these reactions may result in considerable errors. A pretreatment of samples before their irradiation in a reactor is therefore needed. It is recommended to use the destructive distillation method. A nomogram is given with the help of which it is possible to determine the optimal time for the sample irradiation in the reactor after the sup(127)I concentrations have bee nevaluated in the samples, because the considerable amount of the sup(129)I can be generated from the sup(127)I by the triple neutron capture

  1. New porphyrin-polyoxometalate hybrid materials: synthesis, characterization and investigation of catalytic activity in acetylation reactions.

    Science.gov (United States)

    Araghi, Mehdi; Mirkhani, Valiollah; Moghadam, Majid; Tangestaninejad, Shahram; Mohammdpoor-Baltork, Iraj

    2012-10-14

    New hybrid complexes based on covalent interaction between 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatozinc(II) and 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatotin(IV) chloride, and a Lindqvist-type polyoxometalate, Mo(6)O(19)(2-), were prepared. These new porphyrin-polyoxometalate hybrid materials were characterized by (1)H NMR, FT IR and UV-Vis spectroscopic methods and cyclic voltammetry. These spectro- and electrochemical studies provided several spectral data for synthesis of these compounds. Cyclic voltammetry showed the influence of the polyoxometalate on the redox process of the porphyrin ring. The catalytic activity of tin(IV)porphyrin-hexamolybdate hybrid material was investigated in the acetylation of alcohols and phenols with acetic anhydride. The reusability of this catalyst was also investigated.

  2. Dendritic cells for active immunotherapy: optimizing design and manufacture in order to develop commercially and clinically viable products.

    Science.gov (United States)

    Nicolette, C A; Healey, D; Tcherepanova, I; Whelton, P; Monesmith, T; Coombs, L; Finke, L H; Whiteside, T; Miesowicz, F

    2007-09-27

    Dendritic cell (DC) active immunotherapy is potentially efficacious in a broad array of malignant disease settings. However, challenges remain in optimizing DC-based therapy for maximum clinical efficacy within manufacturing processes that permit quality control and scale-up of consistent products. In this review we discuss the critical issues that must be addressed in order to optimize DC-based product design and manufacture, and highlight the DC based platforms currently addressing these issues. Variables in DC-based product design include the type of antigenic payload used, DC maturation steps and activation processes, and functional assays. Issues to consider in development include: (a) minimizing the invasiveness of patient biological material collection; (b) minimizing handling and manipulations of tissue at the clinical site; (c) centralized product manufacturing and standardized processing and capacity for commercial-scale production; (d) rapid product release turnaround time; (e) the ability to manufacture sufficient product from limited starting material; and (f) standardized release criteria for DC phenotype and function. Improvements in the design and manufacture of DC products have resulted in a handful of promising leads currently in clinical development.

  3. PsB multiprotein complex of Dictyostelium discoideum. Demonstration of cellulose binding activity and order of protein subunit assembly.

    Science.gov (United States)

    McGuire, V; Alexander, S

    1996-06-14

    The differentiated spores of Dictyostelium are surrounded by an extracellular matrix, the spore coat, which protects them from environmental factors allowing them to remain viable for extended periods of time. This presumably is a major evolutionary advantage. This unique extracellular matrix is composed of cellulose and glycoproteins. Previous work has shown that some of these spore coat glycoproteins exist as a preassembled multiprotein complex (the PsB multiprotein complex) which is stored in the prespore vesicles (Watson, N., McGuire, V., and Alexander, S (1994) J. Cell Sci. 107, 2567-2579). Later in development, the complex is synchronously secreted from the prespore vesicles and incorporated into the spore coat. We now have shown that the PsB complex has a specific in vitro cellulose binding activity. The analysis of mutants lacking individual subunits of the PsB complex revealed the relative order of assembly of the subunit proteins and demonstrated that the protein subunits must be assembled for cellulose binding activity. These results provide a biochemical explanation for the localization of this multiprotein complex in the spore coat.

  4. Ga-Doped Pt-Ni Octahedral Nanoparticles as a Highly Active and Durable Electrocatalyst for Oxygen Reduction Reaction.

    Science.gov (United States)

    Lim, JeongHoon; Shin, Hyeyoung; Kim, MinJoong; Lee, Hoin; Lee, Kug-Seung; Kwon, YongKeun; Song, DongHoon; Oh, SeKwon; Kim, Hyungjun; Cho, EunAe

    2018-04-11

    Bimetallic PtNi nanoparticles have been considered as a promising electrocatalyst for oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs) owing to their high catalytic activity. However, under typical fuel cell operating conditions, Ni atoms easily dissolve into the electrolyte, resulting in degradation of the catalyst and the membrane-electrode assembly (MEA). Here, we report gallium-doped PtNi octahedral nanoparticles on a carbon support (Ga-PtNi/C). The Ga-PtNi/C shows high ORR activity, marking an 11.7-fold improvement in the mass activity (1.24 A mg Pt -1 ) and a 17.3-fold improvement in the specific activity (2.53 mA cm -2 ) compared to the commercial Pt/C (0.106 A mg Pt -1 and 0.146 mA cm -2 ). Density functional theory calculations demonstrate that addition of Ga to octahedral PtNi can cause an increase in the oxygen intermediate binding energy, leading to the enhanced catalytic activity toward ORR. In a voltage-cycling test, the Ga-PtNi/C exhibits superior stability to PtNi/C and the commercial Pt/C, maintaining the initial Ni concentration and octahedral shape of the nanoparticles. Single cell using the Ga-PtNi/C exhibits higher initial performance and durability than those using the PtNi/C and the commercial Pt/C. The majority of the Ga-PtNi nanoparticles well maintain the octahedral shape without agglomeration after the single cell durability test (30,000 cycles). This work demonstrates that the octahedral Ga-PtNi/C can be utilized as a highly active and durable ORR catalyst in practical fuel cell applications.

  5. Bactericidal activity of self-assembled palmitic and stearic fatty acid crystals on highly ordered pyrolytic graphite.

    Science.gov (United States)

    Ivanova, Elena P; Nguyen, Song Ha; Guo, Yachong; Baulin, Vladimir A; Webb, Hayden K; Truong, Vi Khanh; Wandiyanto, Jason V; Garvey, Christopher J; Mahon, Peter J; Mainwaring, David E; Crawford, Russell J

    2017-09-01

    The wings of insects such as cicadas and dragonflies have been found to possess nanostructure arrays that are assembled from fatty acids. These arrays can physically interact with the bacterial cell membranes, leading to the death of the cell. Such mechanobactericidal surfaces are of significant interest, as they can kill bacteria without the need for antibacterial chemicals. Here, we report on the bactericidal effect of two of the main lipid components of the insect wing epicuticle, palmitic (C16) and stearic (C18) fatty acids. Films of these fatty acids were re-crystallised on the surface of highly ordered pyrolytic graphite. It appeared that the presence of two additional CH 2 groups in the alkyl chain resulted in the formation of different surface structures. Scanning electron microscopy and atomic force microscopy showed that the palmitic acid microcrystallites were more asymmetric than those of the stearic acid, where the palmitic acid microcrystallites were observed to be an angular abutment in the scanning electron micrographs. The principal differences between the two types of long-chain saturated fatty acid crystallites were the larger density of peaks in the upper contact plane of the palmitic acid crystallites, as well as their greater proportion of asymmetrical shapes, in comparison to that of the stearic acid film. These two parameters might contribute to higher bactericidal activity on surfaces derived from palmitic acid. Both the palmitic and stearic acid crystallite surfaces displayed activity against Gram-negative, rod-shaped Pseudomonas aeruginosa and Gram-positive, spherical Staphylococcus aureus cells. These microcrystallite interfaces might be a useful tool in the fabrication of effective bactericidal nanocoatings. Nanostructured cicada and dragonfly wing surfaces have been discovered to be able physically kill bacterial cells. Here, we report on the successful fabrication of bactericidal three-dimensional structures of two main lipid

  6. Luminescence Properties of Self-Activated Mm(VO4)2 (M = Mg, Ca, Sr, and Ba) Phosphors Synthesized by Solid-State Reaction Method.

    Science.gov (United States)

    Min, Xin; Huang, Zhaohui; Fang, Minghao; Liu, Yan'gai; Tang, Chao; Wu, Xiaowen

    2016-04-01

    In this paper, M3(VO4)2 (M = Mg, Ca, Sr, and Ba) self-activated phosphors were prepared by a solid-state reaction method at 1,000 °C for 5 h. The phase formation and micrographs were analyzed by X-ray diffraction and scanning electron microscopy. The Ca3(VO4)2 phosphor does not show any emission peaks under excitation with ultraviolet (UV) light. However, the M3(VO4)2 (M = Mg, Sr, and Ba) samples are effectively excited by UV light chips ranging from 200 nm to 400 nm and exhibit broad emission bands due to the charge transfer from the oxygen 2p orbital to the vacant 3d orbital of the vanadium in the VO4. The color of these phosphors changes from yellow to light blue via blue-green with increasing ionic radius from Mg to Sr to Ba. The luminescence lifetimes and quantum yield decrease with the increasing unit cell volume and V-V distance, in the order of Mg3(VO4)2 to Sr3(VO4)2 to Ba3(VO4)2. The emission intensity decreases with the increase of temperatures, but presents no color shift. This confirms that these self-activated M3(VO4)2 phosphors can be suggested as candidates of the single-phase phosphors for light using UV light emitting diodes (LEDs).

  7. Oxygen plasma etching of graphene: A first-principles dynamical inspection of the reaction mechanisms and related activation barriers

    Science.gov (United States)

    Koizumi, Kenichi; Boero, Mauro; Shigeta, Yasuteru; Oshiyama, Atsushi; Dept. of Applied Physics Team; Institute of Physics and Chemistry of Strasbourg (IPCMS) Collaboration; Department Of Materials Engineering Science Collaboration

    2013-03-01

    Oxygen plasma etching is a crucial step in the fabrication of electronic circuits and has recently received a renovated interest in view of the realization of carbon-based nanodevices. In an attempt at unraveling the atomic-scale details and to provide guidelines for the control of the etching processes mechanisms, we inspected the possible reaction pathways via reactive first principles simulations. These processes involve breaking and formation of several chemical bonds and are characterized by different free-energy barriers. Free-energy sampling techniques (metadynamics and blue moon), used to enhance the standard Car-Parrinello molecular dynamics, provide us a detailed microscopic picture of the etching of graphene surfaces and a comprehensive scenario of the activation barriers involved in the various steps. MEXT, Japan - contract N. 22104005

  8. Activation analysis of thallium by /sup 203/Tl(n,2n)/sup 202/Tl reaction in nuclear reactors

    Energy Technology Data Exchange (ETDEWEB)

    Cohen, I M; Resnizky, S M; Baro, G B [Comision Nacional de Energia Atomica, Buenos Aires (Argentina). Gerencia de Radioisotopos y Radiaciones

    1982-01-01

    Two techniques are described for neutron activation analysis of thallium in biological and geological materials, based on /sup 203/Tl(n,2n)/sup 202/Tl reaction in nuclear reactors. Co-precipitation with bismuth sulphide is used as a pre-concentration method of thallium in urine samples, and post-irradiation chemical separation is also performed. The detection limit is 0.5 ..mu..g/l, for 100 ml urine samples. For thallium determination in blendes a radiochemical separation is carried out after the irradiation. An extension of this technique is presented for glass and silicate rocks. Results for seven blende samples from different places of Argentina are shown. Analysis of two reference materials, the 614 glass from the National Bureau of Standards and the granodiorite GSP-1 from the U.S. Geological Survey were also performed. The results are in very good agreement with the certified or estimated values.

  9. Ag_3PO_4 Microcrystals Synthesized by Room-Temperature Solid State Reaction: Enhanced Photocatalytic Activity and Photoelectronchemistry Performance

    International Nuclear Information System (INIS)

    Hao Chen-Chun; Xu Jie; Shi Hong-Long; Fu Jun-Li; Zou Bin; Meng Shan; Wang Wen-Zhong; Jia Ying

    2015-01-01

    Ag_3PO_4 microcrystals with highly enhanced visible light photocatalytic activity are prepared by a facile and simple solid state reaction at room temperature. The composition, morphology and optical properties of the as-prepared Ag_3PO_4 microcrystals are characterized by x-ray diffraction, scanning electron microscopy and UV-vis diffuse reflectance spectra. The photocatalytic properties of Ag_3PO_4 are investigated by the degradation of both methylene blue and methyl orange dyes under visible light irradiation. The as-prepared Ag_3PO_4 microcrystals possess high photocatalytic oxygen production with the rate of 673 μmolh"−"1 g"−"1. Moreover, the as-prepared Ag_3PO_4 microcrystals show an enhanced photoelectrochemistry performance under irradiation of visible light. (paper)

  10. Direct synthesis of acid-base bifunctionalized hexagonal mesoporous silica and its catalytic activity in cascade reactions.

    Science.gov (United States)

    Shang, Fanpeng; Sun, Jianrui; Wu, Shujie; Liu, Heng; Guan, Jingqi; Kan, Qiubin

    2011-03-01

    A series of efficient acid-base bifunctionalized hexagonal mesoporous silica (HMS) catalysts contained aminopropyl and propanesulfonic acid have been synthesized through a simple co-condensation by protection of amino group. The results of small-angle XRD, TEM, and N(2) adsorption-desorption measurements show that the resultant materials have mesoscopic structures. X-ray photoelectron spectroscopies, elemental analysis (EA), back titration, (29)Si NMR and (13)C NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The resultant catalysts exhibit excellent acid-basic properties, which make them possess high activity for one-pot deacetalization-Knoevenagel and deacetalization-nitroaldol (Henry) reactions. Copyright © 2010 Elsevier Inc. All rights reserved.

  11. Accessing simply-substituted 4-hydroxytetrahydroisoquinolines via Pomeranz–Fritsch–Bobbitt reaction with non-activated and moderately-activated systems

    Directory of Open Access Journals (Sweden)

    Marco Mottinelli

    2017-09-01

    Full Text Available Background: 1,2,3,4-Tetrahydroisoquinolines (THIQs are common motifs in alkaloids and in medicinal chemistry. Synthetic access to THIQs via the Pomeranz–Fritsch–Bobbit (PFB methodology using mineral acids for deactivated, electron-poor aromatic systems, is scarcely represented in the literature. Here, the factors controlling the regiochemical outcome of cyclization are evaluated.Results: A double reductive alkylation was telescoped into a one-pot reaction delivering good to excellent yields of desired aminoacetals for cyclization. Cyclization of activated systems proceeded smoothly under standard PFB conditions, but for non-activated systems the use of HClO4 alone was effective. When cyclization was possible in both para- and ortho-positions to the substituent, 7-substituted derivatives were formed with significant amounts of 5-substituted byproduct. The formation of the 4-hydroxy-THIQs vs the 4-methoxy-THIQ products could be controlled through modification of the reaction concentration. In addition, while a highly-activated system exclusively cyclized to the indole, this seems generally highly disfavored. When competition between 6- and 7-ring formation was investigated in non-activated systems, 5,7,8,13-tetrahydro-6,13-methanodibenzo[c,f]azonine was exclusively obtained. Furthermore, selective ring closure in the para-position could be achieved under standard PFB conditions, while a double ring closure could be obtained utilizing HClO4.Conclusion: Reactivity differences in aminoacetal precursors can be employed to control cyclization using the PFB methodology. It is now possible to select confidently the right conditions for the synthesis of N-aryl-4-hydroxy-1,2,3,4-tetrahydroisoquinolines.

  12. Accessing simply-substituted 4-hydroxytetrahydroisoquinolines via Pomeranz–Fritsch–Bobbitt reaction with non-activated and moderately-activated systems

    Science.gov (United States)

    Mottinelli, Marco; Leese, Mathew P

    2017-01-01

    Background: 1,2,3,4-Tetrahydroisoquinolines (THIQs) are common motifs in alkaloids and in medicinal chemistry. Synthetic access to THIQs via the Pomeranz–Fritsch–Bobbit (PFB) methodology using mineral acids for deactivated, electron-poor aromatic systems, is scarcely represented in the literature. Here, the factors controlling the regiochemical outcome of cyclization are evaluated. Results: A double reductive alkylation was telescoped into a one-pot reaction delivering good to excellent yields of desired aminoacetals for cyclization. Cyclization of activated systems proceeded smoothly under standard PFB conditions, but for non-activated systems the use of HClO4 alone was effective. When cyclization was possible in both para- and ortho-positions to the substituent, 7-substituted derivatives were formed with significant amounts of 5-substituted byproduct. The formation of the 4-hydroxy-THIQs vs the 4-methoxy-THIQ products could be controlled through modification of the reaction concentration. In addition, while a highly-activated system exclusively cyclized to the indole, this seems generally highly disfavored. When competition between 6- and 7-ring formation was investigated in non-activated systems, 5,7,8,13-tetrahydro-6,13-methanodibenzo[c,f]azonine was exclusively obtained. Furthermore, selective ring closure in the para-position could be achieved under standard PFB conditions, while a double ring closure could be obtained utilizing HClO4. Conclusion: Reactivity differences in aminoacetal precursors can be employed to control cyclization using the PFB methodology. It is now possible to select confidently the right conditions for the synthesis of N-aryl-4-hydroxy-1,2,3,4-tetrahydroisoquinolines. PMID:29062406

  13. Accessing simply-substituted 4-hydroxytetrahydroisoquinolines via Pomeranz-Fritsch-Bobbitt reaction with non-activated and moderately-activated systems.

    Science.gov (United States)

    Mottinelli, Marco; Leese, Mathew P; Potter, Barry V L

    2017-01-01

    Background: 1,2,3,4-Tetrahydroisoquinolines (THIQs) are common motifs in alkaloids and in medicinal chemistry. Synthetic access to THIQs via the Pomeranz-Fritsch-Bobbit (PFB) methodology using mineral acids for deactivated, electron-poor aromatic systems, is scarcely represented in the literature. Here, the factors controlling the regiochemical outcome of cyclization are evaluated. Results: A double reductive alkylation was telescoped into a one-pot reaction delivering good to excellent yields of desired aminoacetals for cyclization. Cyclization of activated systems proceeded smoothly under standard PFB conditions, but for non-activated systems the use of HClO 4 alone was effective. When cyclization was possible in both para - and ortho -positions to the substituent, 7-substituted derivatives were formed with significant amounts of 5-substituted byproduct. The formation of the 4-hydroxy-THIQs vs the 4-methoxy-THIQ products could be controlled through modification of the reaction concentration. In addition, while a highly-activated system exclusively cyclized to the indole, this seems generally highly disfavored. When competition between 6- and 7-ring formation was investigated in non-activated systems, 5,7,8,13-tetrahydro-6,13-methanodibenzo[ c , f ]azonine was exclusively obtained. Furthermore, selective ring closure in the para- position could be achieved under standard PFB conditions, while a double ring closure could be obtained utilizing HClO 4 . Conclusion: Reactivity differences in aminoacetal precursors can be employed to control cyclization using the PFB methodology. It is now possible to select confidently the right conditions for the synthesis of N- aryl-4-hydroxy-1,2,3,4-tetrahydroisoquinolines.

  14. Artificial Chemical Reporter Targeting Strategy Using Bioorthogonal Click Reaction for Improving Active-Targeting Efficiency of Tumor.

    Science.gov (United States)

    Yoon, Hong Yeol; Shin, Min Lee; Shim, Man Kyu; Lee, Sangmin; Na, Jin Hee; Koo, Heebeom; Lee, Hyukjin; Kim, Jong-Ho; Lee, Kuen Yong; Kim, Kwangmeyung; Kwon, Ick Chan

    2017-05-01

    Biological ligands such as aptamer, antibody, glucose, and peptide have been widely used to bind specific surface molecules or receptors in tumor cells or subcellular structures to improve tumor-targeting efficiency of nanoparticles. However, this active-targeting strategy has limitations for tumor targeting due to inter- and intraheterogeneity of tumors. In this study, we demonstrated an alternative active-targeting strategy using metabolic engineering and bioorthogonal click reaction to improve tumor-targeting efficiency of nanoparticles. We observed that azide-containing chemical reporters were successfully generated onto surface glycans of various tumor cells such as lung cancer (A549), brain cancer (U87), and breast cancer (BT-474, MDA-MB231, MCF-7) via metabolic engineering in vitro. In addition, we compared tumor targeting of artificial azide reporter with bicyclononyne (BCN)-conjugated glycol chitosan nanoparticles (BCN-CNPs) and integrin α v β 3 with cyclic RGD-conjugated CNPs (cRGD-CNPs) in vitro and in vivo. Fluorescence intensity of azide-reporter-targeted BCN-CNPs in tumor tissues was 1.6-fold higher and with a more uniform distribution compared to that of cRGD-CNPs. Moreover, even in the isolated heterogeneous U87 cells, BCN-CNPs could bind artificial azide reporters on tumor cells more uniformly (∼92.9%) compared to cRGD-CNPs. Therefore, the artificial azide-reporter-targeting strategy can be utilized for targeting heterogeneous tumor cells via bioorthogonal click reaction and may provide an alternative method of tumor targeting for further investigation in cancer therapy.

  15. Stabilization of silver nanoparticles in nonanoic acid: A temperature activated conformation reaction observed with surface enhanced Raman spectroscopy

    International Nuclear Information System (INIS)

    Henneke, Dale E.; Malyavanatham, Gokul; Kovar, Desiderio; O'Brien, D.T.; Becker, M.F.; Nichols, William T.; Keto, J.W.

    2003-01-01

    Silver nanoparticles were synthesized by ultraviolet (λ=248 nm) laser ablation of an aerosol of micron-sized source particles entrained in nitrogen. As a result of thermionic electron emission and photoionization, nanoparticles produced in this manner were highly charged. The resulting aerosol was primarily composed of nanometer sized particles. The charged nanoparticles were deflected by an electric field that was perpendicular to the aerosol flow. Deflected nanoparticles were deposited directly into n-nonanoic acid flowing along the negative collection electrode. Suspensions of nanoparticles collected in this manner were dark gray in color and were found to be flocculated. When the suspensions were heated to temperatures above 75 deg. C, a color change from gray to clear was observed. Ultraviolet/visible extinction spectroscopy was performed on each suspension following annealing at different temperatures and times. By modeling the absorption decrease as a first order reaction, a good fit for the data was found. Analysis by dynamic light scattering (DLS) showed that the initial mean flocculent size of the gray suspensions was 602 nm. DLS analysis of the suspensions taken at different annealing intervals showed that the flocculent size decreased, but maintained a narrow size distribution until the size shrank below the instrument resolution limit. The reduction in flocculent size coincided with the observed color change, and an irreversible transition to a deflocculated primary nanoparticle suspension is observed. Surface enhanced Raman scattering is used to confirm that the reaction results from a change in the orientation of the nonanoic molecule on the surface of the nanoparticle

  16. Impact of reaction vessel pressure on the synthesis of sliced activated carbon from date palm tree fronds

    Directory of Open Access Journals (Sweden)

    Shoaib Muhammad

    2015-01-01

    Full Text Available The effects of the reaction vessel pressure on the BET surface area, pore volume and pore size of the synthesis of sliced activated carbons (SAC at 850°C starting from 0.10 to 0.40 bars were investigated. Other synthetic variables like dwell time, CO2 flow rate and heating ramp rate were kept constant during the whole study. Methodology involves a single step procedure using the mixture of gases (N2 and CO2. During activation flow rate of both gases are kept at 150 and 50ml/min respectively. The BET surface areas of the SAC prepared at 0.10, 0.15, 0.20, 0.25, 0.30, 0.35 and 0.40 bar after 30 minutes activation time are 666, 745, 895, 1094, 835, 658 and 625 m2/g, respectively. Scanning electron microscopy (SEM for surface morphology, Energy dispersive spectroscopy (EDS, Transmission electron microscopy (TEM for nano particle size were also carried out that also confirms the same trend.

  17. Synthesis of a highly active carbon-supported Ir-V/C catalyst for the hydrogen oxidation reaction in PEMFC

    International Nuclear Information System (INIS)

    Li Bing; Qiao Jinli; Yang Daijun; Zheng Junsheng; Ma Jianxin; Zhang Jiujun; Wang Haijiang

    2009-01-01

    The active, carbon-supported Ir and Ir-V nanoclusters with well-controlled particle size, dispersity, and composition uniformity, have been synthesized via an ethylene glycol method using IrCl 3 and NH 4 VO 3 as the Ir and V precursors. The nanostructured catalysts were characterized by X-ray diffraction and high-resolution transmission electron microscopy. The catalytic activities of these carbon-supported nanoclusters were screened by applying on-line cyclic voltammetry and electrochemical impedance spectroscopy techniques, which were used to characterize the electrochemical properties of fuel cells using several anode Ir/C and Ir-V/C catalysts. It was found that Ir/C and Ir-V/C catalysts affect the performance of electrocatalysts significantly based on the discharge characteristics of the fuel cell. The catalyst Ir-V/C at 40 wt.% displayed the highest catalytic activity to hydrogen oxidation reaction and, therefore, high cell performance is achieved which results in a maximum power density of 563 mW cm -2 at 0.512 V and 70 deg. C in a real H 2 /air fuel cell. This performance is 20% higher as compared to the commercial available Pt/C catalyst. Fuel cell life test at a constant current density of 1000 mA cm -2 in a H 2 /O 2 condition shows good stability of anode Ir-V/C after 100 h of continuous operation.

  18. Chemisorption on size-selected metal clusters: activation barriers and chemical reactions for deuterium and aluminum cluster ions

    International Nuclear Information System (INIS)

    Jarrold, M.F.; Bower, J.E.

    1988-01-01

    The authors describe a new approach to investigating chemisorption on size-selected metal clusters. This approach involves investigating the collision-energy dependence of chemisorption using low-energy ion beam techniques. The method provides a direct measure of the activation barrier for chemisorption and in some cases an estimate of the desorption energy as well. They describe the application of this technique to chemisorption of deuterium on size-selected aluminum clusters. The activation barriers increase with cluster size (from a little over 1 eV for Al 10 + to around 2 eV for Al 27 + ) and show significant odd-even oscillations. The activation barriers for the clusters with an odd number of atoms are larger than those for the even-numbered clusters. In addition to chemisorption of deuterium onto the clusters, chemical reactions were observed, often resulting in cluster fragmentation. The main products observed were Al/sub n-1/D + , Al/sub n-2/ + , and Al + for clusters with n + and Al/sub n-1/D + for the larger clusters

  19. On the relationship between lower extremity muscles activation and peak vertical and posterior ground reaction forces during single leg drop landing.

    Science.gov (United States)

    Mahaki, M; Mi'mar, R; Mahaki, B

    2015-10-01

    Anterior cruciate ligament (ACL) injury continues to be an important medical issue for athletes participating in sports. Vertical and posterior ground reaction forces have received considerable attention for their potential influence on ACL injuries. The purpose of this study was to examine the relationship between electromyographic activity of lower extremity muscles and the peak vertical and posterior ground reaction forces during single leg drop landing. Thirteen physical education male students participated in this correlation study. Electromyographic activities of gluteus medius, biceps femoris, medial gastrocnemius, soleus as well as anterior tibialis muscles along with ground reaction forces were measured. Participants performed single-leg landing from a 0.3 m height on to a force platform. Landing was divided into two phases: 100 ms preceding ground contact and 100 ms proceeding ground contact. Pearson correlation test was used to determine the relationships between these muscles activity and peak vertical and posterior ground reaction forces. The results of the study indicated that the activity of soleus and tibialis anterior in pre-landing phase were positively correlated with peak vertical ground reaction force ([P≤0.04], [P≤0.008], respectively). However, no significant correlation was found between the activities of other muscles in pre-landing phase and peak vertical as well as peak posterior ground reaction forces. Also, no significant correlation was found between the activities of muscles in post-landing phase and peak vertical as well as peak posterior ground reaction forces. Soleus loading shifts the proximal tibia posterior at the knee joint and tibialis anterior prevent hyperporonation of the ankle, a mechanisms of ACL injury. Hence, neuromuscular training promoting preparatory muscle activity in these muscles may reduce the incidence of ACL injuries.

  20. Activation analysis of rare-earth elements in opium and cannabis samples. [Neutron reactions

    Energy Technology Data Exchange (ETDEWEB)

    Henke, G [Muenster Univ. (Germany, F.R.). Inst. fuer Pharmazeutische Chemie

    1977-01-01

    Rare-earth concentrations in 65 Opium, Cannabis and Cannabis resin samples seized from various parts of the world were determined by destructive NAA. Because of the greater concentrations of Ca, P, K, Fe, Na and Si in plant materials, rare-earth elements were isolated after neutron irradiation and determined by gamma-spectrometry. The main steps of the method are: Preashing of 1 g Cannabis resin, 2.5 g Cannabis, or 7.5 g Opium, respectively, in quartz ampoules (5 h, 500 deg C). Neutron irradiation, 24 h at 5x10/sup 13/n cm/sup -2/sec/sup -1/. Cooling period 2-3 days. After addition of 0.1 ..mu..Ci /sup 139/Ce and rare-earth carriers wet ashing of irradiated samples with H/sub 2/SO/sub 4//HNO/sub 3/, followed by alternate addition of HNO/sub 3/ and H/sub 2/O/sub 2/ (30%). Precipitation and removal of silicates, precipitation of fluorides, precipitation of hydroxides. Dissolution of hydroxides in HCl. Extraction with di-(2-ethylhexyl)phosphate (DEHP)/toluene and twice back-extraction of rare earths, gamma-spectrometry of HCl phase. Due to sample activity and half-life of nuclides, three measurements were made on each sample: 2 days (for La, Sm, Gd, Ho, Er, Yb); 14 days (for Nd, Lu) and 30 days after irradiation (for Ce, Eu, Tb). Great variations in absolute element concentrations, but only small significant differences of rare earth concentration ratios were found, indicating inconsiderable biogeochemical fractionation. The mean values of these ratios correspond to the relative abundances of the rare earths in the upper continental earth's crust.

  1. Differential cell reaction upon Toll-like receptor 4 and 9 activation in human alveolar and lung interstitial macrophages

    Directory of Open Access Journals (Sweden)

    Meyerhans Andreas

    2010-09-01

    Full Text Available Abstract Background Investigations on pulmonary macrophages (MΦ mostly focus on alveolar MΦ (AM as a well-defined cell population. Characteristics of MΦ in the interstitium, referred to as lung interstitial MΦ (IM, are rather ill-defined. In this study we therefore aimed to elucidate differences between AM and IM obtained from human lung tissue. Methods Human AM and IM were isolated from human non-tumor lung tissue from patients undergoing lung resection. Cell morphology was visualized using either light, electron or confocal microscopy. Phagocytic activity was analyzed by flow cytometry as well as confocal microscopy. Surface marker expression was measured by flow cytometry. Toll-like receptor (TLR expression patterns as well as cytokine expression upon TLR4 or TLR9 stimulation were assessed by real time RT-PCR and cytokine protein production was measured using a fluorescent bead-based immunoassay. Results IM were found to be smaller and morphologically more heterogeneous than AM, whereas phagocytic activity was similar in both cell types. HLA-DR expression was markedly higher in IM compared to AM. Although analysis of TLR expression profiles revealed no differences between the two cell populations, AM and IM clearly varied in cell reaction upon activation. Both MΦ populations were markedly activated by LPS as well as DNA isolated from attenuated mycobacterial strains (M. bovis H37Ra and BCG. Whereas AM expressed higher amounts of inflammatory cytokines upon activation, IM were more efficient in producing immunoregulatory cytokines, such as IL10, IL1ra, and IL6. Conclusion AM appear to be more effective as a non-specific first line of defence against inhaled pathogens, whereas IM show a more pronounced regulatory function. These dissimilarities should be taken into consideration in future studies on the role of human lung MΦ in the inflammatory response.

  2. Differential effect of gamma-irradiated and heat-treated lymphocytes on T cell activation, and interleukin-2 and interleukin-3 release in the human mixed lymphocyte reaction

    International Nuclear Information System (INIS)

    Loertscher, R.; Abbud-Filho, M.; Leichtman, A.B.; Ythier, A.A.; Williams, J.M.; Carpenter, C.B.; Strom, T.B.

    1987-01-01

    Heat-inactivated (45 degrees C/1 hr) lymphocytes selectively activate suppressor T cells in the mixed lymphocyte reaction (MLR), while no significant proliferation and cytotoxic T lymphocyte activation can be detected. It is not well understood why hyperthermic treatment abolishes the stimulatory capacity of lymphocytes since HLA-DR molecules remain detectable immediately following heat exposure. In order to further characterize the requirements for Ts activation we studied the effects of hyperthermic treatment on cellular protein and DNA synthesis and cell surface protein expression in proliferating T and B cells; interleukin (IL)-1, IL-2, and IL-3 release following allogeneic stimulation with heat treated cells (HMLR); and IL-2 receptor expression as an indicator of T cell activation in the HMLR. Hyperthermic treatment reduced cellular protein synthesis as estimated by 14 C-leucine uptake to about 15%, and DNA synthesis ( 3 H-thymidine incorporation) to about 5% of untreated control cells. In contrast to y-irradiated cells, viability of heated cells rapidly declined within the first 24 hr. Hyperthermic treatment doubled binding of mouse immunoglobulin paralleled by an increased expression of IL-2 and transferrin receptors, while expression of HLA-DR and 4F2 proteins appeared unchanged. Stimulation with heated cells triggered the release of IL-1- and an IL-3-like bioactivity but did not induce IL-2 synthesis and/or release, thus explaining the lack of proliferation in the HMLR. Addition of exogenous IL-2 but not IL-1 restored HMLR proliferation. A comparison of allostimulation with y-irradiated and heat-treated cells revealed that significantly fewer T cells were induced to express IL-2 receptors at day 3 (14% vs. 8%, P less than 0.001) and at day 6 (42% vs. 21%, P less than 0.05) with heat-inactivated stimulators

  3. High catalytic activity and stability of Ni/CexZr1-xO2/MSU-H for CH4/CO2 reforming reaction

    Science.gov (United States)

    Chang, Xiaoqian; Liu, Bingsi; Xia, Hong; Amin, Roohul

    2018-06-01

    How to reduce emission of CO2 as greenhouse gases, which resulted in global warming, is of very important significance. A series of Ni/CexZr1-xO2/MSU-H catalysts was prepared by means of hexagonally ordered mesoporous MSU-H with thermal and hydrothermal stabilities, which is cheap and can be synthesized in the large scale. The 10%Ni/Ce0.75Zr0.25O2/MSU-H catalyst presents high catalytic activity, stability and the ability of coke-resistance for CH4/CO2 reforming reaction due to high SBET (428 m2/g) and smaller Nio nanoparticle size (3.14 nm). The high dispersed Nio nanoparticles over MSU-H promoted the decomposition of CH4 and the carbon species accumulated on active Nio sites reacting with crystal lattice oxygen in Ce0.75Zr0.25O2 to form CO molecules. In the meantime, the remained oxygen vacancies on the interface between Nio and Ce0.75Zr0.25O2 could be supplemented via CO2. HRTEM images and XRD results of Ni/Ce0.75Zr0.25O2/MSU-H verified that high dispersion of Ni nanoparticles over Ni/Ce0.75Zr0.25O2/MSU-H correlated closely with the synergistic action between Ce0.75Zr0.25O2 and MSU-H as well as hexagonally ordered structure of MSU-H, which can provide effectively the oxygen storage capacity and inhibit the formation of coke.

  4. Improving the electrocatalytic performance of carbon nanotubes for VO{sup 2+}/VO{sub 2}{sup +} redox reaction by KOH activation

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Lei; Jiang, Yingqiao; Meng, Wei; Zhou, Huizhu [School of Chemical Engineering, North China University of Science and Technology, Tangshan 063009 (China); Wang, Ling, E-mail: tswling@126.com [School of Chemical Engineering, North China University of Science and Technology, Tangshan 063009 (China); He, Zhangxing, E-mail: zxhe@ncst.edu.cn [School of Chemical Engineering, North China University of Science and Technology, Tangshan 063009 (China); State Key Laboratory Breeding Base of Nuclear Resources and Environment, East China Institute of Technology, Nanchang 330013 (China)

    2017-04-15

    Highlights: • KOH-activated carbon nanotubes (CNTs) was investigated as superior catalyst for VO{sup 2+}/VO{sub 2}{sup +} redox reaction for vanadium redox flow battery (VRFB) for the first time. • KOH activation for CNTs can result in the chemical etching of surface and improved wettability, accelerating the mass transfer of vanadium ions. • KOH activation can introduce many oxygen-containing groups as active sites on the surface of CNTs. • KOH-activated CNTs as positive catalyst could increase the comprehensive energy storage performance of VRFB. - Abstract: In this paper, carbon nanotubes (CNTs) was activated by KOH treatment at high temperature and investigated as catalyst for VO{sup 2+}/VO{sub 2}{sup +} redox reaction for vanadium redox flow battery (VRFB). X-ray photoelectron spectroscopy results suggest that the oxygen-containing groups can be introduced on CNTs by KOH activation. The mass transfer of vanadium ions can be accelerated by chemical etching by KOH activation and improved wettability due to the introduction of hydrophilic groups. The electrochemical properties of VO{sup 2+}/VO{sub 2}{sup +} redox reaction can be enhanced by introduced oxygen-containing groups as active sites. The sample treated at 900 °C with KOH/CNTs mass ratio of 3:1 (CNTs-3) exhibits the highest electrocatalytic activity for VO{sup 2+}/VO{sub 2}{sup +} redox reaction. The cell using CNTs-3 as positive catalyst demonstrates the smallest electrochemical polarization, the highest capacity and efficiency among the samples. Using KOH-activated CNTs-3 can increase the average energy efficiency of the cell by 4.4%. This work suggests that KOH-activated CNTs is a low-cost, efficient and promising catalyst for VO{sup 2+}/VO{sub 2}{sup +} redox reaction for VRFB system.

  5. Real-time investigation of human topoisomerase I reaction kinetics using an optical sensor: a fast method for drug screening and determination of active enzyme concentrations

    Science.gov (United States)

    Kristoffersen, Emil L.; Jørgensen, Line A.; Franch, Oskar; Etzerodt, Michael; Frøhlich, Rikke; Bjergbæk, Lotte; Stougaard, Magnus; Ho, Yi-Ping; Knudsen, Birgitta R.

    2015-05-01

    Human DNA topoisomerase I (hTopI) is a nuclear enzyme that catalyzes relaxation of super helical tension that arises in the genome during essential DNA metabolic processes. This is accomplished through a common reaction mechanism shared among the type IB topoisomerase enzymes, including eukaryotic and poxvirus topoisomerase I. The mechanism of hTopI is specifically targeted in cancer treatment using camptothecin derivatives. These drugs convert the hTopI activity into a cellular poison, and hence the cytotoxic effects of camptothecin derivatives correlate with the hTopI activity. Therefore, fast and reliable techniques for high throughput measurements of hTopI activity are of high clinical interest. Here we demonstrate potential applications of a fluorophore-quencher based DNA sensor designed for measurement of hTopI cleavage-ligation activities, which are the catalytic steps affected by camptothecin. The kinetic analysis of the hTopI reaction with the DNA sensor exhibits a characteristic burst profile. This is the result of a two-step ping-pong reaction mechanism, where a fast first reaction, the one creating the signal, is followed by a slower second reaction necessary for completion of the catalytic cycle. Hence, the burst profile holds information about two reactions in the enzymatic mechanism. Moreover, it allows the amount of active enzyme in the reaction to be determined. The presented results pave the way for future high throughput drug screening and the potential of measuring active hTopI concentrations in clinical samples for individualized treatment.Human DNA topoisomerase I (hTopI) is a nuclear enzyme that catalyzes relaxation of super helical tension that arises in the genome during essential DNA metabolic processes. This is accomplished through a common reaction mechanism shared among the type IB topoisomerase enzymes, including eukaryotic and poxvirus topoisomerase I. The mechanism of hTopI is specifically targeted in cancer treatment using

  6. Reaction of 3-Amino-1,2,4-Triazole with Diethyl Phosphite and Triethyl Orthoformate: Acid-Base Properties and Antiosteoporotic Activities of the Products.

    Science.gov (United States)

    Miszczyk, Patrycja; Wieczorek, Dorota; Gałęzowska, Joanna; Dziuk, Błażej; Wietrzyk, Joanna; Chmielewska, Ewa

    2017-02-08

    The reaction of diethyl phosphite with triethyl orthoformate and a primary amine followed by hydrolysis is presented, and the reaction was suitable for the preparation of (aminomethylene)bisphosphonates. 3-Amino-1,2,4-triazole was chosen as an interesting substrate for this reaction because it possesses multiple groups that can serve as the amino component in the reaction-namely, the side-chain and triazole amines. This substrate readily forms 1,2,4-triazolyl-3-yl-aminomethylenebisphosphonic acid (compound 1 ) as a major product, along with N -ethylated bisphosphonates as side products. The in vitro antiproliferative effects of the synthesized aminomethylenebisphosphonic acids against J774E macrophages were determined. These compounds exhibit similar activity to zoledronic acid and higher activity than incadronic acid.

  7. Multi-day activity scheduling reactions to planned activities and future events in a dynamic model of activity-travel behavior

    NARCIS (Netherlands)

    Nijland, L.; Arentze, T.A.; Timmermans, H.J.P.

    2014-01-01

    Modeling multi-day planning has received scarce attention in activity-based transport demand modeling so far. However, new dynamic activity-based approaches are being developed at the current moment. The frequency and inflexibility of planned activities and events in activity schedules of

  8. Multi-Day Activity Scheduling Reactions to Planned Activities and Future Events in a Dynamic Model of Activity-Travel Behavior

    NARCIS (Netherlands)

    Nijland, L.; Arentze, T.; Timmermans, H.

    2014-01-01

    Modeling multi-day planning has received scarce attention in activity-based transport demand modeling so far. However, new dynamic activity-based approaches are being developed at the current moment. The frequency and inflexibility of planned activities and events in activity schedules of

  9. Real-time investigation of human topoisomerase I reaction kinetics using an optical sensor: a fast method for drug screening and determination of active enzyme concentrations.

    Science.gov (United States)

    Kristoffersen, Emil L; Jørgensen, Line A; Franch, Oskar; Etzerodt, Michael; Frøhlich, Rikke; Bjergbæk, Lotte; Stougaard, Magnus; Ho, Yi-Ping; Knudsen, Birgitta R

    2015-06-07

    Human DNA topoisomerase I (hTopI) is a nuclear enzyme that catalyzes relaxation of super helical tension that arises in the genome during essential DNA metabolic processes. This is accomplished through a common reaction mechanism shared among the type IB topoisomerase enzymes, including eukaryotic and poxvirus topoisomerase I. The mechanism of hTopI is specifically targeted in cancer treatment using camptothecin derivatives. These drugs convert the hTopI activity into a cellular poison, and hence the cytotoxic effects of camptothecin derivatives correlate with the hTopI activity. Therefore, fast and reliable techniques for high throughput measurements of hTopI activity are of high clinical interest. Here we demonstrate potential applications of a fluorophore-quencher based DNA sensor designed for measurement of hTopI cleavage-ligation activities, which are the catalytic steps affected by camptothecin. The kinetic analysis of the hTopI reaction with the DNA sensor exhibits a characteristic burst profile. This is the result of a two-step ping-pong reaction mechanism, where a fast first reaction, the one creating the signal, is followed by a slower second reaction necessary for completion of the catalytic cycle. Hence, the burst profile holds information about two reactions in the enzymatic mechanism. Moreover, it allows the amount of active enzyme in the reaction to be determined. The presented results pave the way for future high throughput drug screening and the potential of measuring active hTopI concentrations in clinical samples for individualized treatment.

  10. Oxidation of Tris (2-chloroethyl) phosphate in aqueous solution by UV-activated peroxymonosulfate: Kinetics, water matrix effects, degradation products and reaction pathways.

    Science.gov (United States)

    Xu, Xinxin; Chen, Jing; Qu, Ruijuan; Wang, Zunyao

    2017-10-01

    The feasibility of UV-activated peroxymonosulfate (PMS) technology for the degradation of Tris (2-chloroethyl) phosphate (TCEP) in an aqueous solution was investigated in this study. The conditions of [PMS] 0 : [TCEP] 0  = 20:1, T = 25 ± 2 °C and pH = 5.5 ± 0.5 cause a 94.6% removal of TCEP (1 mg L -1 ) after 30 min of Hg lamp irradiation. The effects of operating parameters (the oxidant doses, pH and presence of typical cations (Fe 3+ , Cu 2+ , Ni 2+ , NH 4 + ), anions (Cl - , HCO 3 - , NO 3 - , HPO 4 2- ) and humic acid (HA)) were evaluated. It was found that an increase of the PMS dose and the presence of Fe 3+ could accelerate the reaction, while the anions and HA inhibited the reaction. Meanwhile, TCEP removal in various water matrices was compared, and the order for TCEP removal was as follows: ultrapure water > tap water > synthetic water > secondary clarifier effluent > Jiuxiang river water. Twenty-two oxidation products were identified using an electrospray time-of-flight mass spectrometer, and the degradation pathways mainly involved radicals' addition and CO bond cleavage. Furthermore, ECOSAR analysis revealed that the intermediate products during the TCEP oxidation process were generally not harmful to three typical aquatic species. Hence, UV/PMS can be used as an efficient technology to treat TCEP-containing water and wastewaters. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. The Influence of Particle Shape and Size on the Activity of Platinum Nanoparticles for Oxygen Reduction Reaction: A Density Functional Theory Study

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Cerri, Isotta; Bligaard, Thomas

    2014-01-01

    We present first principle investigation of the influence of platinum nanoparticle shape and size on the oxygen reduction reaction activity. We compare the activities of nanoparticles with specific shapes (tetrahedron, octahedron, cube and truncated octahedron) with that of equilibrium particle s...

  12. 78 FR 66968 - In the Matter of Landon E. Brittain; Order Prohibiting Involvement In NRC-Licensed Activities...

    Science.gov (United States)

    2013-11-07

    ... apprehended in Venezuela, and has been extradited to the United States. As of the date of this Order, Mr... Enforcement Policy. Any person adversely affected by this Order may submit a written answer within 30 days...

  13. Utilization of boron irradiation filters in reactor neutron activation via epithermal (n,γ) and fast neutron reactions

    International Nuclear Information System (INIS)

    Chisela, F.

    1986-01-01

    The technique of instrumental neutron activation analysis based on irradiation with reactor epithermal and fast neutrons has been described and evaluated. Important characteristics of boron neutron absorbers used to remove thermal neutrons from the reactor neutron spectrum have been examined and compared with those of cadmium. Three boron compound shields, have been designed and constructed at the BER II 5MW reactor for use in epithermal neutron activation analysis of biological materials. The major advantages offered by these filters in this application include the flexibility of varying the filter thickness, the low radioactivity induced in the filters during irradiation, ease of fabrication and the relatively low cost of the filter materials. The radiation heating due to the 10 B(n,α) 7 Li-reaction has been experimentally investigated for the filters used and the results obtained confirm the necessity for efficient cooling of these filters during irradiation. Three irradiation facilities have been characterized with respect to the neutron flux density and the flux spatial distribution. An experiment has been designed and carried out to compensate the flux inhomogeneity in two irradiation positions of the DBV facility caused by the reactor geometry. Several biological samples including well characterized reference materials have been analysed after epithermal activation and the results compared with those obtained with the classical thermal neutron activation method. Improved sensitivity of determination has been found for elements with high resonance integral to thermal neutron cross section ratios (RI/σ 0 ). The range of elements that can be determined instrumentally is extended and the time scale of analysis is considerably reduced. (orig.) [de

  14. Free radical reactions of daunorubicin

    International Nuclear Information System (INIS)

    Houee-Levin, C.

    1991-01-01

    Daunorubicin is an antitumor antibiotic activated in vivo by reduction. Its mechanism of action involves DNA and topoisomerase attack, but side effects are cytotoxicity related to free radical formation. Therefore the mechanism of the one-electron reduction of the drug and the reactions of the daunorubicin transients towards compounds of biological interest have been studied by the methods of radiolysis, in order to provide possible explanations of the drug mechanism of action. Their relative importance in cellular conditions is discussed [fr

  15. Investigation of optically-induced DFB lasing in organic scintillators in order to achieve active ionizing radiation measurement

    International Nuclear Information System (INIS)

    Michel, Maugan

    2014-01-01

    Transducers used for nuclear measurements are divided into two groups. The first one is made of detectors based on the movement of charged carriers created during the interaction of ionizing radiation with materials (ionization chambers, semiconductors, etc.). The second comprises scintillating materials which emit light following such interaction. The present work aims at shifting the current paradigm in order to achieve an active measurement of the interactions between particles and sensor. The aim of this thesis is to investigate the response of nano-structured scintillators when excited by a primary laser beam while in the presence of ionizing radiations. It consists more precisely in optically inducing a laser emission in scintillators so as to benefit from the inherent sensitivity of this kind of wave to any kind of change in its environment. This study is at first focused on controlling the propagation of the electromagnetic waves in nano-structured media. This nano-structuration allows the channeling of the electromagnetic energy in a particular direction and at a precise wavelength and thus to amplify the transduction signal. The second part of this study is dedicated to the attempts at observing any change in the emission in an amplified regime while exposed to ionizing radiations (alpha, beta). The limitation of these sources requires the use of an electron accelerator. The conclusion of this part lays the foundation for future work and provides hypotheses regarding the effects that could be expected from the irradiation with high electron fluxes. (author) [fr

  16. Global synchronization in finite time for fractional-order neural networks with discontinuous activations and time delays.

    Science.gov (United States)

    Peng, Xiao; Wu, Huaiqin; Song, Ka; Shi, Jiaxin

    2017-10-01

    This paper is concerned with the global Mittag-Leffler synchronization and the synchronization in finite time for fractional-order neural networks (FNNs) with discontinuous activations and time delays. Firstly, the properties with respect to Mittag-Leffler convergence and convergence in finite time, which play a critical role in the investigation of the global synchronization of FNNs, are developed, respectively. Secondly, the novel state-feedback controller, which includes time delays and discontinuous factors, is designed to realize the synchronization goal. By applying the fractional differential inclusion theory, inequality analysis technique and the proposed convergence properties, the sufficient conditions to achieve the global Mittag-Leffler synchronization and the synchronization in finite time are addressed in terms of linear matrix inequalities (LMIs). In addition, the upper bound of the setting time of the global synchronization in finite time is explicitly evaluated. Finally, two examples are given to demonstrate the validity of the proposed design method and theoretical results. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Robust non-carbon titanium nitride nanotubes supported Pt catalyst with enhanced catalytic activity and durability for methanol oxidation reaction

    International Nuclear Information System (INIS)

    Xiao, Yonghao; Zhan, Guohe; Fu, Zhenggao; Pan, Zhanchang; Xiao, Chumin; Wu, Shoukun; Chen, Chun; Hu, Guanghui; Wei, Zhigang

    2014-01-01

    By the combination of solvothermal alcoholysis and post-nitriding method, titanium nitride nanotubes (TiN NTs), with high surface area, hollow and interior porous structure are prepared successfully and used at a support for Pt nanoparticles. The TiN NTs supported Pt (Pt/TiN NTs) catalyst displays enhanced activity and durability towards methanol oxidation reaction (MOR) compared with the commercial Pt/C (E-TEK) catalyst. X ray diffraction (XRD), nitrogen adsorption/desorption, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements are performed to investigate the physicochemical properties of the synthesized catalyst. SEM and TEM images reveal that the wall of the TiN NTs is porous and Pt nanoparticles supported on the dendritic TiN nanocrystals exhibit small size and good dispersion. Effects of inherent corrosion-resistant, tubular and porous nanostructures and electron transfer due to the strong metal–support interactions of TiN NTs contribute to the enhanced catalytic activity and stability of Pt/TiN NTs towards the MOR

  18. Pt-Richcore/Sn-Richsubsurface/Ptskin Nanocubes As Highly Active and Stable Electrocatalysts for the Ethanol Oxidation Reaction.

    Science.gov (United States)

    Rizo, Rubén; Arán-Ais, Rosa M; Padgett, Elliot; Muller, David A; Lázaro, Ma Jesús; Solla-Gullón, José; Feliu, Juan M; Pastor, Elena; Abruña, Héctor D

    2018-03-14

    Direct ethanol fuel cells are one of the most promising electrochemical energy conversion devices for portable, mobile and stationary power applications. However, more efficient and stable and less expensive electrocatalysts are still required. Interestingly, the electrochemical performance of the electrocatalysts toward the ethanol oxidation reaction can be remarkably enhanced by exploiting the benefits of structural and compositional sensitivity and control. Here, we describe the synthesis, characterization, and electrochemical behavior of cubic Pt-Sn nanoparticles. The electrochemical activity of the cubic Pt-Sn nanoparticles was found to be about three times higher than that obtained with unshaped Pt-Sn nanoparticles and six times higher than that of Pt nanocubes. In addition, stability tests indicated the electrocatalyst preserves its morphology and remains well-dispersed on the carbon support after 5000 potential cycles, while a cubic (pure) Pt catalyst exhibited severe agglomeration of the nanoparticles after a similar stability testing protocol. A detailed analysis of the elemental distribution in the nanoparticles by STEM-EELS indicated that Sn dissolves from the outer part of the shell after potential cycling, forming a ∼0.5 nm Pt skin. This particular atomic composition profile having a Pt-rich core, a Sn-rich subsurface layer, and a Pt-skin surface structure is responsible for the high activity and stability.

  19. Novel Co3O4 Nanoparticles/Nitrogen-Doped Carbon Composites with Extraordinary Catalytic Activity for Oxygen Evolution Reaction (OER)

    Science.gov (United States)

    Yang, Xiaobing; Chen, Juan; Chen, Yuqing; Feng, Pingjing; Lai, Huixian; Li, Jintang; Luo, Xuetao

    2018-03-01

    Herein, Co3O4 nanoparticles/nitrogen-doped carbon (Co3O4/NPC) composites with different structures were prepared via a facile method. Structure control was achieved by the rational morphology design of ZIF-67 precursors, which were then pyrolyzed in air to obtain Co3O4/NPC composites. When applied as catalysts for the oxygen evolution reaction (OER), the M-Co3O4/NPC composites derived from the flower-like ZIF-67 showed superior catalytic activities than those derived from the rhombic dodecahedron and hollow spherical ZIF-67. The former M-Co3O4/NPC composite displayed a small over-potential of 0.3 V, low onset potential of 1.41 V, small Tafel slope of 83 mV dec-1, and a desirable stability. (94.7% OER activity was retained after 10 h.) The excellent performance of the flower-like M-Co3O4/NPC composite in the OER was attributed to its favorable structure. [Figure not available: see fulltext.

  20. GABAA receptor activity modulating piperine analogs: In vitro metabolic stability, metabolite identification, CYP450 reaction phenotyping, and protein binding.

    Science.gov (United States)

    Zabela, Volha; Hettich, Timm; Schlotterbeck, Götz; Wimmer, Laurin; Mihovilovic, Marko D; Guillet, Fabrice; Bouaita, Belkacem; Shevchenko, Bénédicte; Hamburger, Matthias; Oufir, Mouhssin

    2018-01-01

    In a screening of natural products for allosteric modulators of GABA A receptors (γ-aminobutyric acid type A receptor), piperine was identified as a compound targeting a benzodiazepine-independent binding site. Given that piperine is also an activator of TRPV1 (transient receptor potential vanilloid type 1) receptors involved in pain signaling and thermoregulation, a series of piperine analogs were prepared in several cycles of structural optimization, with the aim of separating GABA A and TRPV1 activating properties. We here investigated the metabolism of piperine and selected analogs in view of further cycles of lead optimization. Metabolic stability of the compounds was evaluated by incubation with pooled human liver microsomes, and metabolites were analyzed by UHPLC-Q-TOF-MS. CYP450 isoenzymes involved in metabolism of compounds were identified by reaction phenotyping with Silensomes™. Unbound fraction in whole blood was determined by rapid equilibrium dialysis. Piperine was the metabolically most stable compound. Aliphatic hydroxylation, and N- and O-dealkylation were the major routes of oxidative metabolism. Piperine was exclusively metabolized by CYP1A2, whereas CYP2C9 contributed significantly in the oxidative metabolism of all analogs. Extensive binding to blood constituents was observed for all compounds. Copyright © 2017 Elsevier B.V. All rights reserved.