WorldWideScience

Sample records for detailed kinetic mechanisms

  1. Development of a Procedure to Apply Detailed Chemical Kinetic Mechanisms to CFD Simulations as Post Processing

    DEFF Research Database (Denmark)

    Skjøth-Rasmussen, Martin Skov; Glarborg, Peter; Jensen, Anker

    2003-01-01

    mechanism. It involves post-processing of data extracted from computational fluid dynamics simulations. Application of this approach successfully describes combustion chemistry in a standard swirl burner, the so-called Harwell furnace. Nevertheless, it needs validation against more complex combustion models......It is desired to make detailed chemical kinetic mechanisms applicable to the complex geometries of practical combustion devices simulated with computational fluid dynamics tools. This work presents a novel general approach to combining computational fluid dynamics and a detailed chemical kinetic...

  2. Kinetic energy budget details

    Indian Academy of Sciences (India)

    Abstract. This paper presents the detailed turbulent kinetic energy budget and higher order statistics of flow behind a surface-mounted rib with and without superimposed acoustic excitation. Pattern recognition technique is used to determine the large-scale structure magnitude. It is observed that most of the turbulence ...

  3. A comprehensive detailed kinetic mechanism for the simulation of transportation fuels

    KAUST Repository

    Mehl, Marco; Zhang, Kuiwen; Wagnon, Scott; Kukkadapu, Goutham; Westbrook, Charles K.; Pitz, William J.; Zhang, Yinjia; Curran, Henry J.; Al Rachidi, Mariam; Atef, Nour; Sarathy, Mani; Ahmed, Ahfaz

    2017-01-01

    This work presents a recently compiled comprehensive model for transportations fuels resulting from the collaboration of three research groups: LLNL, NUI Galway and KAUST. In the past 5 years new fundamental calculations led to significant improvements in the fidelity of detailed kinetic models of important surrogate components (e.g. n-heptane, iso-octane, toluene…) improving predictions of the combustion behavior of pure components and mixtures. By extending the newly adopted reaction rate rules, mechanisms for components that were not included in the previous LLNL gasoline and diesel surrogate mechanisms were developed (e.g. polyalkylated aromatics, cycloalkanes, components from bio-logical sources…). The major features of this updated and extended model are presented together with validation comparisons, examples of applications and future directions.

  4. A comprehensive detailed kinetic mechanism for the simulation of transportation fuels

    KAUST Repository

    Mehl, Marco

    2017-02-27

    This work presents a recently compiled comprehensive model for transportations fuels resulting from the collaboration of three research groups: LLNL, NUI Galway and KAUST. In the past 5 years new fundamental calculations led to significant improvements in the fidelity of detailed kinetic models of important surrogate components (e.g. n-heptane, iso-octane, toluene…) improving predictions of the combustion behavior of pure components and mixtures. By extending the newly adopted reaction rate rules, mechanisms for components that were not included in the previous LLNL gasoline and diesel surrogate mechanisms were developed (e.g. polyalkylated aromatics, cycloalkanes, components from bio-logical sources…). The major features of this updated and extended model are presented together with validation comparisons, examples of applications and future directions.

  5. A Detailed Chemical Kinetic Reaction Mechanism for Oxidation of Four Small Alkyl Esters in Laminar Premixed Flames

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Westmoreland, P R; Dryer, F L; Chaos, M; Osswald, P; Kohse-Hoinghaus, K; Cool, T A; Wang, J; Yang, B; Hansen, N; Kasper, T

    2008-02-08

    A detailed chemical kinetic reaction mechanism has been developed for a group of four small alkyl ester fuels, consisting of methyl formate, methyl acetate, ethyl formate and ethyl acetate. This mechanism is validated by comparisons between computed results and recently measured intermediate species mole fractions in fuel-rich, low pressure, premixed laminar flames. The model development employs a principle of similarity of functional groups in constraining the H atom abstraction and unimolecular decomposition reactions in each of these fuels. As a result, the reaction mechanism and formalism for mechanism development are suitable for extension to larger oxygenated hydrocarbon fuels, together with an improved kinetic understanding of the structure and chemical kinetics of alkyl ester fuels that can be extended to biodiesel fuels. Variations in concentrations of intermediate species levels in these flames are traced to differences in the molecular structure of the fuel molecules.

  6. A path flux analysis method for the reduction of detailed chemical kinetic mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Wenting; Ju, Yiguang [Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544 (United States); Chen, Zheng [State Key Laboratory for Turbulence and Complex Systems, College of Engineering, Peking University, Beijing 100871 (China); Gou, Xiaolong [School of Power Engineering, Chongqing University, Chongqing 400044 (China)

    2010-07-15

    A direct path flux analysis (PFA) method for kinetic mechanism reduction is proposed and validated by using high temperature ignition, perfect stirred reactors, and steady and unsteady flame propagations of n-heptane and n-decane/air mixtures. The formation and consumption fluxes of each species at multiple reaction path generations are analyzed and used to identify the important reaction pathways and the associated species. The formation and consumption path fluxes used in this method retain flux conservation information and are used to define the path indexes for the first and the second generation reaction paths related to a targeted species. Based on the indexes of each reaction path for the first and second generations, different sized reduced chemical mechanisms which contain different number of species are generated. The reduced mechanisms of n-heptane and n-decane obtained by using the present method are compared to those generated by the direct relation graph (DRG) method. The reaction path analysis for n-decane is conducted to demonstrate the validity of the present method. The comparisons of the ignition delay times, flame propagation speeds, flame structures, and unsteady spherical flame propagation processes showed that with either the same or significantly less number of species, the reduced mechanisms generated by the present PFA are more accurate than that of DRG in a broad range of initial pressures and temperatures. The method is also integrated with the dynamic multi-timescale method and a further increase of computation efficiency is achieved. (author)

  7. Comparison of detailed and reduced kinetics mechanisms of silane oxidation in the basis of detonation wave structure problem

    Science.gov (United States)

    Fedorov, A. V.; Tropin, D. A.; Fomin, P. A.

    2018-03-01

    The paper deals with the problem of the structure of detonation waves in the silane-air mixture within the framework of mathematical model of a nonequilibrium gas dynamics. Detailed kinetic scheme of silane oxidation as well as the newly developed reduced kinetic model of detonation combustion of silane are used. On its basis the detonation wave (DW) structure in stoichiometric silane - air mixture and dependences of Chapman-Jouguet parameters of mixture on stoichiometric ratio between the fuel (silane) and an oxidizer (air) were obtained.

  8. Detailed Chemical Kinetic Modeling of Hydrazine Decomposition

    Science.gov (United States)

    Meagher, Nancy E.; Bates, Kami R.

    2000-01-01

    The purpose of this research project is to develop and validate a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. Hydrazine is used extensively in aerospace propulsion, and although liquid hydrazine is not considered detonable, many fuel handling systems create multiphase mixtures of fuels and fuel vapors during their operation. Therefore, a thorough knowledge of the decomposition chemistry of hydrazine under a variety of conditions can be of value in assessing potential operational hazards in hydrazine fuel systems. To gain such knowledge, a reasonable starting point is the development and validation of a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. A reasonably complete mechanism was published in 1996, however, many of the elementary steps included had outdated rate expressions and a thorough investigation of the behavior of the mechanism under a variety of conditions was not presented. The current work has included substantial revision of the previously published mechanism, along with a more extensive examination of the decomposition behavior of hydrazine. An attempt to validate the mechanism against the limited experimental data available has been made and was moderately successful. Further computational and experimental research into the chemistry of this fuel needs to be completed.

  9. A detailed kinetic mechanism including methanol and nitrogen pollutants relevant to the gas-phase combustion and pyrolysis of biomass-derived fuels

    Energy Technology Data Exchange (ETDEWEB)

    Coda Zabetta, Edgardo; Hupa, Mikko [Aabo Akademi Process Chemistry Centre, Piispankatu 8, FI-20500 Turku (Finland)

    2008-01-15

    A detailed chemical kinetic mechanism for the simulation of the gas-phase combustion and pyrolysis of biomass-derived fuels was compiled by assembling selected reaction subsets from existing mechanisms (parents). The mechanism, here referred to as ''AaA,'' includes reaction subsets for the oxidation of hydrogen (H{sub 2}), carbon monoxide (CO), light hydrocarbons (C{sub 1} and C{sub 2}), and methanol (CH{sub 3}OH). The mechanism also takes into account reaction subsets of nitrogen pollutants, including the reactions relevant to staged combustion, reburning, and selective noncatalytic reduction (SNCR). The AaA mechanism was validated against suitable experimental data from the literature. Overall, the AaA mechanism gave more accurate predictions than three other mechanisms of reference, although the reference mechanisms performed better occasionally. The predictions from AaA were also found to be consistent with the predictions of its parent mechanisms within most of their range of validity, thus transferring the validity of the parents to the inheriting mechanism (AaA). In parametric studies the AaA mechanism predicted that the effect of methanol on combustion and pollutants is often similar to that of light hydrocarbons, but it also showed that there are important exceptions, thus suggesting that methanol should be taken into account when simulating biomass combustion. To our knowledge, the AaA mechanism is currently the only mechanism that accounts for the chemistry of methanol and nitrogen relevant to the gas-phase combustion and pyrolysis of biomass-derived fuels. (author)

  10. Cleaner combustion developing detailed chemical kinetic models

    CERN Document Server

    Battin-Leclerc, Frédérique; Simmie, John M

    2013-01-01

    This book describes the reactive chemistry of minor pollutants within extensively validated detailed mechanisms for traditional fuels, and also for innovative surrogates, describing the complex chemistry of new, environmentally important bio-fuels.

  11. Analysis of kinetic reaction mechanisms

    CERN Document Server

    Turányi, Tamás

    2014-01-01

    Chemical processes in many fields of science and technology, including combustion, atmospheric chemistry, environmental modelling, process engineering, and systems biology, can be described by detailed reaction mechanisms consisting of numerous reaction steps. This book describes methods for the analysis of reaction mechanisms that are applicable in all these fields. Topics addressed include: how sensitivity and uncertainty analyses allow the calculation of the overall uncertainty of simulation results and the identification of the most important input parameters, the ways in which mechanisms can be reduced without losing important kinetic and dynamic detail, and the application of reduced models for more accurate engineering optimizations. This monograph is invaluable for researchers and engineers dealing with detailed reaction mechanisms, but is also useful for graduate students of related courses in chemistry, mechanical engineering, energy and environmental science and biology.

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

    Directory of Open Access Journals (Sweden)

    JUNJIE CHEN

    2014-11-01

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

  13. Application of Detailed Chemical Kinetics to Combustion Instability Modeling

    Science.gov (United States)

    2016-01-04

    Clearance Number 15692 Clearance Date 12/3/2015 14. ABSTRACT A comparison of a single step global reaction and the detailed GRI -Mech 1.2 for combustion...comparison of a single step global reaction and the detailed GRI -Mech 1.2 for com- bustion instability modeling in a methane-fueled longitudinal-mode...methane as the fuel. We use the GRI -Mech 1.2 kinetics mechanism for methane oxidation.11 The GRI -Mech 1.2 was chosen over 2.11 because the only

  14. Chemical kinetics and reaction mechanism

    International Nuclear Information System (INIS)

    Jung, Ou Sik; Park, Youn Yeol

    1996-12-01

    This book is about chemical kinetics and reaction mechanism. It consists of eleven chapters, which deal with reaction and reaction speed on reaction mechanism, simple reaction by rate expression, reversible reaction and simultaneous reaction, successive reaction, complicated reaction mechanism, assumption for reaction mechanism, transition state theory, successive reaction and oscillating reaction, reaction by solution, research method high except kinetics on reaction mechanism, high reaction of kinetics like pulsed radiolysis.

  15. Kinetics of ethylcyclohexane pyrolysis and oxidation: An experimental and detailed kinetic modeling study

    KAUST Repository

    Wang, Zhandong

    2015-07-01

    Ethylcyclohexane (ECH) is a model compound for cycloalkanes with long alkyl side-chains. A preliminary investigation on ECH (Wang et al., Proc. Combust. Inst., 35, 2015, 367-375) revealed that an accurate ECH kinetic model with detailed fuel consumption mechanism and aromatic growth pathways, as well as additional ECH pyrolysis and oxidation data with detailed species concentration covering a wide pressure and temperature range are required to understand the ECH combustion kinetics. In this work, the flow reactor pyrolysis of ECH at various pressures (30, 150 and 760Torr) was studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS) and gas chromatography (GC). The mole fraction profiles of numerous major and minor species were evaluated, and good agreement was observed between the PIMS and GC data sets. Furthermore, a fuel-rich burner-stabilized laminar premixed ECH/O2/Ar flame at 30Torr was studied using synchrotron VUV PIMS. A detailed kinetic model for ECH high temperature pyrolysis and oxidation was developed and validated against the pyrolysis and flame data performed in this work. Further validation of the kinetic model is presented against literature data including species concentrations in jet-stirred reactor oxidation, ignition delay times in a shock tube, and laminar flame speeds at various pressures and equivalence ratios. The model well predicts the consumption of ECH, the growth of aromatics, and the global combustion properties. Reaction flux and sensitivity analysis were utilized to elucidate chemical kinetic features of ECH combustion under various reaction conditions. © 2015 The Combustion Institute.

  16. Reduced chemical kinetic mechanisms for hydrocarbon fuels

    International Nuclear Information System (INIS)

    Montgomery, C.J.; Cremer, M.A.; Heap, M.P.; Chen, J-Y.; Westbrook, C.K.; Maurice, L.Q.

    1999-01-01

    Using CARM (Computer Aided Reduction Method), a computer program that automates the mechanism reduction process, a variety of different reduced chemical kinetic mechanisms for ethylene and n-heptane have been generated. The reduced mechanisms have been compared to detailed chemistry calculations in simple homogeneous reactors and experiments. Reduced mechanisms for combustion of ethylene having as few as 10 species were found to give reasonable agreement with detailed chemistry over a range of stoichiometries and showed significant improvement over currently used global mechanisms. The performance of reduced mechanisms derived from a large detailed mechanism for n-heptane was compared to results from a reduced mechanism derived from a smaller semi-empirical mechanism. The semi-empirical mechanism was advantageous as a starting point for reduction for ignition delay, but not for PSR calculations. Reduced mechanisms with as few as 12 species gave excellent results for n-heptane/air PSR calculations but 16-25 or more species are needed to simulate n-heptane ignition delay

  17. Prediction of Combustion Instability with Detailed Chemical Kinetics

    Science.gov (United States)

    2014-12-01

    of combustion instability. The mechanisms used for methane oxidation are the GRI 1.2 set that comprises of 32 chemical species and 177 reactions. All...with a single step global reaction and the GRI -1.2 kinetics mechanism which contains 177 reactions. The paper is organized as follows, Section II...flame speeds10. GRI -1.2 is a more complete set of hydrocarbon reactions consisting of 177 reactions involving 32 species and was optimized for natural

  18. Kinetics of ethylcyclohexane pyrolysis and oxidation: An experimental and detailed kinetic modeling study

    KAUST Repository

    Wang, Zhandong; Zhao, Long; Wang, Yu; Bian, Huiting; Zhang, Lidong; Zhang, Feng; Li, Yuyang; Sarathy, Mani; Qi, Fei

    2015-01-01

    species were evaluated, and good agreement was observed between the PIMS and GC data sets. Furthermore, a fuel-rich burner-stabilized laminar premixed ECH/O2/Ar flame at 30Torr was studied using synchrotron VUV PIMS. A detailed kinetic model for ECH high

  19. Energetic Mapping of Ni Catalysts by Detailed Kinetic Modeling

    DEFF Research Database (Denmark)

    Bjørgum, Erlend; Chen, De; Bakken, Mari G.

    2005-01-01

    Temperature-programmed desorption (TPD) of CO has been performed on supported and unsupported nickel catalysts. The unsupported Ni catalyst consists of a Ni(14 13 13) single crystal which has been studied under ultrahigh vacuum conditions. The desorption energy for CO at low CO surface coverage...... was found to be 119 kJ/mol, and the binding energy of C to the Ni(111) surface of the crystal was 703 kJ/mol. The supported catalysts consist of nickel supported on hydrotalcite-like compounds with three different Mg2+/Al3+ ratios. The experimental results show that for the supported Ni catalysts TPD of CO...... precursor seems to result in more steplike sites, kinks, and defects for carbon monoxide dissociation. A detailed kinetic modeling of the TPO results based on elementary reaction steps has been conducted to give an energetic map of supported Ni catalysts. Experimental results from the ideal Ni surface fit...

  20. Detailed kinetic modeling study of n-pentanol oxidation

    KAUST Repository

    Heufer, Karl Alexander; Sarathy, Mani; Curran, Henry J.; Davis, Alexander C.; Westbrook, Charles K.; Pitz, William J.

    2012-01-01

    To help overcome the world's dependence upon fossil fuels, suitable biofuels are promising alternatives that can be used in the transportation sector. Recent research on internal combustion engines shows that short alcoholic fuels (e.g., ethanol or n-butanol) have reduced pollutant emissions and increased knock resistance compared to fossil fuels. Although higher molecular weight alcohols (e.g., n-pentanol and n-hexanol) exhibit higher reactivity that lowers their knock resistance, they are suitable for diesel engines or advanced engine concepts, such as homogeneous charge compression ignition (HCCI), where higher reactivity at lower temperatures is necessary for engine operation. The present study presents a detailed kinetic model for n-pentanol based on modeling rules previously presented for n-butanol. This approach was initially validated using quantum chemistry calculations to verify the most stable n-pentanol conformation and to obtain C-H and C-C bond dissociation energies. The proposed model has been validated against ignition delay time data, speciation data from a jet-stirred reactor, and laminar flame velocity measurements. Overall, the model shows good agreement with the experiments and permits a detailed discussion of the differences between alcohols and alkanes. © 2012 American Chemical Society.

  1. Detailed kinetic modeling study of n-pentanol oxidation

    KAUST Repository

    Heufer, Karl Alexander

    2012-10-18

    To help overcome the world\\'s dependence upon fossil fuels, suitable biofuels are promising alternatives that can be used in the transportation sector. Recent research on internal combustion engines shows that short alcoholic fuels (e.g., ethanol or n-butanol) have reduced pollutant emissions and increased knock resistance compared to fossil fuels. Although higher molecular weight alcohols (e.g., n-pentanol and n-hexanol) exhibit higher reactivity that lowers their knock resistance, they are suitable for diesel engines or advanced engine concepts, such as homogeneous charge compression ignition (HCCI), where higher reactivity at lower temperatures is necessary for engine operation. The present study presents a detailed kinetic model for n-pentanol based on modeling rules previously presented for n-butanol. This approach was initially validated using quantum chemistry calculations to verify the most stable n-pentanol conformation and to obtain C-H and C-C bond dissociation energies. The proposed model has been validated against ignition delay time data, speciation data from a jet-stirred reactor, and laminar flame velocity measurements. Overall, the model shows good agreement with the experiments and permits a detailed discussion of the differences between alcohols and alkanes. © 2012 American Chemical Society.

  2. Soot formation in a blast furnace - Prediction via a parametric study, using detailed kinetic modeling

    Energy Technology Data Exchange (ETDEWEB)

    Nordstroem, T; Kilpinen, P; Hupa, M [Aabo Akademi, Turku (Finland). Combustion Chemistry Group

    1997-12-31

    The objective of this work has been to investigate the soot formation in a blast furnace fired with heavy fuel oil, using detailed kinetic modelling. This work has been concentrated on parameter studies that could explain under which conditions soot is formed and how that formation could be avoided. The parameters investigated were temperature, pressure, stoichiometric ratio, pyrolysis gas composition and reactor model. The calculations were based on a reaction mechanism that consists of 100 species and 446 reactions including polyaromatic hydrocarbons (PAM) up to 7 aromatic rings SULA 2 Research Programme; 4 refs.

  3. Soot formation in a blast furnace - Prediction via a parametric study, using detailed kinetic modeling

    Energy Technology Data Exchange (ETDEWEB)

    Nordstroem, T.; Kilpinen, P.; Hupa, M. [Aabo Akademi, Turku (Finland). Combustion Chemistry Group

    1996-12-31

    The objective of this work has been to investigate the soot formation in a blast furnace fired with heavy fuel oil, using detailed kinetic modelling. This work has been concentrated on parameter studies that could explain under which conditions soot is formed and how that formation could be avoided. The parameters investigated were temperature, pressure, stoichiometric ratio, pyrolysis gas composition and reactor model. The calculations were based on a reaction mechanism that consists of 100 species and 446 reactions including polyaromatic hydrocarbons (PAM) up to 7 aromatic rings SULA 2 Research Programme; 4 refs.

  4. Detailed Modelling of Kinetic Biodegradation Processes in a Laboratory Mmicrocosm

    Science.gov (United States)

    Watson, I.; Oswald, S.; Banwart, S.; Mayer, U.

    2003-04-01

    Biodegradation of organic contaminants in soil and groundwater usually takes places via different redox processes happening sequentially as well as simultaneously. We used numerical modelling of a long-term lab microcosm experiment to simulate the dynamic behaviour of fermentation and respiration in the aqueous phase in contact with the sandstone material, and to develop a conceptual model describing these processes. Aqueous speciation, surface complexation, mineral dissolution and precipitation were taken into account also. Fermentation can be the first step of the degradation process producing intermediate species, which are subsequently consumed by TEAPs. Microbial growth and substrate utilisation kinetics are coupled via a formulation that also includes aqueous speciation and other geochemical reactions including surface complexation, mineral dissolution and precipitation. Competitive exclusion between TEAPs is integral to the conceptual model of the simulation, and the results indicate that exclusion is not complete, but some overlap is found between TEAPs. The model was used to test approaches like the partial equilibrium approach that currently make use of hydrogen levels to diagnose prevalent TEAPs in groundwater. The observed pattern of hydrogen and acetate concentrations were reproduced well by the simulations, and the results show the relevance of kinetics, lag times and inhibition, and especially that intermediate products play a key role.

  5. Kinetic mechanism for modeling of electrochemical reactions.

    Science.gov (United States)

    Cervenka, Petr; Hrdlička, Jiří; Přibyl, Michal; Snita, Dalimil

    2012-04-01

    We propose a kinetic mechanism of electrochemical interactions. We assume fast formation and recombination of electron donors D- and acceptors A+ on electrode surfaces. These mediators are continuously formed in the electrode matter by thermal fluctuations. The mediators D- and A+, chemically equivalent to the electrode metal, enter electrochemical interactions on the electrode surfaces. Electrochemical dynamics and current-voltage characteristics of a selected electrochemical system are studied. Our results are in good qualitative agreement with those given by the classical Butler-Volmer kinetics. The proposed model can be used to study fast electrochemical processes in microsystems and nanosystems that are often out of the thermal equilibrium. Moreover, the kinetic mechanism operates only with the surface concentrations of chemical reactants and local electric potentials, which facilitates the study of electrochemical systems with indefinable bulk.

  6. Kinetic partitioning mechanism of HDV ribozyme folding

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jiawen; Gong, Sha; Wang, Yujie; Zhang, Wenbing, E-mail: wbzhang@whu.edu.cn [Department of Physics, Wuhan University, Wuhan, Hubei 430072 (China)

    2014-01-14

    RNA folding kinetics is directly tied to RNA biological functions. We introduce here a new approach for predicting the folding kinetics of RNA secondary structure with pseudoknots. This approach is based on our previous established helix-based method for predicting the folding kinetics of RNA secondary structure. In this approach, the transition rates for an elementary step: (1) formation, (2) disruption of a helix stem, and (3) helix formation with concomitant partial melting of an incompatible helix, are calculated with the free energy landscape. The folding kinetics of the Hepatitis delta virus (HDV) ribozyme and the mutated sequences are studied with this method. The folding pathways are identified by recursive searching the states with high net flux-in(out) population starting from the native state. The theory results are in good agreement with that of the experiments. The results indicate that the bi-phasic folding kinetics for the wt HDV sequence is ascribed to the kinetic partitioning mechanism: Part of the population will quickly fold to the native state along the fast pathway, while another part of the population will fold along the slow pathway, in which the population is trapped in a non-native state. Single mutation not only changes the folding rate but also the folding pathway.

  7. KINETICS AND MECHANISM OF REACTION OF ACIDIC ...

    African Journals Online (AJOL)

    The kinetics and mechanism of the oxidation of two phenoxazine dyes namely Nile blue (7-amino-3-diethylamino-8,9-benzo phenoxazine chloride, NB+) and Meldola\\'s blue (3- dimethylamino-8,9-benzo phenoxazine chloride, MB+) with acidic chlorite and hypochlorous acid have been investigated using a UV-visible and a ...

  8. Redox kinetics and mechanism in silicate melts

    International Nuclear Information System (INIS)

    Cochain, B.

    2009-12-01

    This work contributes to better understand iron redox reactions and mechanisms in silicate melts. It was conducted on compositions in both Na 2 O-B 2 O 3 -SiO 2 -FeO and Na 2 O-Al 2 O 3 -SiO 2 -FeO systems. The influence of boron-sodium and aluminum-sodium substitutions and iron content on properties and structure of glasses and on the iron redox kinetics has been studied by Raman, Moessbauer and XANES spectroscopies at the B and Fe K-edges. In borosilicate glasses, an increase in iron content or in the Fe 3+ /ΣFe redox state implies a structural rearrangement of the BO 4 species in the glass network whereas the BO 3 and BO 4 relative proportions remain nearly constant. In all studied glasses and melts, Fe 3+ is a network former in tetrahedral coordination, unless for aluminosilicates of ratio Al/Na≥1 where Fe 3+ is a network modifier in five-fold coordination. Near Tg, diffusion of network modifying cations controls the iron redox kinetics along with a flux of electron holes. At liquidus temperatures, oxygen diffusion is considered to be the mechanism that governs redox reactions. This study shows the role played by the silicate network polymerization on the redox kinetics. In borosilicate melts, iron redox kinetics depends on the boron speciation between BO 3 and BO 4 that depends itself on the sodium content. Furthermore, an increase in the network-former/network-modifier ratio implies a decrease in oxygen diffusion that results in a slowing down of the redox kinetics. The obtained results allow a description of the iron redox kinetics for more complex compositions as natural lavas or nuclear waste model glasses. (author)

  9. CSP-based chemical kinetics mechanisms simplification strategy for non-premixed combustion: An application to hybrid rocket propulsion

    KAUST Repository

    Ciottoli, Pietro P.; Malpica Galassi, Riccardo; Lapenna, Pasquale E.; Leccese, G.; Bianchi, D.; Nasuti, F.; Creta, F.; Valorani, M.

    2017-01-01

    A set of simplified chemical kinetics mechanisms for hybrid rocket applications using gaseous oxygen (GOX) and hydroxyl-terminated polybutadiene (HTPB) is proposed. The starting point is a 561-species, 2538-reactions, detailed chemical kinetics

  10. CFD analysis of municipal solid waste combustion using detailed chemical kinetic modelling.

    Science.gov (United States)

    Frank, Alex; Castaldi, Marco J

    2014-08-01

    Nitrogen oxides (NO x ) emissions from the combustion of municipal solid waste (MSW) in waste-to-energy (WtE) facilities are receiving renewed attention to reduce their output further. While NO x emissions are currently 60% below allowed limits, further reductions will decrease the air pollution control (APC) system burden and reduce consumption of NH3. This work combines the incorporation of the GRI 3.0 mechanism as a detailed chemical kinetic model (DCKM) into a custom three-dimensional (3D) computational fluid dynamics (CFD) model fully to understand the NO x chemistry in the above-bed burnout zones. Specifically, thermal, prompt and fuel NO formation mechanisms were evaluated for the system and a parametric study was utilized to determine the effect of varying fuel nitrogen conversion intermediates between HCN, NH3 and NO directly. Simulation results indicate that the fuel nitrogen mechanism accounts for 92% of the total NO produced in the system with thermal and prompt mechanisms accounting for the remaining 8%. Results also show a 5% variation in final NO concentration between HCN and NH3 inlet conditions, demonstrating that the fuel nitrogen intermediate assumed is not significant. Furthermore, the conversion ratio of fuel nitrogen to NO was 0.33, revealing that the majority of fuel nitrogen forms N2. © The Author(s) 2014.

  11. Analysis of exergy loss of gasoline surrogate combustion process based on detailed chemical kinetics

    International Nuclear Information System (INIS)

    Sun, Hongjie; Yan, Feng; Yu, Hao; Su, W.H.

    2015-01-01

    Highlights: • We explored the exergy loss sources of gasoline engine like combustion process. • The model combined non-equilibrium thermodynamics with detailed chemical kinetics. • We explored effects of initial conditions on exergy loss of combustion process. • Exergy loss decreases 15% of fuel chemical exergy by design of initial conditions. • Correspondingly, the second law efficiency increases from 38.9% to 68.9%. - Abstract: Chemical reaction is the most important source of combustion irreversibility in premixed conditions, but details of the exergy loss mechanisms have not been explored yet. In this study numerical analysis based on non-equilibrium thermodynamics combined with detailed chemical kinetics is conducted to explore the exergy loss mechanism of gasoline engine like combustion process which is simplified as constant volume combustion. The fuel is represented by the common accepted gasoline surrogates which consist of four components: iso-octane (57%), n-heptane (16%), toluene (23%), and 2-pentene (4%). We find that overall exergy loss is mainly composed of three peaks along combustion generated from chemical reactions in three stages, the conversion from large fuel molecules into small molecules (as Stage 1), the H 2 O 2 loop-related reactions (as Stage 2), and the violent oxidation reactions of CO, H, and O (as Stage 3). The effects of individual combustion boundaries, including temperature, pressure, equivalence ratio, oxygen concentration, on combustion exergy loss have been widely investigated. The combined effects of combustion boundaries on the total loss of gasoline surrogates are also investigated. We find that in a gasoline engine with a compression ratio of 10, the total loss can be reduced from 31.3% to 24.3% using lean combustion. The total loss can be further reduced to 22.4% by introducing exhaust gas recirculation and boosting the inlet charge. If the compression ratio is increased to 17, the total loss can be decreased to

  12. Reduced Chemical Kinetic Mechanisms for JP-8 Combustion

    National Research Council Canada - National Science Library

    Montgomery, Christopher J; Cannon, S. M; Mawid, M. A; Sekar, B

    2002-01-01

    Using CARM (Computer Aided Reduction Method), a computer program that automates the mechanism reduction process, six different reduced chemical kinetic mechanisms for JP-8 combustion have been generated...

  13. Studies of combustion kinetics and mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Gutman, D. [Catholic Univ. of America, Washington, DC (United States)

    1993-12-01

    The objective of the current research is to gain new quantitative knowledge of the kinetics and mechanisms of polyatomic free radicals which are important in hydrocarbon combustion processes. The special facility designed and built for these (which includes a heatable tubular reactor coupled to a photoionization mass spectrometer) is continually being improved. Where possible, these experimental studies are coupled with theoretical ones, sometimes conducted in collaboration with others, to obtain an improved understanding of the factors determining reactivity. The decomposition of acetyl radicals, isopropyl radicals, and n-propyl radicals have been studied as well as the oxidation of methylpropargyl radicals.

  14. Comparison of different chemical kinetic mechanisms of methane combustion in an internal combustion engine configuration

    OpenAIRE

    Ennetta Ridha; Hamdi Mohamed; Said Rachid

    2008-01-01

    Three chemical kinetic mechanisms of methane combustion were tested and compared using the internal combustion engine model of Chemkin 4.02 [1]: one-step global reaction mechanism, four-step mechanism, and the standard detailed scheme GRIMECH 3.0. This study shows good concordances, especially between the four-step and the detailed mechanisms in the prediction of temperature and main species profiles. But reduced schemes were incapables to predict pollutant emissions in an internal combustion...

  15. Cyclopentane combustion chemistry. Part I: Mechanism development and computational kinetics

    KAUST Repository

    Rachidi, Mariam El

    2017-06-23

    Cycloalkanes are significant constituents of conventional fossil fuels, in which they are one of the main contributors to soot formation, but also significantly influence the ignition characteristics below ∼900K. This paper discusses the development of a detailed high- and low-temperature oxidation mechanism for cyclopentane, which is an important archetypical cycloalkane. The differences between cyclic and non-cyclic alkane chemistry, and thus the inapplicability of acyclic alkane analogies, required the detailed theoretical investigation of the kinetics of important cyclopentane oxidation reactions as part of the mechanism development. The cyclopentyl+O reaction was investigated at the UCCSD(T)-F12a/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory in a time-dependent master equation framework. Comparisons with analogous cyclohexane or non-cyclic alkane reactions are presented. Our study suggests that beyond accurate quantum chemistry the inclusion of pressure dependence and especially that of formally direct kinetics is crucial even at pressures relevant for practical application.

  16. Cyclopentane combustion chemistry. Part I: Mechanism development and computational kinetics

    KAUST Repository

    Rachidi, Mariam El; Mehl, Marco; Pitz, William J.; Mohamed, Samah; Sarathy, Mani

    2017-01-01

    Cycloalkanes are significant constituents of conventional fossil fuels, in which they are one of the main contributors to soot formation, but also significantly influence the ignition characteristics below ∼900K. This paper discusses the development of a detailed high- and low-temperature oxidation mechanism for cyclopentane, which is an important archetypical cycloalkane. The differences between cyclic and non-cyclic alkane chemistry, and thus the inapplicability of acyclic alkane analogies, required the detailed theoretical investigation of the kinetics of important cyclopentane oxidation reactions as part of the mechanism development. The cyclopentyl+O reaction was investigated at the UCCSD(T)-F12a/cc-pVTZ-F12//M06-2X/6-311++G(d,p) level of theory in a time-dependent master equation framework. Comparisons with analogous cyclohexane or non-cyclic alkane reactions are presented. Our study suggests that beyond accurate quantum chemistry the inclusion of pressure dependence and especially that of formally direct kinetics is crucial even at pressures relevant for practical application.

  17. Kinetics and mechanism of Prussian blue formation

    Directory of Open Access Journals (Sweden)

    R.K. Adhikamsetty

    2009-04-01

    Full Text Available The kinetics of reaction between ferrocyanide and ferric ions under acidic conditions was studied at fixed ionic strength (0.1 M and (25 plus or minus 0.1 oC by using the stopped flow technique, under limiting conditions of [ferrocyanide] and with other reactants in excess. The reaction had first-order dependence on ferrocyanide, Fe(III and H+ ion concentrations and had negative salt effect. On the basis of the experimental findings, a plausible mechanism for the formation of soluble form of Prussian blue (KFe{Fe(CN6}x H2O and rate law are proposed. The activation parameters for the title reaction are estimated. A relatively low energy of activation (23 kJ mol-1 and high negative entropy of activation (-231 J K-1 mol-1 agree well with the proposed mechanism and configuration of complex ion leading to the formation of insoluble Prussian blue, Fe4{Fe(CN6}3 y H2O.

  18. Mechanism and kinetics of hydrated electron diffusion

    International Nuclear Information System (INIS)

    Tay, Kafui A.; Coudert, Francois-Xavier; Boutin, Anne

    2008-01-01

    Molecular dynamics simulations are used to study the mechanism and kinetics of hydrated electron diffusion. The electron center of mass is found to exhibit Brownian-type behavior with a diffusion coefficient considerably greater than that of the solvent. As previously postulated by both experimental and theoretical works, the instantaneous response of the electron to the librational motions of surrounding water molecules constitutes the principal mode of motion. The diffusive mechanism can be understood within the traditional framework of transfer diffusion processes, where the diffusive step is akin to the exchange of an extramolecular electron between neighboring water molecules. This is a second-order process with a computed rate constant of 5.0 ps -1 at 298 K. In agreement with experiment the electron diffusion exhibits Arrhenius behavior over the temperature range of 298-400 K. We compute an activation energy of 8.9 kJ mol -1 . Through analysis of Arrhenius plots and the application of a simple random walk model it is demonstrated that the computed rate constant for exchange of an excess electron is indeed the phenomenological rate constant associated with the diffusive process

  19. Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms

    Science.gov (United States)

    Gao, Connie W.; Allen, Joshua W.; Green, William H.; West, Richard H.

    2016-06-01

    Reaction Mechanism Generator (RMG) constructs kinetic models composed of elementary chemical reaction steps using a general understanding of how molecules react. Species thermochemistry is estimated through Benson group additivity and reaction rate coefficients are estimated using a database of known rate rules and reaction templates. At its core, RMG relies on two fundamental data structures: graphs and trees. Graphs are used to represent chemical structures, and trees are used to represent thermodynamic and kinetic data. Models are generated using a rate-based algorithm which excludes species from the model based on reaction fluxes. RMG can generate reaction mechanisms for species involving carbon, hydrogen, oxygen, sulfur, and nitrogen. It also has capabilities for estimating transport and solvation properties, and it automatically computes pressure-dependent rate coefficients and identifies chemically-activated reaction paths. RMG is an object-oriented program written in Python, which provides a stable, robust programming architecture for developing an extensible and modular code base with a large suite of unit tests. Computationally intensive functions are cythonized for speed improvements.

  20. KINETICS AND MECHANISMS OF NOx - CHAR REDUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Suuberg, E.M.

    1998-06-19

    This study was undertaken in order to improve understanding of several aspects of the NO-carbon reaction. This reaction is of practical importance in combustion systems, but its close examination also provides some fundamental insight into oxidizing gas-carbon reactions. As part of this study, a comprehensive literature review of earlier work on this reaction has been published (Aarna and Suuberg, Fuel, 1997, 76, 475-491). It has been thought for some time that the kinetics of the NO-carbon reaction are unusual, in that they often show a two-regime Arrhenius behavior. It has, however, turned out during this work that NO is not alone in this regard. In this laboratory, we also uncovered evidence of two kinetic regime behavior in CO{sub 2} gasification. In another laboratory, a former colleague has identified the same behavior in N{sub 2}O. The low temperature reaction regime always shows an activation energy which is lower than that in the high temperature regime, leaving little doubt that a shift in mechanism, as opposed to transport limitations, dictates the behavior. The activation energy of the low temperature regime of these reactions is typically less than 100 kJ/mol, and the activation energy of the high temperature regime is generally considerably in excess of this value. In this study, we have resolved some apparent inconsistencies in the explanation of the low temperature regime, whose rate has generally been ascribed to desorption-controlled processes. Part of the problem in characterization of the different temperature regimes is that they overlap to a high degree. It is difficult to probe the low temperature regime experimentally, because of slow relaxation of the surface oxides in that regime. Using careful experimental techniques, we were able to demonstrate that the low temperature regime is indeed characterized by zero order in NO, as it must be. A separate study is being carried out to model the behavior in this regime in NO and in other gases, and

  1. Kinetics and mechanism of oxidation of tellurium (IV) by periodate in alkaline medium

    International Nuclear Information System (INIS)

    Srinivas, K.; Vani, P.; Dikshitulu, L.S.A.

    1995-01-01

    Detailed kinetic study of the oxidation of tellurium (IV) by periodate in alkaline medium has been carried out to compare the mechanisms of oxidation in the acid and alkaline media. It is interesting to note that the rate step involves a two-electron transfer from tellurium (IV) to periodate in alkaline medium although the kinetic pattern is somewhat different from that in the acid medium. 7 refs., 1 tab

  2. Modeling the Emission of CO from Wood Fires using Detailed Chemical Kinetics

    DEFF Research Database (Denmark)

    Dederichs, Anne

    Carbon monoxide is treated as one of the most common and dangerous of gases evolving in fires. Modeling the formation of the toxic gas CO from in fire enclosures using detailed chemical kinetics is the topic of this manuscript. A semi-empirical model is developed to study the formation of CO from......, the model separately treats the process of pyrolysis and combustion. For under ventilated conditions and at high temperatures during pyrolysis it is found that the process of pyrolysation strongly influences the formation of CO in fire. CO2 follows the same trend....

  3. Mathematical modeling provides kinetic details of the human immune response to vaccination

    Directory of Open Access Journals (Sweden)

    Dustin eLe

    2015-01-01

    Full Text Available With major advances in experimental techniques to track antigen-specific immune responses many basic questions on the kinetics of virus-specific immunity in humans remain unanswered. To gain insights into kinetics of T and B cell responses in human volunteers we combine mathematical models and experimental data from recent studies employing vaccines against yellow fever and smallpox. Yellow fever virus-specific CD8 T cell population expanded slowly with the average doubling time of 2 days peaking 2.5 weeks post immunization. Interestingly, we found that the peak of the yellow fever-specific CD8 T cell response is determined by the rate of T cell proliferation and not by the precursor frequency of antigen-specific cells as has been suggested in several studies in mice. We also found that while the frequency of virus-specific T cells increases slowly, the slow increase can still accurately explain clearance of yellow fever virus in the blood. Our additional mathematical model describes well the kinetics of virus-specific antibody-secreting cell and antibody response to vaccinia virus in vaccinated individuals suggesting that most of antibodies in 3 months post immunization are derived from the population of circulating antibody-secreting cells. Taken together, our analysis provides novel insights into mechanisms by which live vaccines induce immunity to viral infections and highlight challenges of applying methods of mathematical modeling to the current, state-of-the-art yet limited immunological data.

  4. Mathematical modeling provides kinetic details of the human immune response to vaccination.

    Science.gov (United States)

    Le, Dustin; Miller, Joseph D; Ganusov, Vitaly V

    2014-01-01

    With major advances in experimental techniques to track antigen-specific immune responses many basic questions on the kinetics of virus-specific immunity in humans remain unanswered. To gain insights into kinetics of T and B cell responses in human volunteers we combined mathematical models and experimental data from recent studies employing vaccines against yellow fever and smallpox. Yellow fever virus-specific CD8 T cell population expanded slowly with the average doubling time of 2 days peaking 2.5 weeks post immunization. Interestingly, we found that the peak of the yellow fever-specific CD8 T cell response was determined by the rate of T cell proliferation and not by the precursor frequency of antigen-specific cells as has been suggested in several studies in mice. We also found that while the frequency of virus-specific T cells increased slowly, the slow increase could still accurately explain clearance of yellow fever virus in the blood. Our additional mathematical model described well the kinetics of virus-specific antibody-secreting cell and antibody response to vaccinia virus in vaccinated individuals suggesting that most of antibodies in 3 months post immunization were derived from the population of circulating antibody-secreting cells. Taken together, our analysis provided novel insights into mechanisms by which live vaccines induce immunity to viral infections and highlighted challenges of applying methods of mathematical modeling to the current, state-of-the-art yet limited immunological data.

  5. Kinetic mechanism of DNA polymerase I (Klenow)

    International Nuclear Information System (INIS)

    Kuchta, R.D.; Mizrahi, V.; Benkovic, P.A.; Johnson, K.A.; Benkovic, S.J.

    1987-01-01

    The minimal kinetic scheme for DNA polymerization catalyzed by the Klenow fragment of DNA polymerase I (KF) from Escherichia coli has been determined with short DNA oligomers of defined sequence, labeled with [ 32 P]-nucleotides. A key feature of this scheme is a minimal two-step sequence that interconverts the ternary KF-DNA/sub n/-dNTP and KF-DNA/sub n+1/-PP/sub i/ complexes. The rate is not limited by the actual polymerization but by a separate step, possibly important in ensuring fidelity. Evidence for this sequence is supplied by the observation of biphasic kinetics in single-turnover pyrophosphorolysis experiments (the microscopic reverse of polymerization). Data analysis then provides an estimate of the internal equilibrium constant. The dissociations of DNA, dNTP, and PP/sub i/ from the various binary and ternary complexes were measured by partitioning (isotope-trapping) experiments. The rate constant for DNA dissociation from KF is sequence dependent and is rate limiting during nonprocessive DNA synthesis. The combination of single-turnover (both directions) and isotope-trapping experiments provides sufficient information to permit a quantitative evaluation of the kinetic scheme for specific DNA sequences

  6. Kinetics and mechanism of synthetic CoS oxidation process

    Directory of Open Access Journals (Sweden)

    Štrbac N.

    2006-01-01

    Full Text Available The results of investigation of kinetics and mechanism for synthetic a-CoS oxidation process are presented in this paper. Based on experimental data obtained using DTA and XRD analysis and constructed PSD diagrams for Co-S-O system, mechanism of synthetic a-CoS oxidation process is suggested. Characteristic kinetic parameters were obtained for experimental isothermal investigations of desulfurization degree using Sharp method.

  7. A detailed chemical kinetic model for pyrolysis of the lignin model compound chroman

    Directory of Open Access Journals (Sweden)

    James Bland

    2013-12-01

    Full Text Available The pyrolysis of woody biomass, including the lignin component, is emerging as a potential technology for the production of renewable fuels and commodity chemicals. Here we describe the construction and implementation of an elementary chemical kinetic model for pyrolysis of the lignin model compound chroman and its reaction intermediate ortho-quinone methide (o-QM. The model is developed using both experimental and theoretical data, and represents a hybrid approach to kinetic modeling that has the potential to provide molecular level insight into reaction pathways and intermediates while accurately describing reaction rates and product formation. The kinetic model developed here can replicate all known aspects of chroman pyrolysis, and provides new information on elementary reaction steps. Chroman pyrolysis is found to proceed via an initial retro-Diels–Alder reaction to form o-QM + ethene (C2H4, followed by dissociation of o-QM to the C6H6 isomers benzene and fulvene (+ CO. At temperatures of around 1000–1200 K and above fulvene rapidly isomerizes to benzene, where an activation energy of around 270 kJ mol-1 is required to reproduce experimental observations. A new G3SX level energy surface for the isomerization of fulvene to benzene supports this result. Our modeling also suggests that thermal decomposition of fulvene may be important at around 950 K and above. This study demonstrates that theoretical protocols can provide a significant contribution to the development of kinetic models for biomass pyrolysis by elucidating reaction mechanisms, intermediates, and products, and also by supplying realistic rate coefficients and thermochemical properties.

  8. Kinetic details of crystallization in supercooled liquid Pb during the isothermal relaxation

    International Nuclear Information System (INIS)

    Zhou Lili; Liu Rangsu; Tian Zean; Liu Hairong; Hou Zhaoyang; Peng Ping; Zhu Xuanmin; Liu Quanhui

    2012-01-01

    The kinetic details of crystallization in supercooled liquid Pb during the isothermal relaxation process have been investigated by molecular dynamics simulations, and the microstructure evolution analyzed by the cluster-type index method (CTIM) and the tracing method. It has been found that, the dynamic features are consistently correlated with the microstructure evolution and the crystallization characteristics in the mean square displacement (MSD) and the non-Gaussian parameter (NGP): the β relaxation regime corresponds to the minor structural rearrangement because of the “cage effect”, and the atoms attempt to escape from the “cages”; the α relaxation regime is related to a more diffusive movement of atoms, and the appearance of the second plateau in MSD and the non-zero plateau in NGP corresponds to the completion of crystallization. In addition, three distinct stages of nucleation, growth of nuclei and coarsening of crystallites in the crystallization process have been clearly revealed.

  9. Kinetics and mechanism of hydrolysis of benzimidazolylcarbamates

    OpenAIRE

    Norberto, F. P.; Santos, S. P.; Iley, J.; Silva, D. B.; Corte Real, M.

    2007-01-01

    Synthesis of new 2-aminobenzimidazole-1-carbamates was accomplished by carbamoylation of 2-aminobenzimidazole using different substituted phenyl chloroformates. The aqueous hydrolysis of the new compounds was examined in the pH range 1-13 at 25 ºC. The evaluated kinetic parameters led to the conclusion that up to pH 4 reaction proceeds by a bimolecular attack of water to the N-protonated substrate. This is the first time this behavior is described for carbamates, and can be ascribed to the hi...

  10. Detailed Reaction Kinetics for CFD Modeling of Nuclear Fuel Pellet Coating for High Temperature Gas-Cooled Reactors

    International Nuclear Information System (INIS)

    Battaglia, Francine

    2008-01-01

    The research project was related to the Advanced Fuel Cycle Initiative and was in direct alignment with advancing knowledge in the area of Nuclear Fuel Development related to the use of TRISO fuels for high-temperature reactors. The importance of properly coating nuclear fuel pellets received a renewed interest for the safe production of nuclear power to help meet the energy requirements of the United States. High-temperature gas-cooled nuclear reactors use fuel in the form of coated uranium particles, and it is the coating process that was of importance to this project. The coating process requires four coating layers to retain radioactive fission products from escaping into the environment. The first layer consists of porous carbon and serves as a buffer layer to attenuate the fission and accommodate the fuel kernel swelling. The second (inner) layer is of pyrocarbon and provides protection from fission products and supports the third layer, which is silicon carbide. The final (outer) layer is also pyrocarbon and provides a bonding surface and protective barrier for the entire pellet. The coating procedures for the silicon carbide and the outer pyrocarbon layers require knowledge of the detailed kinetics of the reaction processes in the gas phase and at the surfaces where the particles interact with the reactor walls. The intent of this project was to acquire detailed information on the reaction kinetics for the chemical vapor deposition (CVD) of carbon and silicon carbine on uranium fuel pellets, including the location of transition state structures, evaluation of the associated activation energies, and the use of these activation energies in the prediction of reaction rate constants. After the detailed reaction kinetics were determined, the reactions were implemented and tested in a computational fluid dynamics model, MFIX. The intention was to find a reduced mechanism set to reduce the computational time for a simulation, while still providing accurate results

  11. Detailed mechanical design of the LIPAc beam dump radiological shielding

    Energy Technology Data Exchange (ETDEWEB)

    Nomen, Oriol, E-mail: onomen@irec.cat [IREC, Barcelona, Catalonia (Spain); CDEI-UPC, Barcelona, Catalonia (Spain); Martínez, José I.; Arranz, Fernando; Iglesias, Daniel; Barrera, Germán; Brañas, Beatriz [CIEMAT, Madrid (Spain); Ogando, Francisco [UNED, Madrid (Spain); Molla, Joaquín [CIEMAT, Madrid (Spain); Sanmartí, Manel [IREC, Barcelona, Catalonia (Spain)

    2013-10-15

    Highlights: ► Mechanical design of the IFMIF LIPAc beam dump shielding has been performed. ► Lead shutter design performed to shield radiation from beam dump when LIPAc is off. ► External loads, working and dismantling conditions, included as design constraints. -- Abstract: The LIPAc is a 9 MeV, D{sup +} linear prototype accelerator for the validation of the IFMIF accelerator design. The high intensity, 125 mA CW beam is stopped in a copper cone involving a high production of neutrons and gamma radiation and activation of its surface. The beam stopper is surrounded by a shielding to attenuate the resulting radiation so that dose rate values comply with the limits at the different zones of the installation. The shielding includes for that purpose polyethylene rings, water tanks and gray cast iron rings. A lead shutter has also been designed to shield the gamma radiation that comes through the beam tube when the linear accelerator is not in operation, in order to allow access inside the building for maintenance tasks. The present work summarizes the detailed mechanical design of the beam dump shielding and the lead shutter taking into account the design constraints, such as working conditions and other external loads, as well as including provisions for dismantling.

  12. Kinetics and mechanism of DNA repair

    International Nuclear Information System (INIS)

    Meldrum, R.A.; Wharton, C.W.; Shall, S.

    1990-01-01

    Experiments are described in which the feasibility of using caged dideoxy and other nucleoside triphosphate analogues for trapping breaks induced by u.v. radiation damage to mammalian cell DNA is evaluated. These nucleotide analogues that have a photolabile 1-(2-nitrophenyl)ethyl-protecting group attached to the γ-phosphate are placed in situ by permeabilizing cells by exposure to hypo-osmotic medium. The nucleoside triphosphate is released by a 351 nm u.v. laser pulse whence it may incorporate in the growing chain of DNA induced by the excision-repair process and terminate chain elongation. If the photoreleased dideoxynucleoside trisphosphate is isotopically labelled in the α-phosphate position the break is trapped and labelled. Incorporation of radioactivity into trichloroacetic acid insoluble material in these experiments confirms their potential for use in studies of the kinetics of mammalian cell DNA repair. (author)

  13. Microsecond reaction kinetics and catalytic mechanism of bacterial cytochrome oxidases

    NARCIS (Netherlands)

    Paulus, A.

    2017-01-01

    Fundamental biochemical research is of crucial importance for a complete and detailed
    understanding of what drives enzyme activity and how enzyme kinetic properties are
    optimized towards survival of the host organism. When cells fail to produce a fully functional
    enzyme, the organism’s

  14. Kinetics and oxidation mechanisms of polycrystaline niobium

    International Nuclear Information System (INIS)

    Paschoal, J.O.A.

    1979-01-01

    The oxidation kinetics of annealed niobium was determined by thermogravimetric analysis between 450 and 800 0 C and for oxygen pressures varying from 20 to 700 mmHg. The oxidation kinetics of cold worked and/or irradiated niobium for temperatures between 500 and 700 0 C, with oxygen pressures varying from 100 to 300 mmHg. Was also determined. Using X-ray diffraction it was found that the oxide formed in the range of temperature and oxygen pressure considered in this research is γ-Nb 2 O 5 . Optical and scanning eletronic microscopy showed that for annealed niobium oxidized under 600 0 C there was formation of non-uniform oxide layers, containing cracks and pores, presenting very irregular metal/pentoxide interface. The presence of sub-oxide NbOsub(z) platelets was observed in this interface. This sub-oxide platelets where not observed in annealed oxidized niobium samples over 600 0 C; the oxide layers formed were compact. At 800 0 C and the beginning at 700 0 C the interfaces were quite regular. Through microhardness measurements for the metal near the metal/pentoxide interface, the formation of oxygen solid solution was found and the oxygen diffusion coefficient was calculated. The results showed that at 600 0 C the oxygen diffusion coefficient in cold worked niobium is three times larger than the value obtained for annealed niobium. The results suggest that the reaction between annealed niobium and oxygen undaer 600 0 C is controlled by reaction in interface where the oxide layers are not compacted, parcially due to Nb sub(z) platelets formation.(Author) [pt

  15. A comprehensive experimental and detailed chemical kinetic modelling study of 2,5-dimethylfuran pyrolysis and oxidation

    Science.gov (United States)

    Somers, Kieran P.; Simmie, John M.; Gillespie, Fiona; Conroy, Christine; Black, Gráinne; Metcalfe, Wayne K.; Battin-Leclerc, Frédérique; Dirrenberger, Patricia; Herbinet, Olivier; Glaude, Pierre-Alexandre; Dagaut, Philippe; Togbé, Casimir; Yasunaga, Kenji; Fernandes, Ravi X.; Lee, Changyoul; Tripathi, Rupali; Curran, Henry J.

    2013-01-01

    The pyrolytic and oxidative behaviour of the biofuel 2,5-dimethylfuran (25DMF) has been studied in a range of experimental facilities in order to investigate the relatively unexplored combustion chemistry of the title species and to provide combustor relevant experimental data. The pyrolysis of 25DMF has been re-investigated in a shock tube using the single-pulse method for mixtures of 3% 25DMF in argon, at temperatures from 1200–1350 K, pressures from 2–2.5 atm and residence times of approximately 2 ms. Ignition delay times for mixtures of 0.75% 25DMF in argon have been measured at atmospheric pressure, temperatures of 1350–1800 K at equivalence ratios (ϕ) of 0.5, 1.0 and 2.0 along with auto-ignition measurements for stoichiometric fuel in air mixtures of 25DMF at 20 and 80 bar, from 820–1210 K. This is supplemented with an oxidative speciation study of 25DMF in a jet-stirred reactor (JSR) from 770–1220 K, at 10.0 atm, residence times of 0.7 s and at ϕ = 0.5, 1.0 and 2.0. Laminar burning velocities for 25DMF-air mixtures have been measured using the heat-flux method at unburnt gas temperatures of 298 and 358 K, at atmospheric pressure from ϕ = 0.6–1.6. These laminar burning velocity measurements highlight inconsistencies in the current literature data and provide a validation target for kinetic mechanisms. A detailed chemical kinetic mechanism containing 2768 reactions and 545 species has been simultaneously developed to describe the combustion of 25DMF under the experimental conditions described above. Numerical modelling results based on the mechanism can accurately reproduce the majority of experimental data. At high temperatures, a hydrogen atom transfer reaction is found to be the dominant unimolecular decomposition pathway of 25DMF. The reactions of hydrogen atom with the fuel are also found to be important in predicting pyrolysis and ignition delay time experiments. Numerous proposals are made on the mechanism and kinetics of the previously

  16. Kinetics and mechanism of oxidation of chloramphenicol by 1 ...

    Indian Academy of Sciences (India)

    Unknown

    the kinetics and mechanism of oxidation of CAP by. CBT in HClO4 medium at 323 K for elucidating the mechanism of oxidation of this drug. 2. Experimental. Chloramphenicol (Sigma, USA) was purified before use. CBT was prepared and purified as reported ear- lier.10 AnalaR grade chemicals and double distilled.

  17. Routing the asteroid surface vehicle with detailed mechanics

    Science.gov (United States)

    Yu, Yang; Baoyin, He-Xi

    2014-06-01

    The motion of a surface vehicle on/above an irregular object is investigated for a potential interest in the insitu explorations to asteroids of the solar system. A global valid numeric method, including detailed gravity and geomorphology, is developed to mimic the behaviors of the test particles governed by the orbital equations and surface coupling effects. A general discussion on the surface mechanical environment of a specified asteroid, 1620 Geographos, is presented to make a global evaluation of the surface vehicle's working conditions. We show the connections between the natural trajectories near the ground and differential features of the asteroid surface, which describes both the good and bad of typical terrains from the viewpoint of vehicles' dynamic performances. Monte Carlo simulations are performed to take a further look at the trajectories of particles initializing near the surface. The simulations reveal consistent conclusions with the analysis, i.e., the open-field flat ground and slightly concave basins/valleys are the best choices for the vehicles' dynamical security. The dependence of decending trajectories on the releasing height is studied as an application; the results show that the pole direction (where the centrifugal force is zero) is the most stable direction in which the shift of a natural trajectory will be well limited after landing. We present this work as an example for pre-analysis that provides guidance to engineering design of the exploration site and routing the surface vehicles.

  18. Detailed mechanism of squalene epoxidase inhibition by terbinafine.

    Science.gov (United States)

    Nowosielski, Marcin; Hoffmann, Marcin; Wyrwicz, Lucjan S; Stepniak, Piotr; Plewczynski, Dariusz M; Lazniewski, Michal; Ginalski, Krzysztof; Rychlewski, Leszek

    2011-02-28

    Squalene epoxidase (SE) is a key flavin adenine dinucleotide (FAD)-dependent enzyme of ergosterol and cholesterol biosynthetic pathways and an attractive potential target for drugs used to inhibit the growth of pathogenic fungi or to lower cholesterol level. Although many studies on allylamine drugs activity have been published during the last 30 years, up until now no detailed mechanism of the squalene epoxidase inhibition has been presented. Our study brings such a model at atomic resolution in the case of yeast Saccharomyces cerevisiae . Presented data resulting from modeling studies are in excellent agreement with experimental findings. A fully atomic three-dimensional (3D) model of squalene epoxidase (EC 1.14.99.7) from S. cerevisiae was built with the help of 3D-Jury approach and further screened based on data known from mutation experiments leading to terbinafine resistance. Docking studies followed by molecular dynamics simulations and quantum interaction energy calculations [MP2/6-31G(d)] resulted in the identification of the terbinafine-squalene epoxidase mode of interaction. In the energetically most likely orientation of terbinafine its interaction energy with the protein is ca. 120 kJ/mol. In the favorable position the terbinafine lipophilic moiety is located vertically inside the squalene epoxidase binding pocket with the tert-butyl group oriented toward its center. Such a position results in the SE conformational changes and prevents the natural substrate from being able to bind to the enzyme's active site. That would explain the noncompetitive manner of SE inhibition. We found that the strongest interaction between terbinafine and SE stems from hydrogen bonding between hydrogen-bond donors, hydroxyl group of Tyr90 and amine nitrogen atom of terbinafine. Moreover, strong attractive interactions were recorded for amino acids whose mutations resulted in terbinafine resistance. Our results, elucidating at a molecular level the mode of terbinafine

  19. Kinetics and mechanism of dimethylzinc pyrolysis

    International Nuclear Information System (INIS)

    Lambert-Pacht, I.

    1964-05-01

    We have studied the pyrolysis of dimethyl-zinc in sealed bulbs between 250 and 400 Celsius degrees with and without cyclohexane, one or other of the reactants being completely deuterated. We have thus shown that the following mechanism occurs: -1) CH 3 Zn CH 3 → CH 3 + Zn CH 3 , -2) CH 3 + C 6 H 12 → CH 4 + C 6 H 11 , -3) 2 CH 3 Zn → (CH 3 Zn) 2 which decomposes to give methane. We have calculated the activation energy for step I: E I = 45.5 ± 3.3 kCal/mole. The study of the reaction in the absence of cyclohexane has made it possible to show that it is not a chain reaction; also the lower limit of the activation energy for the reaction: -4) CH 3 + CH 3 Zn CH 3 → CH 4 + CH 2 Zn CH 3 , has been calculated. It has been found that E 4 ≥ 15 kCal/mole. (author) [fr

  20. Kinetics and mechanism of polymerization of methyl methacrylate ...

    Indian Academy of Sciences (India)

    Unknown

    Kinetics and mechanism of polymerization of methyl methacrylate initiated by stibonium ylide. A K SRIVASTAVA and AJEY KUMAR CHAURASIA. Department of Chemistry, H B Technological Institute, Kanpur 208 002, India e-mail: akspolym@rediffmail.com. MS received 6 September 2002; revised 25 July 2003. Abstract.

  1. Kinetics and mechanism of oxidation of aliphatic primary alcohols by ...

    Indian Academy of Sciences (India)

    Unknown

    Kinetics and mechanism of oxidation of aliphatic primary alcohols by quinolinium bromochromate. SONU SARASWAT, VINITA SHARMA and K K BANERJI*. Department of Chemistry, JNV University, Jodhpur 342 005, India e-mail: banerjikk@rediffmail.com. MS received 4 December 2001; revised 2 November 2002.

  2. Kinetics and Mechanism of the Oxidation of Coomassie Brilliant Blue ...

    African Journals Online (AJOL)

    NICOLAAS

    Kinetics and Mechanism of the Oxidation of Coomassie Brilliant Blue-R dye by Hypochlorite and Role of Acid there in. Srinivasu Nadupalli, Venkata D.B.C. Dasireddy, Neil A. Koorbanally and Sreekantha B. Jonnalagadda*. School of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Private.

  3. Kinetic mechanism and nucleotide specificity of NADH peroxidase

    International Nuclear Information System (INIS)

    Stoll, V.S.; Blanchard, J.S.

    1988-01-01

    NADH peroxidase is a flavoprotein isolated from Streptococcus faecalis which catalyzes the pyridine nucleotide-dependent reduction of hydrogen peroxide to water. Initial velocity, product, and dead-end inhibition studies have been performed at pH 7.5 and support a ping-pong kinetic mechanism. In the absence of hydrogen peroxide, both transhydrogenation between NADH and thioNAD, and isotope exchange between [ 14 C]NADH and NAD, have been demonstrated, although in both these experiments, the maximal velocity of nucleotide exchange was less than 1.5% the maximal velocity of the peroxidatic reaction. We propose that NADH binds tightly to both oxidized and two-electron reduced enzyme. NADH oxidation proceeds stereospecifically with the transfer of the 4S hydrogen to enzyme, and then, via exchange, to water. No primary tritium kinetic isotope effect was observed, and no statistically significant primary deuterium kinetic isotope effects on V/K were determined, although primary deuterium kinetic isotope effects on V were observed in the presence and absence of sodium acetate. NADH peroxidase thus shares with other flavoprotein reductases striking kinetic, spectroscopic, and stereochemical similarities. On this basis, we propose a chemical mechanism for the peroxide cleaving reaction catalyzed by NADH peroxidase which involves the obligate formation of a flavinperoxide, and peroxo bond cleavage by nucleophilic attack by enzymatic dithiols

  4. Numerical analysis of knock during HCCI in a high compression ratio methanol engine based on LES with detailed chemical kinetics

    International Nuclear Information System (INIS)

    Zhen, Xudong; Wang, Yang

    2015-01-01

    Highlights: • Knock during HCCI in a high compression ratio methanol engine was modeled. • A detailed methanol mechanism was used to simulate the knocking combustion. • Compared with the SI engines, the HCCI knocking combustion burnt faster. • The reaction rate of HCO had two obvious peaks, one was positive, and another was negative. • Compared with the SI engines, the values of the reaction rates of CH 2 O, H 2 O 2 , and HO 2 were higher, and it had negative peaks. - Abstract: In this study, knock during HCCI (homogeneous charge compression ignition) was studied based on LES (large eddy simulation) with methanol chemical kinetics (84-reaction, 21-species) in a high compression ratio methanol engine. The non-knocking and knocking combustion of SI (spark ignition) and HCCI engines were compared. The results showed that the auto-ignition spots were initially occurred near the combustion chamber wall. The knocking combustion burnt faster during HCCI than SI methanol engine. The HCO reaction rate was different from SI engine, it had two obvious peaks, one was positive peak, and another was negative peak. Compared with the SI methanol engine, in addition to the concentration of HCO, the concentrations of the other intermediate products and species such as CO, OH, CH 2 O, H 2 O 2 , HO 2 were increased significantly; the reaction rates of CH 2 O, H 2 O 2 , and HO 2 had negative peaks, and whose values were several times higher than SI methanol engine

  5. Functional Insights Revealed by the Kinetic Mechanism of CRISPR/Cas9.

    Science.gov (United States)

    Raper, Austin T; Stephenson, Anthony A; Suo, Zucai

    2018-02-28

    The discovery of prokaryotic adaptive immunity prompted widespread use of the RNA-guided clustered regularly interspaced short palindromic repeat (CRISPR)-associated (Cas) endonuclease Cas9 for genetic engineering. However, its kinetic mechanism remains undefined, and details of DNA cleavage are poorly characterized. Here, we establish a kinetic mechanism of Streptococcus pyogenes Cas9 from guide-RNA binding through DNA cleavage and product release. Association of DNA to the binary complex of Cas9 and guide-RNA is rate-limiting during the first catalytic turnover, while DNA cleavage from a pre-formed ternary complex of Cas9, guide-RNA, and DNA is rapid. Moreover, an extremely slow release of DNA products essentially restricts Cas9 to be a single-turnover enzyme. By simultaneously measuring the contributions of the HNH and RuvC nuclease activities of Cas9 to DNA cleavage, we also uncovered the kinetic basis by which HNH conformationally regulates the RuvC cleavage activity. Together, our results provide crucial kinetic and functional details regarding Cas9 which will inform gene-editing experiments, guide future research to understand off-target DNA cleavage by Cas9, and aid in the continued development of Cas9 as a biotechnological tool.

  6. Kinetic parameters and TL mechanism in cadmium tetra borate phosphor

    International Nuclear Information System (INIS)

    Annalakshmi, O.; Jose, M.T.; Sridevi, J.; Venkatraman, B.; Amarendra, G.; Mandal, A.B.

    2014-01-01

    Polycrystalline powder samples of cadmium tetra borate were synthesized by a simple solid state sintering technique and gamma irradiated sample showed a simple Thermoluminescence (TL) glow peak around 460 K. The TL kinetic parameters of gamma irradiated phosphor were determined by initial rise (IR), isothermal decay (ID), peak shape (PS), variable heating rate (VHR) and glow curve de-convolution method. The kinetic parameters such as activation energy (E), frequency factor (s) and order of kinetics (b) were calculated by IR, ID, PS and VHR methods are in the order of ∼1.05 eV, 10 9 –10 12 s −1 and 1.58, respectively. From the results of TL and PL emission studies carried out on the phosphor revealed that the defect centers related to TL is different from that for PL. EPR measurements were carried out to identify the defect centers formed in cadmium tetra borate phosphor on gamma irradiation. Based on EPR studies the mechanism for TL process in cadmium tetra borate is proposed in this paper -- Highlights: • Polycrystalline powder samples of undoped cadmium tetra borate synthesized. • Cadmium tetra borate phosphor exhibits a dosimetric peak at 458 K. • Kinetic parameters of the trap responsible for TL evaluated. • TL mechanism is proposed from TL to EPR correlation studies

  7. Kinetic parameters and TL mechanism in cadmium tetra borate phosphor

    Energy Technology Data Exchange (ETDEWEB)

    Annalakshmi, O. [Radiological Safety Division, Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Jose, M.T., E-mail: mtj@igcar.gov.in [Radiological Safety Division, Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Sridevi, J. [Central Leather Research Institute, Council of Scientific and Industrial Research, Chennai 600 020, Tamilnadhu (India); Venkatraman, B. [Radiological Safety Division, Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Amarendra, G. [Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Mandal, A.B. [Central Leather Research Institute, Council of Scientific and Industrial Research, Chennai 600 020, Tamilnadhu (India)

    2014-03-15

    Polycrystalline powder samples of cadmium tetra borate were synthesized by a simple solid state sintering technique and gamma irradiated sample showed a simple Thermoluminescence (TL) glow peak around 460 K. The TL kinetic parameters of gamma irradiated phosphor were determined by initial rise (IR), isothermal decay (ID), peak shape (PS), variable heating rate (VHR) and glow curve de-convolution method. The kinetic parameters such as activation energy (E), frequency factor (s) and order of kinetics (b) were calculated by IR, ID, PS and VHR methods are in the order of ∼1.05 eV, 10{sup 9}–10{sup 12} s{sup −1} and 1.58, respectively. From the results of TL and PL emission studies carried out on the phosphor revealed that the defect centers related to TL is different from that for PL. EPR measurements were carried out to identify the defect centers formed in cadmium tetra borate phosphor on gamma irradiation. Based on EPR studies the mechanism for TL process in cadmium tetra borate is proposed in this paper -- Highlights: • Polycrystalline powder samples of undoped cadmium tetra borate synthesized. • Cadmium tetra borate phosphor exhibits a dosimetric peak at 458 K. • Kinetic parameters of the trap responsible for TL evaluated. • TL mechanism is proposed from TL to EPR correlation studies.

  8. Fuel spray combustion of waste cooking oil and palm oil biodiesel: Direct photography and detailed chemical kinetics

    KAUST Repository

    Kuti, Olawole

    2013-10-14

    This paper studies the ignition processes of two biodiesel from two different feedstock sources, namely waste cooked oil (WCO) and palm oil (PO). They were investigated using the direct photography through high-speed video observations and detailed chemical kinetics. The detailed chemical kinetics modeling was carried out to complement data acquired using the high-speed video observations. For the high-speed video observations, an image intensifier combined with OH* filter connected to a high-speed video camera was used to obtain OH* chemiluminscence image near 313 nm. The OH* images were used to obtain the experimental ignition delay of the biodiesel fuels. For the high-speed video observations, experiments were done at an injection pressure of 100, 200 and 300 MPa using a 0.16 mm injector nozzle. Also a detailed chemical kinetics for the biodiesel fuels was carried out using ac chemical kinetics solver adopting a 0-D reactor model to obtain the chemical ignition delay of the combusting fuels. Equivalence ratios obtained from the experimental ignition delay were used for the detailed chemical kinetics analyses. The Politecnico di Milano\\'s thermochemical and reaction kinetic data were adopted to simulate the ignition processes of the biodiesels using the five fatty acid methyl esters (FAME) major components in the biodiesel fuels. From the high-speed video observations, it was observed that at increasing injection pressure, experimental ignition delay increased as a result of improvement in fuel and air mixing effects. Also the palm oil biodiesel has a shorter ignition delay compared to waste cooked oil biodiesel. This phenomenon could be attributed to the higher cetane number of palm biodiesel. The fuel spray ignition properties depend on both the physical ignition delay and chemical ignition delay. From the detailed chemical kinetic results it was observed that at the low temperature, high ambient pressure conditions reactivity increased as equivalent ratio

  9. Fuel spray combustion of waste cooking oil and palm oil biodiesel: Direct photography and detailed chemical kinetics

    KAUST Repository

    Kuti, Olawole; Nishida, Keiya; Sarathy, Mani; Zhu, Jingyu

    2013-01-01

    This paper studies the ignition processes of two biodiesel from two different feedstock sources, namely waste cooked oil (WCO) and palm oil (PO). They were investigated using the direct photography through high-speed video observations and detailed chemical kinetics. The detailed chemical kinetics modeling was carried out to complement data acquired using the high-speed video observations. For the high-speed video observations, an image intensifier combined with OH* filter connected to a high-speed video camera was used to obtain OH* chemiluminscence image near 313 nm. The OH* images were used to obtain the experimental ignition delay of the biodiesel fuels. For the high-speed video observations, experiments were done at an injection pressure of 100, 200 and 300 MPa using a 0.16 mm injector nozzle. Also a detailed chemical kinetics for the biodiesel fuels was carried out using ac chemical kinetics solver adopting a 0-D reactor model to obtain the chemical ignition delay of the combusting fuels. Equivalence ratios obtained from the experimental ignition delay were used for the detailed chemical kinetics analyses. The Politecnico di Milano's thermochemical and reaction kinetic data were adopted to simulate the ignition processes of the biodiesels using the five fatty acid methyl esters (FAME) major components in the biodiesel fuels. From the high-speed video observations, it was observed that at increasing injection pressure, experimental ignition delay increased as a result of improvement in fuel and air mixing effects. Also the palm oil biodiesel has a shorter ignition delay compared to waste cooked oil biodiesel. This phenomenon could be attributed to the higher cetane number of palm biodiesel. The fuel spray ignition properties depend on both the physical ignition delay and chemical ignition delay. From the detailed chemical kinetic results it was observed that at the low temperature, high ambient pressure conditions reactivity increased as equivalent ratio

  10. Mechanisms and kinetics models for ultrasonic waste activated sludge disintegration.

    Science.gov (United States)

    Wang, Fen; Wang, Yong; Ji, Min

    2005-08-31

    Ultrasonic energy can be applied as pre-treatment to disintegrate sludge flocs and disrupt bacterial cells' walls, and the hydrolysis can be improved, so that the rate of sludge digestion and methane production is improved. In this paper, by adding NaHCO3 to mask the oxidizing effect of OH, the mechanisms of disintegration are investigated. In addition, kinetics models for ultrasonic sludge disintegration are established by applying multi-variable linear regression method. It has been found that hydro-mechanical shear forces predominantly responsible for the disintegration, and the contribution of oxidizing effect of OH increases with the amount of the ultrasonic density and ultrasonic intensity. It has also been inferred from the kinetics model which dependent variable is SCOD+ that both sludge pH and sludge concentration significantly affect the disintegration.

  11. GENERAL EQUATIONS OF CARBONIZATION OF EUCALYPTUS SPP KINETIC MECHANISMS

    Directory of Open Access Journals (Sweden)

    Túlio Jardim Raad

    2006-06-01

    Full Text Available In the present work, a set of general equations related to kinetic mechanism of wood compound carbonization: hemicelluloses, cellulose and lignin was obtained by Avrami-Eroffev and Arrhenius equations and Thermogravimetry of Eucalyptus cloeziana, Eucalyptus camaldulensis, Corymbia citriodora, Eucalyptus urophylla and Eucalyptus grandis samples, TG-Isothermal and TG-Dynamic. The different thermal stabilities and decomposition temperature bands of those species compounds were applied as strategy to obtain the kinetic parameters: activation energy, exponential factor and reaction order. The kinetic model developed was validated by thermogravimetric curves from carbonization of others biomass such as coconut. The kinetic parameters found were - Hemicelluloses: E=98,6 kJmol, A=3,5x106s-1 n=1,0; - Cellulose: E=182,2 kJmol, A=1,2x1013s-1 n=1,5; - Lignin: E=46,6 kJmol, A=2,01s-1 n=0,41. The set of equations can be implemented in a mathematical model of wood carbonization simulation (with heat and mass transfer equations with the aim of optimizing the control and charcoal process used to produce pig iron.

  12. Systems biology from micro-organisms to human metabolic diseases: the role of detailed kinetic models.

    Science.gov (United States)

    Bakker, Barbara M; van Eunen, Karen; Jeneson, Jeroen A L; van Riel, Natal A W; Bruggeman, Frank J; Teusink, Bas

    2010-10-01

    Human metabolic diseases are typically network diseases. This holds not only for multifactorial diseases, such as metabolic syndrome or Type 2 diabetes, but even when a single gene defect is the primary cause, where the adaptive response of the entire network determines the severity of disease. The latter may differ between individuals carrying the same mutation. Understanding the adaptive responses of human metabolism naturally requires a systems biology approach. Modelling of metabolic pathways in micro-organisms and some mammalian tissues has yielded many insights, qualitative as well as quantitative, into their control and regulation. Yet, even for a well-known pathway such as glycolysis, precise predictions of metabolite dynamics from experimentally determined enzyme kinetics have been only moderately successful. In the present review, we compare kinetic models of glycolysis in three cell types (African trypanosomes, yeast and skeletal muscle), evaluate their predictive power and identify limitations in our understanding. Although each of these models has its own merits and shortcomings, they also share common features. For example, in each case independently measured enzyme kinetic parameters were used as input. Based on these 'lessons from glycolysis', we will discuss how to make best use of kinetic computer models to advance our understanding of human metabolic diseases.

  13. Non-Linear Response to Periodic Forcing of Methane-Air Global and Detailed Kinetics in Continuous Stirred Tank Reactors Close to Extinction Conditions

    Directory of Open Access Journals (Sweden)

    Francesco Saverio Marra

    2015-09-01

    Full Text Available This paper focus on the behavior of a continuous stirred tank reactor (CSTR subject to perturbations of finite amplitude and frequency. Two main objectives are pursued: to determine the extinction line in the equivalence ratio (φ - residence time (τ plane, fixed the thermodynamic state conditions; and to characterize the response of the chemical system to periodic forcing of the residence time. Transient simulations of combustion of methane with air, using both global single-step and detailed chemical kinetic mechanisms, have been conducted and the corresponding asymptotic solutions analyzed. Results indicate very different dynamical behaviors, posing the issue of a proper choice of the kinetic scheme for the numerical study of combustion oscillations.

  14. NDMA formation by chloramination of ranitidine: Kinetics and mechanism

    KAUST Repository

    Le Roux, Julien

    2012-10-16

    The kinetics of decomposition of the pharmaceutical ranitidine (a major precursor of NDMA) during chloramination was investigated and some decomposition byproducts were identified by using high performance liquid chromatography coupled with mass spectrometry (HPLC-MS). The reaction between monochloramine and ranitidine followed second order kinetics and was acid-catalyzed. Decomposition of ranitidine formed different byproducts depending on the applied monochloramine concentration. Most identified products were chlorinated and hydroxylated analogues of ranitidine. In excess of monochloramine, nucleophilic substitution between ranitidine and monochloramine led to byproducts that are critical intermediates involved in the formation of NDMA, for example, a carbocation formed from the decomposition of the methylfuran moiety of ranitidine. A complete mechanism is proposed to explain the high formation yield of NDMA from chloramination of ranitidine. These results are of great importance to understand the formation of NDMA by chloramination of tertiary amines. © 2012 American Chemical Society.

  15. Kinetic modelling and mechanism of dye adsorption on unburned carbon

    Energy Technology Data Exchange (ETDEWEB)

    Wang, S.B.; Li, H.T. [Curtin University of Technology, Perth, WA (Australia). Dept. of Chemical Engineering

    2007-07-01

    Textile dyeing processes are among the most environmentally unfriendly industrial processes by producing coloured wastewaters. The adsorption method using unburned carbon from coal combustion residue was studied for the decolourisation of typical acidic and basic dyes. It was discovered that the unburned carbon showed high adsorption capacity at 1.97 x 10{sup -4} and 5.27 x 10{sup -4} mol/g for Basic Violet 3 and Acid Black 1, respectively. The solution pH, particle size and temperature significantly influenced the adsorption capacity. Higher solution pH favoured the adsorption of basic dye while reduced the adsorption of acid dye. The adsorption of dye increased with increasing temperature but decreased with increasing particle size. Sorption kinetic data indicated that the adsorption kinetics followed the pseudo-second-order model. The adsorption mechanism consisted of two processes, external diffusion and intraparticle diffusion, and the external diffusion was the dominating process.

  16. Evaluation and Development of Chemical Kinetic Mechanism Reduction Scheme for Biodiesel and Diesel Fuel Surrogates

    DEFF Research Database (Denmark)

    Poon, Hiew Mun; Ng, Hoon Kiat; Gan, Suyin

    2013-01-01

    The aim of this study is to evaluate the existing chemical kinetic mechanism reduction techniques. From here, an appropriate reduction scheme was developed to create compact yet comprehensive surrogate models for both diesel and biodiesel fuels for diesel engine applications. The reduction...... techniques applied here were Directed Relation Graph (DRG), DRG with Error Propagation, DRG-aided Sensitivity Analysis, and DRG with Error Propagation and Sensitivity Analysis. Nonetheless, the reduced mechanisms generated via these techniques were not sufficiently small for application in multi......-dimensional computational fluid dynamics (CFD) study. A new reduction scheme was therefore formulated. A 68-species mechanism for biodiesel surrogate and a 49-species mechanism for diesel surrogate were successfully derived from the respective detailed mechanisms. An overall 97% reduction in species number...

  17. Estimating kinetic mechanisms with prior knowledge I: Linear parameter constraints.

    Science.gov (United States)

    Salari, Autoosa; Navarro, Marco A; Milescu, Mirela; Milescu, Lorin S

    2018-02-05

    To understand how ion channels and other proteins function at the molecular and cellular levels, one must decrypt their kinetic mechanisms. Sophisticated algorithms have been developed that can be used to extract kinetic parameters from a variety of experimental data types. However, formulating models that not only explain new data, but are also consistent with existing knowledge, remains a challenge. Here, we present a two-part study describing a mathematical and computational formalism that can be used to enforce prior knowledge into the model using constraints. In this first part, we focus on constraints that enforce explicit linear relationships involving rate constants or other model parameters. We develop a simple, linear algebra-based transformation that can be applied to enforce many types of model properties and assumptions, such as microscopic reversibility, allosteric gating, and equality and inequality parameter relationships. This transformation converts the set of linearly interdependent model parameters into a reduced set of independent parameters, which can be passed to an automated search engine for model optimization. In the companion article, we introduce a complementary method that can be used to enforce arbitrary parameter relationships and any constraints that quantify the behavior of the model under certain conditions. The procedures described in this study can, in principle, be coupled to any of the existing methods for solving molecular kinetics for ion channels or other proteins. These concepts can be used not only to enforce existing knowledge but also to formulate and test new hypotheses. © 2018 Salari et al.

  18. Ammonia removal in electrochemical oxidation: Mechanism and pseudo-kinetics

    International Nuclear Information System (INIS)

    Li Liang; Liu Yan

    2009-01-01

    This paper investigated the mechanism and pseudo-kinetics for removal of ammonia by electrochemical oxidation with RuO 2 /Ti anode using batch tests. The results show that the ammonia oxidation rates resulted from direct oxidation at electrode-liquid interfaces of the anode by stepwise dehydrogenation, and from indirect oxidation by hydroxyl radicals were so slow that their contribution to ammonia removal was negligible under the condition with Cl - . The oxidation rates of ammonia ranged from 1.0 to 12.3 mg N L -1 h -1 and efficiency reached nearly 100%, primarily due to the indirect oxidation of HOCl, and followed pseudo zero-order kinetics in electrochemical oxidation with Cl - . About 88% ammonia was removed from the solution. The removed one was subsequently found in the form of N 2 in the produced gas. The rate at which Cl - lost electrons at the anode was a major factor in the overall ammonia oxidation. Current density and Cl - concentration affected the constant of the pseudo zero-order kinetics, expressed by k = 0.0024[Cl - ] x j. The ammonia was reduced to less than 0.5 mg N L -1 after 2 h of electrochemical oxidation for the effluent from aerobic or anaerobic reactors which treated municipal wastewater. This result was in line with the strict discharge requirements

  19. Study of ignition in a high compression ratio SI (spark ignition) methanol engine using LES (large eddy simulation) with detailed chemical kinetics

    International Nuclear Information System (INIS)

    Zhen, Xudong; Wang, Yang

    2013-01-01

    Methanol has been recently used as an alternative to conventional fuels for internal combustion engines in order to satisfy some environmental and economical concerns. In this paper, the ignition in a high compression ratio SI (spark ignition) methanol engine was studied by using LES (large eddy simulation) with detailed chemical kinetics. A 21-species, 84-reaction methanol mechanism was adopted to simulate the auto-ignition process of the methanol/air mixture. The MIT (minimum ignition temperature) and MIE (minimum ignition energy) are two important properties for designing safety standards and understanding the ignition process of combustible mixtures. The effects of the flame kernel size, flame kernel temperature and equivalence ratio were also examined on MIT, MIE and IDP (ignition delay period). The methanol mechanism was validated by experimental test. The simulated results showed that the flame kernel size, temperature and energy dramatically affected the values of the MIT, MIE and IDP for a methanol/air mixture, the value of the ignition delay period was not only related to the flame kernel energy, but also to the flame kernel temperature. - Highlights: • We used LES (large eddy simulation) coupled with detailed chemical kinetics to simulate methanol ignition. • The flame kernel size and temperature affected the minimum ignition temperature. • The flame kernel temperature and energy affected the ignition delay period. • The equivalence ratio of methanol–air mixture affected the ignition delay period

  20. A computational environment for creating and testing reduced chemical kinetic mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Montgomery, C.J.; Swensen, D.A.; Harding, T.V.; Cremer, M.A.; Bockelie, M.J. [Reaction Engineering International, Salt Lake City, UT (USA)

    2002-02-01

    This paper describes software called computer assisted reduced mechanism problem solving environment (CARM-PSE) that gives the engineer the ability to rapidly set up, run and examine large numbers of problems comparing detailed and reduced (approximate) chemistry. CARM-PSE integrates the automatic chemical mechanism reduction code CARM and the codes that simulate perfectly stirred reactors and plug flow reactors into a user-friendly computational environment. CARM-PSE gives the combustion engineer the ability to easily test chemical approximations over many hundreds of combinations of inputs in a multidimensional parameter space. The demonstration problems compare detailed and reduced chemical kinetic calculations for methane-air combustion, including nitrogen oxide formation, in a stirred reactor and selective non-catalytic reduction of NOx, in coal combustion flue gas.

  1. Uranium dioxide sintering Kinetics and mechanisms under controlled oxygen potentials

    International Nuclear Information System (INIS)

    Freitas, C.T. de.

    1980-06-01

    The initial, intermediate, and final sintering stages of uranium dioxide were investigated as a function of stoichiometry and temperature by following the kinetics of the sintering reaction. Stoichiometry was controlled by means of the oxygen potential of the sintering atmosphere, which was measured continuously by solid-state oxygen sensors. Included in the kinetic study were microspheres originated from UO 2 gels and UO 2 pellets produced by isostatic pressing ceramic grade powders. The microspheres sintering behavior was examined using hot-stage microscopy and a specially designed high-temperature, controlled atmosphere furnace. This same furnace was employed as part of an optical dilatometer, which was utilized in the UO 2 pellet sintering investigations. For controlling the deviations from stoichiometry during heat treatment, the oxygen partial pressure in the sintering atmosphere was varied by passing the gas through a Cu-Ti-Cu oxygen trap. The trap temperature determined the oxygen partial pressure of the outflowing mixture. Dry hydrogen was also used in some of the UO sub(2+x) sintering experiments. The determination of diametrial shrinkages and sintering indices was made utilizing high-speed microcinematography and ultra-microbalance techniques. It was observed that the oxygen potential has a substantial influence on the kinetics of the three sintering stages. The control of the sintering atmosphere oxygen partial pressure led to very fast densification of UO sub(2+x). Values in the interval 95.0 to 99.5% of theoretical density were reached in less than one minute. Uranium volume diffusion is the dominant mechanism in the initial and intermediate sintering stages. For the final stage, uranium grain boundary diffusion was found to be the main sintering mechanism. (Author) [pt

  2. Kinetics and mechanisms of reactions involving small aromatic reactive intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Lin, M.C. [Emory Univ., Atlanta, GA (United States)

    1993-12-01

    Small aromatic radicals such as C{sub 6}H{sub 5}, C{sub 6}H{sub 5}O and C{sub 6}H{sub 4} are key prototype species of their homologs. C{sub 6}H{sub 5} and its oxidation product, C{sub 6}H{sub 5}O are believed to be important intermediates which play a pivotal role in hydrocarbon combustion, particularly with regard to soot formation. Despite their fundamental importance, experimental data on the reaction mechanisms and reactivities of these species are very limited. For C{sub 6}H{sub 5}, most kinetic data except its reactions with NO and NO{sub 2}, were obtained by relative rate measurements. For C{sub 6}H{sub 5}O, the authors have earlier measured its fragmentation reaction producing C{sub 5}H{sub 5} + CO in shock waves. For C{sub 6}H{sub 4}, the only rate constant measured in the gas phase is its recombination rate at room temperature. The authors have proposed to investigate systematically the kinetics and mechanisms of this important class of molecules using two parallel laser diagnostic techniques--laser resonance absorption (LRA) and resonance enhanced multiphoton ionization mass spectrometry (REMPI/MS). In the past two years, study has been focused on the development of a new multipass adsorption technique--the {open_quotes}cavity-ring-down{close_quotes} technique for kinetic applications. The preliminary results of this study appear to be quite good and the sensitivity of the technique is at least comparable to that of the laser-induced fluorescence method.

  3. Tabulated chemical kinetics for efficient and detailed simulations of diesel engine combustion

    NARCIS (Netherlands)

    Bekdemir, C.

    2012-01-01

    Efficient and detailed computational tools to simulate engine combustion are of great importance. The internal combustion engine will remain the primary mean for transportation in the decades to come. Especially diesel engines are, and become increasingly more, popular because of their high

  4. Kinetics and mechanism of oxidation of carbidized electrolytic chromium coatings

    International Nuclear Information System (INIS)

    Arkharov, V.I.; Yar-Mukhamedov, Sh.Kh.

    1978-01-01

    Thermal stability carbidized electrolytic chromium coatings has been studied depending on the conditions of their formation; the specific features of the mechanism of oxidation at 1200 deg in an air atmosphere have been elucidated. It has been established that kinetics of high temperature oxidation of the coatings depends essentially on the conditions of their formation and on the composition of steel to which the coating is applied. It has been shown that two oxidation mechanisms are possible: by diffusion of the residual chromium through a carbide layer along the carbide grain boundaries outwards or, when there is no residual chromium, by chemical reaction of carbon combustion and oxidation of the liberated chromium. The comparison of oxidation kinetic curves of the samples of 38KhMYuA, 35KhGSA, and DI-22 steels with and without coating has shown that the coatings under study have a better protective effect on 38KhMYuA steel than on 35KhGSA, although without coating oxidability of the first steel is higher than that of the second

  5. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    Energy Technology Data Exchange (ETDEWEB)

    Gorman, Brian P [Colorado School of Mines, Golden, CO (United States)

    2015-09-02

    Project Description: The general objective of the proposed research is to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, pCO2, and modest ranges in T and P. This will be accomplished by studying both reaction rates and solubility from changes in solution chemistry, and making nanoscale observations of calcite precipitate surface morphology and composition at the micro-to-nano-scale to provide an understanding of controlling reaction mechanisms and pathways. The specific objectives necessary to reach the general objective are: a) determination of how pCO2, Ca2+, ionic strength and “foreign” ions influence reaction rates; and b) investigate the influence of these parameters on apparent kinetic solubility from dissolution and precipitation reactions. This information will clearly be central to the construction of reliable reaction-transport models to predict reservoir and formation response to increased CO2 in saline waters. This program was initially collaborative with John Morse at Texas A&M, however his passing shortly after the beginning of this program resulted in abbreviated research time and effort. Summary of Results: Early studies using electron microscopy and spectroscopy indicated that carbonate precipitation from natural seawater (NSW) conditions onto aragonite substrates was mediated by a surface amorphous calcium carbonate layer. It was hypothesized that this ACC layer (observed after < 5days reaction time) was responsible for the abnormal reaction kinetics and also served as a metastable seed layer for growth of epitaxial aragonite. Further studies of the ACC formation mechanism indicated a strong dependence on the Mg concentration in solution. Subsequent studies at shorter times (10 hrs) on calcite substrates and in a wide range of supersaturation conditions did not indicate any ACC layer. Instead, an epitaxial layer by layer

  6. Precipitation kinetics and mechanical behavior in a solution treated and aged dual phase stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Badji, R., E-mail: riadbadji1@yahoo.fr [Welding and NDT Research Centre (CSC), B.P. 64, Cheraga (Algeria); Kherrouba, N.; Mehdi, B.; Cheniti, B. [Welding and NDT Research Centre (CSC), B.P. 64, Cheraga (Algeria); Bouabdallah, M. [LGSDS – ENP, 10, Avenue Hassan Badi, 16200 El Harrah, Alger (Algeria); Kahloun, C.; Bacroix, B. [LSPM – CNRS, Université Paris 13, 93430 Villetaneuse (France)

    2014-12-15

    The precipitation kinetics and the mechanical behavior in a solution treated and aged dual phase stainless steel (DSS) are investigated. X-ray diffraction, transmission and scanning electron microscopy techniques are used to characterize the microstructure and to identify its constituents. The precipitation kinetics analysis shows that the ferrite to σ phase transformation follows the modified Johnson Mehl Avrami (JMA) model containing an impingement parameter c that is adjusted to 0.3. Activation energies calculation leads to conclude that interface reaction is the main mechanism that controls the σ phase formation. Detailed analysis of the extent of the different tensile deformation domains reveals the significant contribution of both σ phase particles and dislocation accumulation to the strain hardening of the material. - Highlights: • The precipitation kinetics of the σ phase is affected by both soft and hard impingement phenomena. • Interface reaction is found to be the main mechanism that controls the ferrite to σ phase transformation. • Both σ phase particles and dislocation accumulation contribute to the strain hardening of the dual phase steel studied.

  7. Mechanism and kinetics of dithiobenzoate-mediated RAFT polymerization. I. The current situation

    NARCIS (Netherlands)

    Barner-Kowollik, C.; Buback, M.; Charleux, B.; Coote, M.L.; Drache, M.; Fukuda, T.; Goto, A.; Klumperman, B.; Lowe, A.B.; McLeary, J.B.; Moad, G.; Monteiro, M.J.; Sanderson, R.D.; Tonge, M.P.; Vana, P.

    2006-01-01

    Investigations into the kinetics and mechanism of dithiobenzoate-mediated Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerizations, which exhibit nonideal kinetic behavior, such as induction periods and rate retardation, are comprehensively reviewed. The appreciable uncertainty in the

  8. Kinetics and mechanism of styrene epoxidation by chlorite: role of chlorine dioxide.

    Science.gov (United States)

    Leigh, Jessica K; Rajput, Jonathan; Richardson, David E

    2014-07-07

    An investigation of the kinetics and mechanism for epoxidation of styrene and para-substituted styrenes by chlorite at 25 °C in the pH range of 5-6 is described. The proposed mechanism in water and water/acetonitrile includes seven oxidation states of chlorine (-I, 0, I, II, III, IV, and V) to account for the observed kinetics and product distributions. The model provides an unusually detailed quantitative mechanism for the complex reactions that occur in mixtures of chlorine species and organic substrates, particularly when the strong oxidant chlorite is employed. Kinetic control of the reaction is achieved by the addition of chlorine dioxide to the reaction mixture, thereby eliminating a substantial induction period observed when chlorite is used alone. The epoxidation agent is identified as chlorine dioxide, which is continually formed by the reaction of chlorite with hypochlorous acid that results from ClO produced by the epoxidation reaction. The overall stoichiometry is the result of two competing chain reactions in which the reactive intermediate ClO reacts with either chlorine dioxide or chlorite ion to produce hypochlorous acid and chlorate or chloride, respectively. At high chlorite ion concentrations, HOCl is rapidly eliminated by reaction with chlorite, minimizing side reactions between HOCl and Cl2 with the starting material. Epoxide selectivity (>90% under optimal conditions) is accurately predicted by the kinetic model. The model rate constant for direct reaction of styrene with ClO2(aq) to produce epoxide is (1.16 ± 0.07) × 10(-2) M(-1) s(-1) for 60:40 water/acetonitrile with 0.20 M acetate buffer. Rate constants for para substituted styrenes (R = -SO3(-), -OMe, -Me, -Cl, -H, and -NO2) with ClO2 were determined. The results support the radical addition/elimination mechanism originally proposed by Kolar and Lindgren to account for the formation of styrene oxide in the reaction of styrene with chlorine dioxide.

  9. The JH2 domain and SH2-JH2 linker regulate JAK2 activity: A detailed kinetic analysis of wild type and V617F mutant kinase domains.

    Science.gov (United States)

    Sanz Sanz, Arturo; Niranjan, Yashavanthi; Hammarén, Henrik; Ungureanu, Daniela; Ruijtenbeek, Rob; Touw, Ivo P; Silvennoinen, Olli; Hilhorst, Riet

    2014-10-01

    JAK2 tyrosine kinase regulates many cellular functions. Its activity is controlled by the pseudokinase (JH2) domain by still poorly understood mechanisms. The V617F mutation in the pseudokinase domain activates JAK2 and causes myeloproliferative neoplasms. We conducted a detailed kinetic analysis of recombinant JAK2 tyrosine kinase domain (JH1) and wild-type and V617F tandem kinase (JH1JH2) domains using peptide microarrays to define the functions of the kinase domains. The results show that i) JAK2 follows a random Bi-Bi reaction mechanism ii) JH2 domain restrains the activity of the JH1 domain by reducing the affinity for ATP and ATP competitive inhibitors iii) V617F decreases affinity for ATP but increases catalytic activity compared to wild-type and iv) the SH2-JH2 linker region participates in controlling activity by reducing the affinity for ATP. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. An optimized chemical kinetic mechanism for HCCI combustion of PRFs using multi-zone model and genetic algorithm

    International Nuclear Information System (INIS)

    Neshat, Elaheh; Saray, Rahim Khoshbakhti

    2015-01-01

    Highlights: • A new chemical kinetic mechanism for PRFs HCCI combustion is developed. • New mechanism optimization is performed using genetic algorithm and multi-zone model. • Engine-related combustion and performance parameters are predicted accurately. • Engine unburned HC and CO emissions are predicted by the model properly. - Abstract: Development of comprehensive chemical kinetic mechanisms is required for HCCI combustion and emissions prediction to be used in engine development. The main purpose of this study is development of a new chemical kinetic mechanism for primary reference fuels (PRFs) HCCI combustion, which can be applied to combustion models to predict in-cylinder pressure and exhaust CO and UHC emissions, accurately. Hence, a multi-zone model is developed for HCCI engine simulation. Two semi-detailed chemical kinetic mechanisms those are suitable for premixed combustion are used for n-heptane and iso-octane HCCI combustion simulation. The iso-octane mechanism contains 84 species and 484 reactions and the n-heptane mechanism contains 57 species and 296 reactions. A simple interaction between iso-octane and n-heptane is considered in new mechanism. The multi-zone model is validated using experimental data for pure n-heptane and iso-octane. A new mechanism is prepared by combination of these two mechanisms for n-heptane and iso-octane blended fuel, which includes 101 species and 594 reactions. New mechanism optimization is performed using genetic algorithm and multi-zone model. Mechanism contains low temperature heat release region, which decreases with increasing octane number. The results showed that the optimized chemical kinetic mechanism is capable of predicting engine-related combustion and performance parameters. Also after implementing the optimized mechanism, engine unburned HC and CO emissions predicted by the model are in good agreement with the corresponding experimental data

  11. Interactions between polyphenols in thinned young apples and porcine pancreatic α-amylase: Inhibition, detailed kinetics and fluorescence quenching.

    Science.gov (United States)

    Sun, Lijun; Chen, Weiqi; Meng, Yonghong; Yang, Xingbin; Yuan, Li; Guo, Yurong; Warren, Frederick J; Gidley, Michael J

    2016-10-01

    Young apple polyphenols (YAP) and nine types of phenolic compounds were investigated regarding the inhibitory activity against porcine pancreatic α-amylase (PPA) in vitro. Tannic acid, chlorogenic acid and caffeic acid in YAP showed relatively high inhibition with the IC50 values of 0.30, 1.96 and 3.69mg/mL, respectively. A detailed kinetics of inhibition study revealed that YAP and tannic acid were competitive inhibitors of PPA, whereas chlorogenic acid and caffeic acid were mixed inhibitors, exhibiting both competitive and uncompetitive characteristics. The fluorescence of PPA could be significantly quenched by YAP and the three polyphenols, and their quenching constants were determined. The results showed that for the polyphenols investigated, the order of the apparent static quenching constants (KFQ) was in agreement with that of the reciprocal competitive inhibition constants (1/Kic) (tannic acid>chlorogenic acid>caffeic acid>epicatechin); both of the parameters were contrary to the order of the IC50 values. Thus, combining detailed kinetics and fluorescence quenching studies can be applied to characterise the interactions between polyphenols in young apples and α-amylase. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Mechanism of nitric acid reduction and kinetic modelling

    International Nuclear Information System (INIS)

    Sicsic, David; Balbaud-Celerier, Fanny; Tribollet, Bernard

    2014-01-01

    In France, the recycling of nuclear waste fuels involves the use of hot concentrated nitric acid. The understanding and prediction of the behaviour of the structural materials (mainly austenitic stainless steels) requires the determination and modelling of the nitric acid reduction process. Nitric acid is indirectly reduced by an autocatalytic mechanism depending on the cathodic overpotential and acid concentration. This mechanism has been widely studied. All the authors agree on its autocatalytic nature, characterized by the predominant role of the reduction products. It is also generally admitted that neither nitric acid nor the nitrate ion is the electro-active species. However, the nature of the electro-active species, the place where the catalytic species regenerates and the thermodynamic and kinetic behaviour of the reaction intermediates remain uncertain. The aim of this study was to clarify some of these uncertainties by performing an electrochemical investigation of the reduction of 4 M nitric acid at 40 C at an inert electrode (platinum or gold). An inert electrode was chosen as the working electrode in a first step to avoid its oxidation and focus the research on the reduction mechanism. This experimental work enabled us to suggest a coherent sequence of electrochemical and chemical reactions. Kinetic modelling of this sequence was then carried out for a gold rotating disk electrode. A thermodynamic study at 25 C allowed the composition of the liquid and gaseous phases of nitric acid solutions in the concentration range 0.5-22 M to be evaluated. The kinetics of the reduction of 4 M nitric acid was investigated by cyclic voltammetry and chrono-amperometry at an inert electrode at 40 C. The coupling of chrono-amperometry and FTIR spectroscopy in the gaseous phase led to the identification of the gaseous reduction products as a function of the cathodic overpotential. The results showed that the reduction process is autocatalytic for potentials between 0

  13. Hydrodenitrogenation mechanism of aromatic amines. Kinetic study and simulation

    International Nuclear Information System (INIS)

    D'Araujo, P.A.P.

    1994-06-01

    The decomposition of model molecules reacting alone or in competition was studied in a fixed bed reactor at 623 K and 7 MPa over a sulfided NiMo/Al 2 O 3 catalyst. The inhibiting effect of H 2 S and some nitrogen molecules, namely quinoline type compounds plays a major role in the transformation of anilines intermediates. On the other hand H 2 S acts as a cocatalyst and promote carbon-nitrogen bond cleavage, specially at low H 2 S partial pressure. When the H 2 S partial pressure is greater than the nitrogen compound partial pressure an inhibiting effect of H 2 S occurs and its promoting effect on carbon-nitrogen bond cleavage is cancelled. Hydrogen has a positive but moderate effect in hydrogenation steps. The mechanism of carbon-nitrogen bond scission depends on the structure of the nitrogen molecule namely on the hybridization of the carbon atom bearing the nitrogen atom. If the carbon a with respect to the nitrogen is monosubstituted the mechanism is essentially a nucleophilic substitution. When the degree of substitution increases the elimination mechanism becomes more important and the two mechanisms are in competition. With a sulfided catalyst, H 2 S from the gas phase doesn't change the importance of each mechanism, it just increases the rate of the reaction. In the presence of an oxide catalyst the contribution of the two mechanisms change. This result shows the importance of the sulphur species from the surface. Using isotopic exchange we could demonstrate that the sites able to dissociate H 2 S and H 2 are the same, and that the dissociation is of heterolytic nature. The kinetic modeling of hydrotreatment reactions using the CHEMKIN/SURFACE CHEMKIN package seems to be a convenient method in order to understand the kinetic and mechanistic phenomena in hydrodenitrogenation. The preliminary simulations in the case of 2.6 diethylaniline showed that only one type of site is not sufficient in order to account for the experimental results. Further simulations

  14. Kinetics and mechanism of methane oxidation in supercritical water

    International Nuclear Information System (INIS)

    Rofer, C.K.; Streit, G.E.

    1988-10-01

    This project, is a Hazardous Waste Remedial Actions Program (HAZWRAP) Research and Development task being carried out by the Los Alamos National Laboratory. Its objective is to achieve an understanding of the technology for use in scaling up and applying oxidation in supercritical water as a viable process for treating a variety of Department of Energy Defense Programs (DOE-DP) waste streams. This report presents experimental results for the kinetics of the oxidation of methane and methanol in supercritical water and computer modeling results for the oxidation of carbonmonoxide and methane in supercritical water. The experimental and modeling results obtained to date on these one-carbon model compounds indicate that the mechanism of oxidation in supercritical water can be represented by free-radical reactions with appropriate modifications for high pressure and the high water concentration. If these current trends are sustained, a large body of existing literature data on the kinetics of elementary reactions can be utilized to predict the behavior of other compounds and their mixtures. 7 refs., 4 figs., 3 tabs

  15. Mechanisms and kinetics of granulated sewage sludge combustion.

    Science.gov (United States)

    Kijo-Kleczkowska, Agnieszka; Środa, Katarzyna; Kosowska-Golachowska, Monika; Musiał, Tomasz; Wolski, Krzysztof

    2015-12-01

    This paper investigates sewage sludge disposal methods with particular emphasis on combustion as the priority disposal method. Sewage sludge incineration is an attractive option because it minimizes odour, significantly reduces the volume of the starting material and thermally destroys organic and toxic components of the off pads. Additionally, it is possible that ashes could be used. Currently, as many as 11 plants use sewage sludge as fuel in Poland; thus, this technology must be further developed in Poland while considering the benefits of co-combustion with other fuels. This paper presents the results of experimental studies aimed at determining the mechanisms (defining the fuel combustion region by studying the effects of process parameters, including the size of the fuel sample, temperature in the combustion chamber and air velocity, on combustion) and kinetics (measurement of fuel temperature and mass changes) of fuel combustion in an air stream under different thermal conditions and flow rates. The combustion of the sludge samples during air flow between temperatures of 800 and 900°C is a kinetic-diffusion process. This process determines the sample size, temperature of its environment, and air velocity. The adopted process parameters, the time and ignition temperature of the fuel by volatiles, combustion time of the volatiles, time to reach the maximum temperature of the fuel surface, maximum temperature of the fuel surface, char combustion time, and the total process time, had significant impacts. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Kinetics and mechanisms of thiol-disulfide exchange covering direct substitution and thiol oxidation-mediated pathways.

    Science.gov (United States)

    Nagy, Péter

    2013-05-01

    Disulfides are important building blocks in the secondary and tertiary structures of proteins, serving as inter- and intra-subunit cross links. Disulfides are also the major products of thiol oxidation, a process that has primary roles in defense mechanisms against oxidative stress and in redox regulation of cell signaling. Although disulfides are relatively stable, their reduction, isomerisation, and interconversion as well as their production reactions are catalyzed by delicate enzyme machineries, providing a dynamic system in biology. Redox homeostasis, a thermodynamic parameter that determines which reactions can occur in cellular compartments, is also balanced by the thiol-disulfide pool. However, it is the kinetic properties of the reactions that best represent cell dynamics, because the partitioning of the possible reactions depends on kinetic parameters. This review is focused on the kinetics and mechanisms of thiol-disulfide substitution and redox reactions. It summarizes the challenges and advances that are associated with kinetic investigations in small molecular and enzymatic systems from a rigorous chemical perspective using biological examples. The most important parameters that influence reaction rates are discussed in detail. Kinetic studies of proteins are more challenging than small molecules, and quite often investigators are forced to sacrifice the rigor of the experimental approach to obtain the important kinetic and mechanistic information. However, recent technological advances allow a more comprehensive analysis of enzymatic systems via using the systematic kinetics apparatus that was developed for small molecule reactions, which is expected to provide further insight into the cell's machinery.

  17. Construction and validation of detailed kinetic models for the combustion of gasoline surrogates; Construction et validation de modeles cinetiques detailles pour la combustion de melanges modeles des essences

    Energy Technology Data Exchange (ETDEWEB)

    Touchard, S.

    2005-10-15

    The irreversible reduction of oil resources, the CO{sub 2} emission control and the application of increasingly strict standards of pollutants emission lead the worldwide researchers to work to reduce the pollutants formation and to improve the engine yields, especially by using homogenous charge combustion of lean mixtures. The numerical simulation of fuel blends oxidation is an essential tool to study the influence of fuel formulation and motor conditions on auto-ignition and on pollutants emissions. The automatic generation helps to obtain detailed kinetic models, especially at low temperature, where the number of reactions quickly exceeds thousand. The main purpose of this study is the generation and the validation of detailed kinetic models for the oxidation of gasoline blends using the EXGAS software. This work has implied an improvement of computation rules for thermodynamic and kinetic data, those were validated by numerical simulation using CHEMKIN II softwares. A large part of this work has concerned the understanding of the low temperature oxidation chemistry of the C5 and larger alkenes. Low and high temperature mechanisms were proposed and validated for 1 pentene, 1-hexene, the binary mixtures containing 1 hexene/iso octane, 1 hexene/toluene, iso octane/toluene and the ternary mixture of 1 hexene/toluene/iso octane. Simulations were also done for propene, 1-butene and iso-octane with former models including the modifications proposed in this PhD work. If the generated models allowed us to simulate with a good agreement the auto-ignition delays of the studied molecules and blends, some uncertainties still remains for some reaction paths leading to the formation of cyclic products in the case of alkenes oxidation at low temperature. It would be also interesting to carry on this work for combustion models of gasoline blends at low temperature. (author)

  18. Investigation kinetics mechanisms of adsorption malachite green onto activated carbon

    International Nuclear Information System (INIS)

    Onal, Y.; Akmil-Basar, C.; Sarici-Ozdemir, C.

    2007-01-01

    Lignite was used to prepare activated carbon (T3K618) by chemical activation with KOH. Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by t-plot based on N 2 adsorption isotherm. BET surface area of activated carbon is determined as 1000 m 2 /g. Adsorption capacity of malachite green (MG) onto T3K618 activated carbon was investigated in a batch system by considering the effects of various parameters like initial concentration (100, 150 and 200 mg/L) and temperature (25, 40 and 50 deg. C). The adsorption process was relatively fast and equilibrium was reached after about 20 min for 100, 150 mg/L at all adsorption temperature. Equilibrium time for 200 mg/L was determined as 20 min and 40 min at 298, 313 and 323 K, respectively. Simple mass and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate controlling steps such as external mass transfer, intraparticle diffusion. Pseudo second-order model was found to explain the kinetics of MG adsorption most effectively. It was found that both mass transfer and pore diffusion are important in determining the adsorption rates. The intraparticle diffusion rate constant, external mass transfer coefficient, film and pore diffusion coefficient at various temperatures were evaluated. The activation energy (E a ) was determined as 48.56, 63.16, 67.93 kJ/mol for 100, 150, 200 mg/L, respectively. The Langmiur and Freundlich isotherm were used to describe the adsorption equilibrium studies at different temperatures. Langmiur isotherm shows better fit than Freundlich isotherm in the temperature range studied. The thermodynamic parameters, such as ΔG o , ΔS and ΔH o were calculated. The thermodynamics of dyes-T3K618 system indicates endothermic process

  19. Integrating chemistry into 3D climate models: Detailed kinetics in the troposphere and stratosphere of a global climate model

    Energy Technology Data Exchange (ETDEWEB)

    Kao, C.Y.J.; Elliott, S. [Los Alamos National Lab., NM (United States). Earth and Environmental Sciences Div.; Turco, R.P.; Zhao, X. [Univ. of California, Los Angeles, CA (United States)

    1997-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The motivation for the project is to create the first complete, three-dimensional climate model that enfolds atmospheric photochemistry. The LANL chemical global climate model (GCM) not only distributes the trace greenhouse gases and modifies their concentrations within the detailed photochemical web, but also permits them to influence the radiation field and so force their own transport. Both atmospheric chemistry and fluid dynamics are nonlinear and zonally asymmetric phenomena. They can only be adequately modeled in three dimensions on the global grid. The kinetics-augmented GCM is the only program within the atmospheric community capable of investigating interaction involving chemistry and transport. The authors have conducted case studies of timely three-dimensional chemistry issues. Examples include ozone production from biomass burning plumes, kinetic feedbacks in zonally asymmetric transport phenomena with month- to year-long time scales, and volcano sulfate aerosols with respect to their potential effects on tropospheric ozone depletion.

  20. DETAILED CHEMICAL KINETIC MODELING OF ISO-OCTANE SI-HCCI TRANSITION

    Energy Technology Data Exchange (ETDEWEB)

    Havstad, M A; Aceves, S M; McNenly, M J; Piggott, W T; Edwards, K D; Wagner, R M; Daw, C S; Finney, C A

    2009-10-12

    The authors describe a CHEMKIN-based multi-zone model that simulates the expected combustion variations in a single-cylinder engine fueled with iso-octane as the engine transitions from spark-ignited (ST) combustion to homogeneous charge compression ignition (HCCI) combustion. The model includes a 63-species reaction mechanism and mass and energy balances for the cylinder and the exhaust flow. For this study they assumed that the SI-to-HCCI transition is implemented by means of increasing the internal exhaust gas recirculation (EGR) at constant engine speed. This transition scneario is consistent with that implemented in previously reported experimental measurements on an experimental engine equipped with variable valve actuation. They find that the model captures many of the important experimental trends, including stable SI combustion at low EGR ({approx} 0.10), a transition to highly unstable combustion at intermediate EGR, and finally stable HCCI combustion at very high EGR ({approx} 0.75). Remaining differences between the predicted and experimental instability patterns indicate that there is further room for model improvement.

  1. Kinetics, mechanism and thermodynamics of bisulfite-aldehyde adduct formation

    Energy Technology Data Exchange (ETDEWEB)

    Olson, T.M.; Boyce, S.D.; Hoffmann, M.R.

    1986-04-01

    The kinetics and mechanism of bisulfite addition to benzaldehyde were studied at low pH in order to assess the importance of this reaction in stabilizing S(IV) in fog-, cloud-, and rainwater. Previously, the authors established that appreciable concentrations of the formaldehyde-bisulfite adduct (HMSA) are often present in fogwater. Measured HMSA concentrations in fogwater often do not fully account for observed excess S(IV) concentrations, however, so that other S(IV)-aldehyde adducts may be present. Reaction rates were determined by monitoring the disappearance of benzaldehyde by U.V. spectrophotometry under pseudo-first order conditions, (S(IV))/sub T/ >>(phi-CHO)/sub T/, in the pH range 0 - 4.4 at 25/sup 0/C. The equilibrium constant was determined by dissolving the sodium salt of the addition compound in a solution adjusted to pH 3.9, and measuring the absorbance of the equilibrated solution at 250 nm. A literature value of the extinction coefficient for benzaldehyde was used to calculate the concentration of free benzaldehyde. All solutions were prepared under an N/sub 2/ atmosphere using deoxygenated, deionized water and ionic strength was maintained at 1.0 M with sodium chloride.

  2. Kinetic mechanism of the decomposition of dimethyltin dichloride

    NARCIS (Netherlands)

    Mol, van A.M.B.; Croon, de M.H.J.M.; Spee, C.I.M.A.; Schouten, J.C.

    1999-01-01

    Results are reported of a study of the intrinsic kinetics of gas phase reactions. For this purpose a reactor system is designed in such a way that concentration and temperature variations throughout the reactor can be neglected enabling investigation of intrinsic reaction kinetics. The gas phase

  3. Kinetics and mechanism of oxidation of chloramphenicol by 1

    Indian Academy of Sciences (India)

    Chloramphenicol (CAP) is an antibiotic drug having a wide spectrum of activity. The kinetics of oxidation of chloramphenicol by 1-chlorobenzotriazole (CBT) in HClO4 medium over the temperature range 293-323 K has been investigated. The reaction exhibits first-order kinetics with respect to [CBT]o and zero-order with ...

  4. Analysis of the kinetic mechanism of recombinant human isoprenylcysteine carboxylmethyltransferase (Icmt

    Directory of Open Access Journals (Sweden)

    Baron Rudi A

    2004-12-01

    Full Text Available Abstract Background Isoprenylcysteine carboxyl methyltransferase (Icmt is the third of three enzymes that posttranslationally modify proteins that contain C-terminal CaaX motifs. The processing of CaaX proteins through this so-called prenylation pathway via a route initiated by addition of an isoprenoid lipid is required for both membrane targeting and function of the proteins. The involvement of many CaaX proteins such as Ras GTPases in oncogenesis and other aberrant proliferative disorders has led to the targeting of the enzymes involved in their processing for therapeutic development, necessitating a detailed understanding of the mechanisms of the enzymes. Results In this study, we have investigated the kinetic mechanism of recombinant human Icmt. In the reaction catalyzed by Icmt, S-adenosyl-L-methionine (AdoMet provides the methyl group that is transferred to the second substrate, the C-terminal isoprenylated cysteine residue of a CaaX protein, thereby generating a C-terminal prenylcysteine methyl ester on the protein. To facilitate the kinetic analysis of Icmt, we synthesized a new small molecule substrate of the enzyme, biotin-S-farnesyl-L-cysteine (BFC. Initial kinetic analysis of Icmt suggested a sequential mechanism for the enzyme that was further analyzed using a dead end competitive inhibitor, S-farnesylthioacetic acid (FTA. Inhibition by FTA was competitive with respect to BFC and uncompetitive with respect to AdoMet, indicating an ordered mechanism with SAM binding first. To investigate the order of product dissociation, product inhibition studies were undertaken with S-adenosyl-L-homocysteine (AdoHcy and the N-acetyl-S-farnesyl-L-cysteine methylester (AFCME. This analysis indicated that AdoHcy is a competitive inhibitor with respect to AdoMet, while AFCME shows a noncompetitive inhibition with respect to BFC and a mixed-type inhibition with respect to AdoMet. These studies established that AdoHcy is the final product released, and

  5. Development of a detailed chemical mechanism (MCMv3.1 for the atmospheric oxidation of aromatic hydrocarbons

    Directory of Open Access Journals (Sweden)

    C. Bloss

    2005-01-01

    Full Text Available The Master Chemical Mechanism has been updated from MCMv3 to MCMv3.1 in order to take into account recent improvements in the understanding of aromatic photo-oxidation. Newly available kinetic and product data from the literature have been incorporated into the mechanism. In particular, the degradation mechanisms for hydroxyarenes have been revised following the observation of high yields of ring-retained products, and product studies of aromatic oxidation under relatively low NOx conditions have provided new information on the branching ratios to first generation products. Experiments have been carried out at the European Photoreactor (EUPHORE to investigate key subsets of the toluene system. These results have been used to test our understanding of toluene oxidation, and, where possible, refine the degradation mechanisms. The evaluation of MCMv3 and MCMv3.1 using data on benzene, toluene, p-xylene and 1,3,5-trimethylbenzene photosmog systems is described in a companion paper, and significant model shortcomings are identified. Ideas for additional modifications to the mechanisms, and for future experiments to further our knowledge of the details of aromatic photo-oxidation are discussed.

  6. Active mechanics in living oocytes reveal molecular-scale force kinetics

    Science.gov (United States)

    Ahmed, Wylie; Fodor, Etienne; Almonacid, Maria; Bussonnier, Matthias; Verlhac, Marie-Helene; Gov, Nir; Visco, Paolo; van Wijland, Frederic; Betz, Timo

    Unlike traditional materials, living cells actively generate forces at the molecular scale that change their structure and mechanical properties. This nonequilibrium activity is essential for cellular function, and drives processes such as cell division. Single molecule studies have uncovered the detailed force kinetics of isolated motor proteins in-vitro, however their behavior in-vivo has been elusive due to the complex environment inside the cell. Here, we quantify active forces and intracellular mechanics in living oocytes using in-vivo optical trapping and laser interferometry of endogenous vesicles. We integrate an experimental and theoretical framework to connect mesoscopic measurements of nonequilibrium properties to the underlying molecular- scale force kinetics. Our results show that force generation by myosin-V drives the cytoplasmic-skeleton out-of-equilibrium (at frequencies below 300 Hz) and actively softens the environment. In vivo myosin-V activity generates a force of F ~ 0 . 4 pN, with a power-stroke of length Δx ~ 20 nm and duration τ ~ 300 μs, that drives vesicle motion at vv ~ 320 nm/s. This framework is widely applicable to characterize living cells and other soft active materials.

  7. Integration of large chemical kinetic mechanisms via exponential methods with Krylov approximations to Jacobian matrix functions

    KAUST Repository

    Bisetti, Fabrizio

    2012-06-01

    Recent trends in hydrocarbon fuel research indicate that the number of species and reactions in chemical kinetic mechanisms is rapidly increasing in an effort to provide predictive capabilities for fuels of practical interest. In order to cope with the computational cost associated with the time integration of stiff, large chemical systems, a novel approach is proposed. The approach combines an exponential integrator and Krylov subspace approximations to the exponential function of the Jacobian matrix. The components of the approach are described in detail and applied to the ignition of stoichiometric methane-air and iso-octane-air mixtures, here described by two widely adopted chemical kinetic mechanisms. The approach is found to be robust even at relatively large time steps and the global error displays a nominal third-order convergence. The performance of the approach is improved by utilising an adaptive algorithm for the selection of the Krylov subspace size, which guarantees an approximation to the matrix exponential within user-defined error tolerance. The Krylov projection of the Jacobian matrix onto a low-dimensional space is interpreted as a local model reduction with a well-defined error control strategy. Finally, the performance of the approach is discussed with regard to the optimal selection of the parameters governing the accuracy of its individual components. © 2012 Copyright Taylor and Francis Group, LLC.

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

    International Nuclear Information System (INIS)

    Walker, M.C.

    1988-01-01

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

  9. High-temperature oxidation chemistry of n-butanol--experiments in low-pressure premixed flames and detailed kinetic modeling.

    Science.gov (United States)

    Hansen, N; Harper, M R; Green, W H

    2011-12-07

    An automated reaction mechanism generator is used to develop a predictive, comprehensive reaction mechanism for the high-temperature oxidation chemistry of n-butanol. This new kinetic model is an advancement of an earlier model, which had been extensively tested against earlier experimental data (Harper et al., Combust. Flame, 2011, 158, 16-41). In this study, the model's predictive capabilities are improved by targeting isomer-resolved quantitative mole fraction profiles of flame species in low-pressure flames. To this end, a total of three burner-stabilized premixed flames are isomer-selectively analyzed by flame-sampling molecular-beam time-of-flight mass spectrometry using photoionization by tunable vacuum-ultraviolet synchrotron radiation. For most species, the newly developed chemical kinetic model is capable of accurately reproducing the experimental trends in these flames. The results clearly indicate that n-butanol is mainly consumed by H-atom abstraction with H, O, and OH, forming predominantly the α-C(4)H(9)O radical (CH(3)CH(2)CH(2)˙CHOH). Fission of C-C bonds in n-butanol is only predicted to be significant in a similar, but hotter flame studied by Oßwald et al. (Combust. Flame, 2011, 158, 2-15). The water-elimination reaction to 1-butene is found to be of no importance under the premixed conditions studied here. The initially formed isomeric C(4)H(9)O radicals are predicted to further oxidize by reacting with H and O(2) or to decompose to smaller fragments via β-scission. Enols are detected experimentally, with their importance being overpredicted by the model.

  10. A computational study on kinetics, mechanism and thermochemistry ...

    Indian Academy of Sciences (India)

    level procedure employing the optimization at .... for a better understanding of mechanistic pathways, kinetics and thermochemistry we must rely on quantum chemical methods. The aim of this paper is to have .... The search was made along.

  11. Mechanism and kinetics of mineral weathering under acid conditions

    NARCIS (Netherlands)

    Anbeek, C.

    1994-01-01

    This study deals with the relationships between crystal structure, grain diameter, surface morphology and dissolution kinetics for feldspar and quartz under acid conditions.

    Intensively ground samples from large, naturally weathered mineral fragments are frequently used in

  12. NDMA formation by chloramination of ranitidine: Kinetics and mechanism

    KAUST Repository

    Le Roux, Julien; Gallard, Hervé ; Croue, Jean-Philippe; Papot, Sé bastien; Deborde, Marie

    2012-01-01

    The kinetics of decomposition of the pharmaceutical ranitidine (a major precursor of NDMA) during chloramination was investigated and some decomposition byproducts were identified by using high performance liquid chromatography coupled with mass

  13. Kinetics and Mechanism of the Oxidation of Coomassie Brilliant Blue ...

    African Journals Online (AJOL)

    , in aqueous solution by hypochlorite as a function of pH was investigated. While the degradation of dye obeyed pseudo-first-order kinetics, the oxidation of the dye occurred through two competitive reactions facilitated by [OCl–] and [HOCl].

  14. Development and Validation of Chemical Kinetic Mechanism Reduction Scheme for Large-Scale Mechanisms

    DEFF Research Database (Denmark)

    Poon, Hiew Mun; Ng, Hoon Kiat; Gan, Suyin

    2014-01-01

    This work is an extension to a previously reported work on chemical kinetic mechanism reduction scheme for large-scale mechanisms. Here, Perfectly Stirred Reactor (PSR) was added as a criterion of data source for mechanism reduction instead of using only auto-ignition condition. As a result......) simulations were performed to study the spray combustion phenomena within a constant volume bomb. Both non-reacting and reacting conditions were applied in this study. Liquid and vapor penetration lengths were replicated for non-reacting diesel spray. For reacting diesel spray, both ignition delay and lift......-off length were simulated. The simulation results were then compared to the experimental data of Sandia National Laboratories and No. 2 Diesel Fuel (D2) was designated as the reference fuel. Both liquid and vapor penetrations for non-reacting condition were well-matched, while ignition delay was advanced...

  15. Kinetics and Mechanisms of Thiol–Disulfide Exchange Covering Direct Substitution and Thiol Oxidation-Mediated Pathways

    Science.gov (United States)

    2013-01-01

    Abstract Significance: Disulfides are important building blocks in the secondary and tertiary structures of proteins, serving as inter- and intra-subunit cross links. Disulfides are also the major products of thiol oxidation, a process that has primary roles in defense mechanisms against oxidative stress and in redox regulation of cell signaling. Although disulfides are relatively stable, their reduction, isomerisation, and interconversion as well as their production reactions are catalyzed by delicate enzyme machineries, providing a dynamic system in biology. Redox homeostasis, a thermodynamic parameter that determines which reactions can occur in cellular compartments, is also balanced by the thiol–disulfide pool. However, it is the kinetic properties of the reactions that best represent cell dynamics, because the partitioning of the possible reactions depends on kinetic parameters. Critical Issues: This review is focused on the kinetics and mechanisms of thiol–disulfide substitution and redox reactions. It summarizes the challenges and advances that are associated with kinetic investigations in small molecular and enzymatic systems from a rigorous chemical perspective using biological examples. The most important parameters that influence reaction rates are discussed in detail. Recent Advances and Future Directions: Kinetic studies of proteins are more challenging than small molecules, and quite often investigators are forced to sacrifice the rigor of the experimental approach to obtain the important kinetic and mechanistic information. However, recent technological advances allow a more comprehensive analysis of enzymatic systems via using the systematic kinetics apparatus that was developed for small molecule reactions, which is expected to provide further insight into the cell's machinery. Antioxid. Redox Signal. 18, 1623–1641. PMID:23075118

  16. Kinetics and mechanism of nitrobenzene hydrogenation to phenylhydroxylamine in rhenium thiocomplexes solutions

    International Nuclear Information System (INIS)

    Korenyako, G.I.; Belousov, V.M.

    1985-01-01

    A study was made on kinetics of nitrobenzene hydrogenation to phenylhydroxylamine in dimethylformamide solutions of rhenium thiocomplexes. The mechanism of hydrogenation was suggested. Formation of hydride catalyst complex represents the first stage of the process. Kinetic equation derived on the basis of suggested mechanism corresponds satisfactorily with experimental results. Thermodynamic parameters of separate process stages calculated on the basis of equilibrium constant values testify as well to the benefit of suggested mechanism

  17. THEORETICAL RESEARCH ON THE MULTI-CHANNEL REACTION MECHANISM AND KINETICS OF HNCS WITH OH-

    Directory of Open Access Journals (Sweden)

    Li-Jie Hou

    Full Text Available We presented a theoretical study on the detailed reaction mechanism and kinetics of the HNCS molecule with the OH-. The barrierless minimum energy path and the most favorable entrance channel have been determined by study the thermodynamic and kinetic characters of the channel with low energy barrier. The B3LYP/6-311++G** method was employed for all the geometrical optimizations and a multi-level extrapolation method based on the G3 energies was employed for further energy refinements. In addition, the analysis of the combining interaction between hydroxide ion and HNCS was performed by natural bond orbitals (NBO analysis. The calculation results indicated that the reaction of OH- with HNCS had four channels, and the channel of H-atom in HNCS direct extraction to OH- (OH-+HNCS→IM1→TS3→IM4→P2(SCN- +H2O in singlet state was the main channel with the low potential energy and high equilibrium constant and reaction rate constant. SCN- and H2O were main products.

  18. Renormalizing the kinetic energy operator in elementary quantum mechanics

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-09-15

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

  19. Renormalizing the kinetic energy operator in elementary quantum mechanics

    International Nuclear Information System (INIS)

    Coutinho, F A B; Amaku, M

    2009-01-01

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

  20. Development and validation of a generic reduced chemical kinetic mechanism for CFD spray combustion modelling of biodiesel fuels

    DEFF Research Database (Denmark)

    Cheng, Xinwei; Ng, Hoon Kiat; Ho, Jee Hou

    2015-01-01

    In this reported work, a generic reduced biodiesel chemical kinetic mechanism, with components of methyl decanoate (C11H22O2, MD), methyl-9-decenoate (C11H20O2, MD9D) and n-heptane (C7H16) was built to represent the methyl esters of coconut, palm, rapeseed and soybean. The reduced biodiesel...... and detailed mechanism predictions, for each zero-dimensional (0D) auto-ignition and extinction process using CHEMKIN-PRO. Maximum percentage errors of less than 40.0% were recorded when the predicted ignition delay (ID) periods for coconut, palm, rapeseed and soybean methyl esters were compared to those...

  1. A Comparison of Kinetic Energy and Momentum in Special Relativity and Classical Mechanics

    Science.gov (United States)

    Riggs, Peter J.

    2016-01-01

    Kinetic energy and momentum are indispensable dynamical quantities in both the special theory of relativity and in classical mechanics. Although momentum and kinetic energy are central to understanding dynamics, the differences between their relativistic and classical notions have not always received adequate treatment in undergraduate teaching.…

  2. Kinetic and mechanism studies of the adsorption of lead onto waste cow bone powder (WCBP) surfaces.

    Science.gov (United States)

    Cha, Jihoon; Cui, Mingcan; Jang, Min; Cho, Sang-Hyun; Moon, Deok Hyun; Khim, Jeehyeong

    2011-01-01

    This study examines the adsorption isotherms, kinetics and mechanisms of Pb²(+) sorption onto waste cow bone powder (WCBP) surfaces. The concentrations of Pb²(+) in the study range from 10 to 90 mg/L. Although the sorption data follow the Langmuir and Freundlich isotherm, a detailed examination reveals that surface sorption or complexation and co-precipitation are the most important mechanisms, along with possibly ion exchange and solid diffusion also contributing to the overall sorption process. The co-precipitation of Pb²(+) with the calcium hydroxyapatite (Ca-HAP) is implied by significant changes in Ca²(+) and PO₄³⁻ concentrations during the metal sorption processes. The Pb²(+) sorption onto the WCBP surface by metal complexation with surface functional groups such as ≡ POH. The major metal surface species are likely to be ≡ POPb(+). The sorption isotherm results indicated that Pb²(+) sorption onto the Langmuir and Freundlich constant q(max) and K( F ) is 9.52 and 8.18 mg g⁻¹, respectively. Sorption kinetics results indicated that Pb²(+) sorption onto WCBP was pseudo-second-order rate constants K₂ was 1.12 g mg⁻¹ h⁻¹. The main mechanism is adsorption or surface complexation (≡POPb(+): 61.6%), co-precipitation or ion exchange [Ca₃(.)₉₃ Pb₁(.)₀₇ (PO₄)₃ (OH): 21.4%] and other precipitation [Pb 50 mg L⁻¹ and natural pH: 17%). Sorption isotherms showed that WCBP has a much higher Pb²(+) removal rate in an aqueous solution; the greater capability of WCBP to remove aqueous Pb²(+) indicates its potential as another promising way to remediate Pb²(+)-contaminated media.

  3. General theory of the multistage geminate reactions of the isolated pairs of reactants. II. Detailed balance and universal asymptotes of kinetics.

    Science.gov (United States)

    Kipriyanov, Alexey A; Doktorov, Alexander B

    2014-10-14

    The analysis of general (matrix) kinetic equations for the mean survival probabilities of any of the species in a sample (or mean concentrations) has been made for a wide class of the multistage geminate reactions of the isolated pairs. These kinetic equations (obtained in the frame of the kinetic approach based on the concept of "effective" particles in Paper I) take into account various possible elementary reactions (stages of a multistage reaction) excluding monomolecular, but including physical and chemical processes of the change in internal quantum states carried out with the isolated pairs of reactants (or isolated reactants). The general basic principles of total and detailed balance have been established. The behavior of the reacting system has been considered on macroscopic time scales, and the universal long-term kinetics has been determined.

  4. Oxyhalogen-Sulfur Chemistry: Kinetics and Mechanism of Oxidation ...

    African Journals Online (AJOL)

    NICOLAAS

    The oxidation of N-acetylthiourea (ACTU) by acidic bromate has been studied by observing formation of bromine in excess .... kinetics experiments were performed at 25.0 ± 0.1 °C and at an ..... thiourea compounds with potent anti-HIV activity.

  5. Renormalizing the Kinetic Energy Operator in Elementary Quantum Mechanics

    Science.gov (United States)

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

    2009-01-01

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

  6. Kinetics and mechanism of the oxidation of some diols by ...

    Indian Academy of Sciences (India)

    Abstract. The kinetics of oxidation of five vicinal and four non-vicinal diols, and two of their monoethers by benzyltrimethylammonium tribromide (BTMAB) have been studied in 3:7 (v/v) acetic acid–water mixture. The vicinal diols yield the carbonyl compounds arising out of the glycol bond fission while the other diols give.

  7. Kinetics and mechanism of oxidation of aliphatic alcohols by ...

    Indian Academy of Sciences (India)

    TBATB) in aqueous acetic acid leads to the formation of the corresponding aldehydes. The reaction is first order with respect to TBATB. Michaelis-Menten type kinetics is observed with respect to alcohols. The reaction failed to induce the ...

  8. Development of multi-component diesel surrogate fuel models – Part I: Validation of reduced mechanisms of diesel fuel constituents in 0-D kinetic simulations

    DEFF Research Database (Denmark)

    Poon, Hiew Mun; Pang, Kar Mun; Ng, Hoon Kiat

    2016-01-01

    In the present work, development and validation of reduced chemical kinetic mechanisms for several different hydrocarbons are performed. These hydrocarbons are potential representative for practical diesel fuel constituents. n-Hexadecane (HXN), 2,2,4,4,6,8,8-heptamethylnonane (HMN), cyclohexane...... (CHX) and toluene are selected to represent straight-alkane, branched-alkane, cyclo-alkane and aromatic compounds in the diesel fuel. A five-stage chemical kinetic mechanism reduction scheme formulated in the previous work is applied to develop the reduced HMN and CHX models based on their respective...... detailed mechanisms. Alongside with the development of the reduced CHX model, a skeletal toluene sub-mechanism is constructed since the elementary reactions for toluene are subset of the detailed CHX mechanism. The final reduced HMN mechanism comprises 89 species with 319 elementary reactions, while...

  9. Detailed Assessment of the Kinetics of Hg-Cell Association, Hg Methylation, and Methylmercury Degradation in Several Desulfovibrio Species

    Science.gov (United States)

    Graham, Andrew M.; Bullock, Allyson L.; Maizel, Andrew C.; Elias, Dwayne A.

    2012-01-01

    The kinetics of inorganic Hg [Hg(II)i] association, methylation, and methylmercury (MeHg) demethylation were examined for a group of Desulfovibrio species with and without MeHg production capability. We employed a detailed method for assessing MeHg production in cultures, including careful control of medium chemistry, cell density, and growth phase, plus mass balance of Hg(II)i and MeHg during the assays. We tested the hypothesis that differences in Hg(II)i sorption and/or uptake rates drive observed differences in methylation rates among Desulfovibrio species. Hg(II)i associated rapidly and with high affinity to both methylating and nonmethylating species. MeHg production by Hg-methylating strains was rapid, plateauing after ∼3 h. All MeHg produced was rapidly exported. We also tested the idea that all Desulfovibrio species are capable of Hg(II)i methylation but that rapid demethylation masks its production, but we found this was not the case. Therefore, the underlying reason why MeHg production capability is not universal in the Desulfovibrio is not differences in Hg affinity for cells nor differences in the ability of strains to degrade MeHg. However, Hg methylation rates varied substantially between Hg-methylating Desulfovibrio species even in these controlled experiments and after normalization to cell density. Thus, biological differences may drive cross-species differences in Hg methylation rates. As part of this study, we identified four new Hg methylators (Desulfovibrio aespoeensis, D. alkalitolerans, D. psychrotolerans, and D. sulfodismutans) and four nonmethylating species (Desulfovibrio alcoholivorans, D. tunisiensis, D. carbinoliphilus, and D. piger) in our ongoing effort to generate a library of strains for Hg methylation genomics. PMID:22885751

  10. CH4/air homogeneous autoignition: A comparison of two chemical kinetics mechanisms

    KAUST Repository

    Tingas, Efstathios Al.; Manias, Dimitris M.; Sarathy, Mani; Goussis, Dimitris A.

    2018-01-01

    Reactions contributing to the generation of the explosive time scale that characterise autoignition of homogeneous stoichiometric CH4/air mixture are identified using two different chemical kinetics models; the well known GRI-3.0 mechanism (53

  11. Compact Kinetic Mechanisms for Petroleum-Derived and Alternative Aviation Fuels, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — To be useful for computational combustor design and analysis using tools like the National Combustion Code (NCC), low-dimensional chemical kinetic mechanisms for...

  12. Kinetics and mechanism of polymerization of methyl methacrylate ...

    Indian Academy of Sciences (India)

    Homopolymerization of methyl methacrylate (MMA) was carried out in the presence of triphenylstibonium 1,2,3,4-tetraphenyl-cyclopentadienylide as an initiator in dioxane at 65°C ± 0·1°C. The system follows non-ideal radical kinetics ( ∝ [M]1.4 [I]0.44) due to primary radical termination as well as degradative ...

  13. Kinetics and mechanism of auto- and copper-catalyzed oxidation of 1,4-naphthohydroquinone.

    Science.gov (United States)

    Yuan, Xiu; Miller, Christopher J; Pham, A Ninh; Waite, T David

    2014-06-01

    Although quinones represent a class of organic compounds that may exert toxic effects both in vitro and in vivo, the molecular mechanisms involved in quinone species toxicity are still largely unknown, especially in the presence of transition metals, which may both induce the transformation of the various quinone species and result in generation of harmful reactive oxygen species. In this study, the oxidation of 1,4-naphthohydroquinone (NH2Q) in the absence and presence of nanomolar concentrations of Cu(II) in 10 mM NaCl solution over a pH range of 6.5-7.5 has been investigated, with detailed kinetic models developed to describe the predominant mechanisms operative in these systems. In the absence of copper, the apparent oxidation rate of NH2Q increased with increasing pH and initial NH2Q concentration, with concomitant oxygen consumption and peroxide generation. The doubly dissociated species, NQ(2-), has been shown to be the reactive species with regard to the one-electron oxidation by O2 and comproportionation with the quinone species, both generating the semiquinone radical (NSQ(·-)). The oxidation of NSQ(·-) by O2 is shown to be the most important pathway for superoxide (O2(·-)) generation with a high intrinsic rate constant of 1.0×10(8)M(-1)s(-1). Both NSQ(·-) and O2(·-) served as chain-propagating species in the autoxidation of NH2Q. Cu(II) is capable of catalyzing the oxidation of NH2Q in the presence of O2 with the oxidation also accelerated by increasing the pH. Both the uncharged (NH2Q(0)) and the mono-anionic (NHQ(-)) species were found to be the kinetically active forms, reducing Cu(II) with an intrinsic rate constant of 4.0×10(4) and 1.2×10(7)M(-1)s(-1), respectively. The presence of O2 facilitated the catalytic role of Cu(II) by rapidly regenerating Cu(II) via continuous oxidation of Cu(I) and also by efficient removal of NSQ(·-) resulting in the generation of O2(·-). The half-cell reduction potentials of various redox couples at neutral p

  14. Fundamental and semi-global kinetic mechanisms for hydrocarbon combustion. Final report, March 1977-October 1980

    Energy Technology Data Exchange (ETDEWEB)

    Dryer, F L; Glassman, I; Brezinsky, K

    1981-03-01

    Over the past three and one half years, substantial research efforts of the Princeton Fuels Research Group have been directed towards the development of simplified mechanisms which would accurately describe the oxidation of hydrocarbons fuels. The objectives of this combustion research included the study of semi-empirical modeling (that is an overall description) of the chemical kinetic mechanisms of simple hydrocarbon fuels. Such fuels include the alkanes: ethane, propane, butane, hexane and octane as well as the critically important alkenes: ethene, propene and butene. As an extension to this work, the study of the detailed radical species characteristics of combustion systems was initiated as another major aspect of the program, with emphasis on the role of the OH and HO/sub 2/ radicals. Finally, the studies of important alternative fuel problems linked the program to longer range approaches to the energy supply question. Studies of alternative fuels composed the major elements of this area of the program. The efforts on methanol research were completed, and while the aromatics aspects of the DOE work have been a direct extension of efforts supported by the Air Force Office of Scientific Research, they represented a significant part of the overall research effort. The emphasis in the proposed program is to provide further fundamental understanding of the oxidation of hydrocarbon fuels which will be useful in guiding engineering approaches. Although the scope of program ranges from the fundamentals of chemical kinetics to that of alternative fuel combustion, the objective in mind is to provide insight and guidance to the understanding of practical combustion environments. The key to our approach has been our understanding of the fundamental combustion chemistry and its relation to the important practical combustion problems which exist in implementing energy efficient, alternate fuels technologies.

  15. Chlorine dioxide oxidation of Escherichia coli in water - A study of the disinfection kinetics and mechanism.

    Science.gov (United States)

    Ofori, Isaac; Maddila, Suresh; Lin, Johnson; Jonnalagadda, Sreekantha B

    2017-06-07

    This study investigated the kinetics and mechanism of chlorine dioxide (ClO 2 ) inactivation of a Gram-negative bacteria Escherichia coli (ATCC 35218) in oxidant demand free (ODF) water in detail as a function of disinfectant concentration (0.5-5.0 mg/L), water pH (6.5-8.5), temperature variations (4-37°C) and bacterial density (10 5 -10 7 cfu/mL). The effects of ClO 2 on bacterial cell morphology, outer membrane permeability, cytoplasmic membrane disruption and intracellular enzymatic activity were also studied to elucidate the mechanism of action on the cells. Increasing temperature and disinfectant concentration were proportional to the rate of cell killing, but efficacy was found to be significantly subdued at 0.5 mg/L and less dependent on the bacterial density. The bactericidal efficiency was higher at alkaline pH of 8 or above as compared to neutral and slightly acidic pH of 7 and 6.5 respectively. The disinfection kinetic curves followed a biphasic pattern of rapid inactivation within the initial 2 min which were followed by a tailing even in the presence of residual biocide. The curves were adequately described by the C avg Hom model. Transmission Electron Microscopy images of the bacteria cells exposed to lethal concentrations of ClO 2 indicated very little observable morphological damage to the outer membranes of the cells. ClO 2 however was found to increase the permeability of the outer and cytoplasmic membranes leading to the leakage of membrane components such as 260 nm absorbing materials and inhibiting the activity of the intracellular enzyme β-D-galactosidase. It is suggested that the disruption of the cytoplasmic membrane and subsequent efflux of intracellular components result in the inactivation of the Gram-negative bacteria.

  16. Insights into the Mechanism and Kinetics of Thermo-Oxidative Degradation of HFPE High Performance Polymer.

    Science.gov (United States)

    Kunnikuruvan, Sooraj; Parandekar, Priya V; Prakash, Om; Tsotsis, Thomas K; Nair, Nisanth N

    2016-06-02

    The growing requisite for materials having high thermo-oxidative stability makes the design and development of high performance materials an active area of research. Fluorination of the polymer backbone is a widely applied strategy to improve various properties of the polymer, most importantly the thermo-oxidative stability. Many of these fluorinated polymers are known to have thermo-oxidative stability up to 700 K. However, for space and aerospace applications, it is important to improve its thermo-oxidative stability beyond 700 K. Molecular-level details of the thermo-oxidative degradation of such polymers can provide vital information to improve the polymer. In this spirit, we have applied quantum mechanical and microkinetic analysis to scrutinize the mechanism and kinetics of the thermo-oxidative degradation of a fluorinated polymer with phenylethenyl end-cap, HFPE. This study gives an insight into the thermo-oxidative degradation of HFPE and explains most of the experimental observations on the thermo-oxidative degradation of this polymer. Thermolysis of C-CF3 bond in the dianhydride component (6FDA) of HFPE is found to be the rate-determining step of the degradation. Reaction pathways that are responsible for the experimentally observed weight loss of the polymer is also scrutinized. On the basis of these results, we propose a modification of HFPE polymer to improve its thermo-oxidative stability.

  17. Study on reaction mechanism by analysis of kinetic energy spectra of light particles and formation of final products

    Science.gov (United States)

    Giardina, G.; Mandaglio, G.; Nasirov, A. K.; Anastasi, A.; Curciarello, F.; Fazio, G.

    2018-05-01

    The sensitivity of reaction mechanism in the formation of compound nucleus (CN) by the analysis of kinetic energy spectra of light particles and of reaction products are shown. The dependence of the P CN fusion probability of reactants and W sur survival probability of CN against fission at its deexcitation on the mass and charge symmetries in the entrance channel of heavy-ion collisions, as well as on the neutron numbers is discussed. The possibility of conducting a complex program of investigations of the complete fusion by reliable ways depends on the detailed and refined methods of experimental and theoretical analyses.

  18. Biological mechanisms and translocation kinetics of particulate plutonium

    International Nuclear Information System (INIS)

    Bruenger, F.W.; Stevens, W.; Atherton, D.R.; Roswell, R.L.; Smith, J.M.

    1981-01-01

    The dissolution and elimination of particulate 239 Pu from its initial sites of deposition in phagocytic organs (the liver, spleen, and lung), as well as its translocation and redeposition in soft tissue organs and skeleton have been investigated. Beagles were injected intravenously with particulate Pu and sacrificed sequentially at times ranging from 33 to 830 days after injection. Equations that describe the overall retention of Pu in liver, spleen, lung, and bone were calculated. Plutonium mobilized from these organs either re-entered the blood stream and redeposited in the skeleton and liver parenchyma or was excreted. The protracted translocation of Pu to bone surfaces potentially exposes all cells involved in osteogenesis to continuous α-radiation, a situation that could enhance the hazard of developing osteosarcoma. A kinetic model that describes the translocation of Pu from the phagocytic compartments to blood and its subsequent redistribution to bone, liver, and other organs was formulated

  19. Kinetics of coal combustion: Part 3, Mechanisms and kinetics of char combustion

    Energy Technology Data Exchange (ETDEWEB)

    Gavalas, G. R.; Flagan, R. C. [California Inst. of Tech., Pasadena, CA (USA)

    1988-09-01

    This report summarizes a three-year research program aimed at developing this level of understanding of char combustion through a combination of detailed analysis of chars as produced during devolatilization and as they evolve during oxidation, and theoretical studies of the porous microstructures and of pore diffusion and reaction within the coal particles. A small number of coals have been studied in detail, namely a HVA bituminous (PSOC 1451), a sub-bituminous (PSOC 1488), and a lignite (PSOC 1443). Chars have been generated from size-classified samples of these coals by pyrolysis in an inert atmosphere in a drop tube furnace. The chars were then characterized both chemically and physically. Subsequent oxidation studies were performed on these chars. 42 refs., 54 figs., 4 tabs.

  20. Detailed analysis of surface asperity deformation mechanism in diffusion bonding of steel hollow structural components

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, C. [School of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an 710072 (China); Laboratoire de Mecanique des Contacts et des Structures (LaMCoS), INSA Lyon, 20 Avenue des Sciences, F-69621 Villeurbanne Cedex (France); Li, H. [School of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an 710072 (China); Li, M.Q., E-mail: zc9997242256@126.com [School of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an 710072 (China)

    2016-05-15

    Graphical abstract: This study focused on the detailed analysis of surface asperity deformation mechanism in diffusion bonding of steel hollow structural component. A special surface with regular patterns was processed to be joined so as to observe the extent of surface asperity deformation under different applied bonding pressures. Fracture surface characteristic combined with surface roughness profiles distinctly revealed the enhanced surface asperity deformation as the applied pressure increases. The influence of surface asperity deformation mechanism on joint formation was analyzed: (a) surface asperity deformation not only directly expanded the interfacial contact areas, but also released deformation heat and caused defects, indirectly accelerating atomic diffusion, then benefits to void shrinkage; (b) surface asperity deformation readily introduced stored energy difference between two opposite sides of interface grain boundary, resulting in strain induced interface grain boundary migration. In addition, the influence of void on interface grain boundary migration was analyzed in detail. - Highlights: • A high quality hollow structural component has been fabricated by diffusion bonding. • Surface asperity deformation not only expands the interfacial contact areas, but also causes deformation heat and defects to improve the atomic diffusion. • Surface asperity deformation introduces the stored energy difference between the two opposite sides of interface grain boundary, leading to strain induced interface grain boundary migration. • The void exerts a dragging force on the interface grain boundary to retard or stop interface grain boundary migration. - Abstract: This study focused on the detailed analysis of surface asperity deformation mechanism in similar diffusion bonding as well as on the fabrication of high quality martensitic stainless steel hollow structural components. A special surface with regular patterns was processed to be joined so as to

  1. Detailed mechanical design and manufacturing study for the ITER reference breeding blanket

    International Nuclear Information System (INIS)

    Zacchia, F.; Daenner, W.; Stefanis, L. de; Ferrari, M.; Gerber, A.; Mustoe, J.

    1998-01-01

    This papers relates on the detailed mechanical design, manufacturing feasibility and assembly analysis of a water-cooled solid breeding blanket concept, selected as the ITER reference design. This breeding blanket design is characterised by: i) pressurised water flowing inside flat steel panels for cooling of the internals; each panel is welded along its contour onto the first wall structure and to the rear shield plate after closure of the module (last assembly step). ii) Beryllium (neutronic multiplier) in the form of micro-spheres filling the volume between parallel flat coolant panels. iii) Breeder pebbles enclosed in rods, which form bundles and are themselves embedded inside the Beryllium micro-spheres. (authors)

  2. A study of sodium oxide crystallization mechanisms and kinetics in cold traps

    International Nuclear Information System (INIS)

    Latge, C.

    1984-04-01

    After showing up the present lack of data on crystallization mechanisms and kinetics, a number of tests were conducted on a sodium test loop equipped with two experimental cold traps. The effects of several geometric and thermohydraulic parameters on purification efficiency were also studied. The test results were used to develop a simulation model. An optimization code based on the model can be used to determine the nucleation and growth kinetics

  3. Detailed kinetic analysis of the interaction between the FOXO4–DNA-binding domain and DNA

    Czech Academy of Sciences Publication Activity Database

    Vácha, P.; Zusková, Iva; Bumba, Ladislav; Večeř, J.; Obšilová, Veronika; Obšil, T.

    2013-01-01

    Roč. 184, DEC 31 (2013), s. 68-78 ISSN 0301-4622 R&D Projects: GA ČR(CZ) GAP207/11/0717 Institutional support: RVO:67985823 ; RVO:61388971 Keywords : binding kinetics * DNA-binding domain * FOXO4 forkhead transcription factor Subject RIV: BO - Biophysics; CE - Biochemistry (MBU-M) Impact factor: 2.319, year: 2013

  4. The Kinetic Chain Revisited: New Concepts on Throwing Mechanics and Injury.

    Science.gov (United States)

    Chu, Samuel K; Jayabalan, Prakash; Kibler, W Ben; Press, Joel

    2016-03-01

    The overhead throwing motion is a complex activity that is achieved through activation of the kinetic chain. The kinetic chain refers to the linkage of multiple segments of the body that allows for transfer of forces and motion. The lower extremities and core provide a base of support, generating energy that is transferred eventually through the throwing arm and hand, resulting in release of the ball. The kinetic chain requires optimal anatomy, physiology, and mechanics and is involved in all 6 phases of overhead throwing: windup, stride, arm cocking, acceleration, deceleration, and follow-through. Breaks or deficits in the kinetic chain can lead to injury or decreased performance. Through an understanding of the mechanics and pathomechanics seen in each phase of throwing, the clinician can better evaluate and screen for potential kinetic chain deficits in the overhead throwing athlete. The purpose of this article is to review the biomechanics of the overhead throwing motion, the role of the kinetic chain in throwing, and the clinical evaluation and management of abnormal throwing mechanics and related injuries. Copyright © 2016 American Academy of Physical Medicine and Rehabilitation. Published by Elsevier Inc. All rights reserved.

  5. CSP-based chemical kinetics mechanisms simplification strategy for non-premixed combustion: An application to hybrid rocket propulsion

    KAUST Repository

    Ciottoli, Pietro P.

    2017-08-14

    A set of simplified chemical kinetics mechanisms for hybrid rocket applications using gaseous oxygen (GOX) and hydroxyl-terminated polybutadiene (HTPB) is proposed. The starting point is a 561-species, 2538-reactions, detailed chemical kinetics mechanism for hydrocarbon combustion. This mechanism is used for predictions of the oxidation of butadiene, the primary HTPB pyrolysis product. A Computational Singular Perturbation (CSP) based simplification strategy for non-premixed combustion is proposed. The simplification algorithm is fed with the steady-solutions of classical flamelet equations, these being representative of the non-premixed nature of the combustion processes characterizing a hybrid rocket combustion chamber. The adopted flamelet steady-state solutions are obtained employing pure butadiene and gaseous oxygen as fuel and oxidizer boundary conditions, respectively, for a range of imposed values of strain rate and background pressure. Three simplified chemical mechanisms, each comprising less than 20 species, are obtained for three different pressure values, 3, 17, and 36 bar, selected in accordance with an experimental test campaign of lab-scale hybrid rocket static firings. Finally, a comprehensive strategy is shown to provide simplified mechanisms capable of reproducing the main flame features in the whole pressure range considered.

  6. Mechanism and kinetics of parathion degradation under ultrasonic irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Yao Juanjuan, E-mail: yao_juanjuan@yahoo.cn [State Key laboratory of Pollution Control and Resources Reuse, Tongji University, Shanghai, 200092 (China); Gao Naiyun; Li Cong; Li Lei; Xu Bin [State Key laboratory of Pollution Control and Resources Reuse, Tongji University, Shanghai, 200092 (China)

    2010-03-15

    The parathion degradation under ultrasonic irradiation in aqueous solution was investigated. The results indicate that at the conditions in question, degradation rate of parathion decreased with increasing initial concentration and decreasing power. The optimal frequency for parathion degradation was 600 kHz. The free radical reactions predominate in the sonochemical degradation of parathion and the reaction zones are predominately at the bubble interface and, to a much lesser extent, in bulk solution. The gas/liquid interfacial regions are the real effective reaction sites for sonochemical degradation of parathion. The reaction can be well described as a gas/liquid heterogeneous reaction which obeys a kinetic model based on Langmuir-Hinshelwood model. The main pathways of parathion degradation by ultrasonic irradiation were also proposed by qualitative and quantitative analysis of organic and inorganic byproducts. It is indicated that the N{sub 2} in air takes part in the parathion degradation through the formation of {center_dot}NO{sub 2} under ultrasonic irradiation. Parathion is decomposed into paraoxon and 4-nitrophenol in the first step via two different pathways, respectively, which is in agreement with the theoretical molecular orbital (MO) calculations.

  7. Students' Misconceptions about Heat Transfer Mechanisms and Elementary Kinetic Theory

    Science.gov (United States)

    Pathare, S. R.; Pradhan, H. C.

    2010-01-01

    Heat and thermodynamics is a conceptually rich area of undergraduate physics. In the Indian context in particular there has been little work done in this area from the point of view of misconceptions. This prompted us to undertake a study in this area. We present a study of students' misconceptions about heat transfer mechanisms, i.e. conduction,…

  8. Kinetic process of mechanical alloying in Fe50Cu50

    DEFF Research Database (Denmark)

    Huang, J.Y.; Jiang, Jianzhong; Yasuda, H.

    1998-01-01

    It is shown that mechanical alloying in the immiscible Fe-Cu system is governed by the atomic shear event and shear-induced diffusion process. We found that an alpha-to-gamma phase transformation, as evidenced by the Nishiyama-Wasserman orientation relationship, occurs by simultaneous shearing...

  9. Reaction kinetics and mechanism of magnetic field effects in cryptochrome

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Schulten, Klaus

    2012-01-01

    Creatures as varied as mammals, fish, insects, reptiles, and birds have an intriguing sixth sense that allows them to orient themselves in the Earth's magnetic field. Despite decades of study, the physical basis of this magnetic sense remains elusive. A likely mechanism is furnished by magnetically...

  10. Saturation mechanism of decaying ion temperature gradient driven turbulence with kinetic electrons

    International Nuclear Information System (INIS)

    Idomura, Yasuhiro

    2016-01-01

    We present full-f gyrokinetic simulations of the ion temperature gradient driven (ITG) turbulence including kinetic electrons. By comparing decaying ITG turbulence simulations with adiabatic and kinetic electron models, an impact of kinetic electrons on the ITG turbulence is investigated. It is found that significant electron transport occurs even in the ITG turbulence, and both ion and electron temperature profiles are relaxed. In steady states, both cases show upshifts of nonlinear critical ion temperature gradients from linear ones, while their saturation mechanisms are qualitatively different. In the adiabatic electron case, the ITG mode is stabilized by turbulence driven zonal flows. On the other hand, in the kinetic electron case, passing electrons transport shows fine resonant structures at mode rational surfaces, which generate corrugated density profiles. Such corrugated density profiles lead to fine radial electric fields following the neoclassical force balance relation. The resulting E × B shearing rate greatly exceeds the linear growth rate of the ITG mode. (author)

  11. Influence of ammonium nitrate on kinetics and mechanism of thermal decomposition of ammonium polyuranates

    International Nuclear Information System (INIS)

    Karelin, A.I.; Lobas, O.P.; Zhiganov, A.N.; Vasil'ev, K.F.; Zhiganova, A.A.

    1988-01-01

    The influence of ammonium nitrate on the mechanism and kinetics of dehydration and thermal decomposition of ammonium polyuranates was studied. An appreciable influence of the nitrate ion content in the samples of ammonium polyuranates on the development of thermal stability has been noted. The kinetic parameters of the thermal decomposition of ammonium polyuranates have been evaluated. A mechanism of the dehydration and thermal decomposition of ammonium polyuranates in the presence of ammonium nitrate has been proposed. It was shown that increase in the content of ammonium nitrate in the precipitate of ammonium polyuranates leads to a decrease in the specific surface of uranoso-uranic oxide

  12. Investigation of ammonium nitrate effect on kinetics and mechanism of thermal decomposition of ammonium polyuranates

    International Nuclear Information System (INIS)

    Karelin, A.I.; Lobas, O.P.; Zhiganov, A.N.; Vasil'ev, K.F.; Zhiganova, A.A.

    1987-01-01

    A study was made on ammonium nitrate effect on the mechanism and kinetics of dehydration and thermal decomposition of ammonium polyuranates. Sufficient effect of nitrate ion content in ammonium polyuranate samples on their thermal stability was noted. Kinetic parameters of thermal decomposition of ammonium polyuranates were evaluated. Mechanism of dehydration and thermal decomposition of ammonium polyuranates in the presence of ammonium nitrate was suggested. It was shown that increase of ammonium nitrate content in ammonium polyuranate precipitate resulted to reduction of the specific surface of prepared uranium mixed oxide

  13. Mechanistic, kinetic, and processing aspects of tungsten chemical mechanical polishing

    Science.gov (United States)

    Stein, David

    This dissertation presents an investigation into tungsten chemical mechanical polishing (CMP). CMP is the industrially predominant unit operation that removes excess tungsten after non-selective chemical vapor deposition (CVD) during sub-micron integrated circuit (IC) manufacture. This work explores the CMP process from process engineering and fundamental mechanistic perspectives. The process engineering study optimized an existing CMP process to address issues of polish pad and wafer carrier life. Polish rates, post-CMP metrology of patterned wafers, electrical test data, and synergy with a thermal endpoint technique were used to determine the optimal process. The oxidation rate of tungsten during CMP is significantly lower than the removal rate under identical conditions. Tungsten polished without inhibition during cathodic potentiostatic control. Hertzian indenter model calculations preclude colloids of the size used in tungsten CMP slurries from indenting the tungsten surface. AFM surface topography maps and TEM images of post-CMP tungsten do not show evidence of plow marks or intergranular fracture. Polish rate is dependent on potassium iodate concentration; process temperature is not. The colloid species significantly affects the polish rate and process temperature. Process temperature is not a predictor of polish rate. A process energy balance indicates that the process temperature is predominantly due to shaft work, and that any heat of reaction evolved during the CMP process is negligible. Friction and adhesion between alumina and tungsten were studied using modified AFM techniques. Friction was constant with potassium iodate concentration, but varied with applied pressure. This corroborates the results from the energy balance. Adhesion between the alumina and the tungsten was proportional to the potassium iodate concentration. A heuristic mechanism, which captures the relationship between polish rate, pressure, velocity, and slurry chemistry, is presented

  14. Kinetics and mechanism of hydrolysis of scandium sulfate

    International Nuclear Information System (INIS)

    Koshchej, E.V.; Stryapkov, A.V.; Podosenov, D.E.; Makarov, G.V.; Razdobreev, D.A.

    1998-01-01

    The Sc 2 (SO 4 ) 3 -H 2 SO 4 -H 2 O system is studied through the methods of pH-potentiometry, conductometry and turbidimetry at 298 and 318 K and ion force 0.01, 0.1 and 1.0. The hydrolysis mechanism including the processes in the system homogenous and heterogeneous constituents. The hydrolysis rates of scandium salts and their dependences on OH-ions concentration, solution ions force and temperature are found; the constants of the processes rate with participation of OH - and SO 4 2- ions and constants of the solid phase formation rate are calculated [ru

  15. Complex Reaction Kinetics in Chemistry: A Unified Picture Suggested by Mechanics in Physics

    Directory of Open Access Journals (Sweden)

    Elena Agliari

    2018-01-01

    Full Text Available Complex biochemical pathways can be reduced to chains of elementary reactions, which can be described in terms of chemical kinetics. Among the elementary reactions so far extensively investigated, we recall the Michaelis-Menten and the Hill positive-cooperative kinetics, which apply to molecular binding and are characterized by the absence and the presence, respectively, of cooperative interactions between binding sites. However, there is evidence of reactions displaying a more complex pattern: these follow the positive-cooperative scenario at small substrate concentration, yet negative-cooperative effects emerge as the substrate concentration is increased. Here, we analyze the formal analogy between the mathematical backbone of (classical reaction kinetics in Chemistry and that of (classical mechanics in Physics. We first show that standard cooperative kinetics can be framed in terms of classical mechanics, where the emerging phenomenology can be obtained by applying the principle of least action of classical mechanics. Further, since the saturation function plays in Chemistry the same role played by velocity in Physics, we show that a relativistic scaffold naturally accounts for the kinetics of the above-mentioned complex reactions. The proposed formalism yields to a unique, consistent picture for cooperative-like reactions and to a stronger mathematical control.

  16. Kinetic study on ferulic acid production from banana stem waste via mechanical extraction

    Science.gov (United States)

    Zainol, Norazwina; Masngut, Nasratun; Khairi Jusup, Muhamad

    2018-04-01

    Banana is the tropical plants associated with lots of medicinal properties. It has been reported to be a potential source of phenolic compounds such as ferulic acid (FA). FA has excellent antioxidant properties higher than vitamin C and E. FA also have a wide range of biological activities, such as antioxidant activities and anti-microbial activities. This paper presents an experimental and kinetic study on ferulic acid (FA) production from banana stem waste (BSW) via mechanical extraction. The objective of this research is to determine the kinetic parameters in the ferulic acid production. The banana stem waste was randomly collected from the local banana plantation in Felda Lepar Hilir, Pahang. The banana stem juice was mechanically extracted by using sugarcane press machine (KR3176) and further analyzed in high performance liquid chromatography. The differential and integral method was applied to determine the kinetic parameter of the extraction process and the data obtained were fitted into the 0th, 1st and 2nd order of extraction process. Based on the results, the kinetic parameter and R2 value from were 0.05 and 0.93, respectively. It was determined that the 0th kinetic order fitted the reaction processes to best represent the mechanical extraction.

  17. Pleural liquid and kinetic friction coefficient of mesothelium after mechanical ventilation.

    Science.gov (United States)

    Bodega, Francesca; Sironi, Chiara; Porta, Cristina; Zocchi, Luciano; Agostoni, Emilio

    2015-01-15

    Volume and protein concentration of pleural liquid in anesthetized rabbits after 1 or 3h of mechanical ventilation, with alveolar pressure equal to atmospheric at end expiration, were compared to those occurring after spontaneous breathing. Moreover, coefficient of kinetic friction between samples of visceral and parietal pleura, obtained after spontaneous or mechanical ventilation, sliding in vitro at physiological velocity under physiological load, was determined. Volume of pleural liquid after mechanical ventilation was similar to that previously found during spontaneous ventilation. This finding is contrary to expectation of Moriondo et al. (2005), based on measurement of lymphatic and interstitial pressure. Protein concentration of pleural liquid after mechanical ventilation was also similar to that occurring after spontaneous ventilation. Coefficient of kinetic friction after mechanical ventilation was 0.023±0.001, similar to that obtained after spontaneous breathing. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Modelling of the photooxidation of toluene: conceptual ideas for validating detailed mechanisms

    Directory of Open Access Journals (Sweden)

    V. Wagner

    2003-01-01

    Full Text Available Toluene photooxidation is chosen as an example to examine how simulations of smog-chamber experiments can be used to unravel shortcomings in detailed mechanisms and to provide information on complex reaction systems that will be crucial for the design of future validation experiments. The mechanism used in this study is extracted from the Master Chemical Mechanism Version 3 (MCM v3 and has been updated with new modules for cresol and g-dicarbonyl chemistry. Model simulations are carried out for a toluene-NOx experiment undertaken at the European Photoreactor (EUPHORE. The comparison of the simulation with the experimental data reveals two fundamental shortcomings in the mechanism: OH production is too low by about 80%, and the ozone concentration at the end of the experiment is over-predicted by 55%. The radical budget was analysed to identify the key intermediates governing the radical transformation in the toluene system. Ring-opening products, particularly conjugated g-dicarbonyls, were identified as dominant radical sources in the early stages of the experiment. The analysis of the time evolution of radical production points to a missing OH source that peaks when the system reaches highest reactivity. First generation products are also of major importance for the ozone production in the system. The analysis of the radical budget suggests two options to explain the concurrent under-prediction of OH and over-prediction of ozone in the model: 1 missing oxidation processes that produce or regenerate OH without or with little NO to NO2 conversion or 2 NO3 chemistry that sequesters reactive nitrogen oxides into stable nitrogen compounds and at the same time produces peroxy radicals. Sensitivity analysis was employed to identify significant contributors to ozone production and it is shown how this technique, in combination with ozone isopleth plots, can be used for the design of validation experiments.

  19. Kinetics and mechanism of the oxidation of ZrC

    International Nuclear Information System (INIS)

    Rama Rao, G.A.; Venugopal, V.; Sood, D.D.

    1993-01-01

    The oxidation behaviour of sintered ZrC powder was studied under iso and non-isothermal heating conditions under varied oxygen pressures from 0.05 to 0.5 atm and the weight changes during the reaction were followed by thermogravimetry. The sample ignited under oxygen pressure of 1 atm when heated non-isothermally at 5 K/min. The end product was identified by X-ray diffraction method as cubic ZrO 2 at temperatures below 1073 K and monoclinic above that. The rate of the reaction was found to be diffusion controlled. The mechanism of the reaction was discussed in terms of the diffusion of oxygen through the product layer. (author). 8 refs., 1 fig., 1 tab

  20. Mechanism, kinetics and application studies on enhanced activated sludge by interior microelectrolysis.

    Science.gov (United States)

    Yang, Xiaoyi; Xue, Yu; Wang, Wenna

    2009-01-01

    Enhanced activated sludge by interior microelectrolysis (EAIM) was studied to treat textile wastewater, kinetics, mechanism and application of which were also discussed in comparison with traditional activated sludge and interior microelectrolysis, respectively. The results of kinetics study indicated three different processes all followed first-order kinetics well. In EAIM, three impact factors take effects on COD removal, which are flocculation, activated sludge and electrophoresis and redox. In terms of assumption of no interaction among three COD removal mechanisms, 49.6% of the total COD removal is ascribed to flocculation, 30.1% to activated sludge and 20.3% to electrophoresis and redox. EAIM showed its advantages in COD removal efficiency, extensive adaptability to complex composition and wide range of pH. EAIM-aerobic process provided an efficient and economic performance for dealing with textile wastewater.

  1. Plasma-assisted ignition and combustion: nanosecond discharges and development of kinetic mechanisms

    Science.gov (United States)

    Starikovskaia, S. M.

    2014-09-01

    This review covers the results obtained in the period 2006-2014 in the field of plasma-assisted combustion, and in particular the results on ignition and combustion triggered or sustained by pulsed nanosecond discharges in different geometries. Some benefits of pulsed high voltage discharges for kinetic study and for applications are demonstrated. The necessity of and the possibility of building a particular kinetic mechanism of plasma-assisted ignition and combustion are discussed. The most sensitive regions of parameters for plasma-combustion kinetic mechanisms are selected. A map of the pressure and temperature parameters (P-T diagram) is suggested, to unify the available data on ignition delay times, ignition lengths and densities of intermediate species reported by different authors.

  2. Revisiting the Kinetics and Mechanism of Bromate-Bromide Reaction

    Directory of Open Access Journals (Sweden)

    Côrtes Carlos Eduardo S.

    2001-01-01

    Full Text Available The bromate-bromide reaction was investigated in an acidity range not studied yet. The reaction was followed at the Br2/Br3- isosbestic point (lambda = 446 nm. It was observed a first-order behavior for bromate and bromide ions and a second-order behavior for H+ ion that results in the rate law nu = k[BrO3-][Br- ][H+]². This rate law suggests a mechanism involving two successive protonation of bromate followed by the interaction of the intermediate species H2BrO3+ with bromide. These results disagree with the obtained by other authors who observed a second-order behavior for the bromide and first-order for H+, and have proposed intermediate species like H2Br2O3 and HBr2O3-. The second-order for [H+] observed in the range 0.005 <= [H+] <= 2.77 mol L-1 sets down that the pKa of bromic acid, HBrO3, must be lower than -0.5 (T = 25 °C, different from all other values for this pKa proposed in the literature.

  3. A Simulational approach to teaching statistical mechanics and kinetic theory

    International Nuclear Information System (INIS)

    Karabulut, H.

    2005-01-01

    A computer simulation demonstrating how Maxwell-Boltzmann distribution is reached in gases from a nonequilibrium distribution is presented. The algorithm can be generalized to the cases of gas particles (atoms or molecules) with internal degrees of freedom such as electronic excitations and vibrational-rotational energy levels. Another generalization of the algorithm is the case of mixture of two different gases. By choosing the collision cross sections properly one can create quasi equilibrium distributions. For example by choosing same atom cross sections large and different atom cross sections very small one can create mixture of two gases with different temperatures where two gases slowly interact and come to equilibrium in a long time. Similarly, for the case one kind of atom with internal degrees of freedom one can create situations that internal degrees of freedom come to the equilibrium much later than translational degrees of freedom. In all these cases the equilibrium distribution that the algorithm gives is the same as expected from the statistical mechanics. The algorithm can also be extended to cover the case of chemical equilibrium where species A and B react to form AB molecules. The laws of chemical equilibrium can be observed from this simulation. The chemical equilibrium simulation can also help to teach the elusive concept of chemical potential

  4. Devitrification kinetics and phase selection mechanisms in Cu-Zr metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Kalay, Ilkay [Iowa State Univ., Ames, IA (United States)

    2010-01-01

    research on the behaviors of glass forming alloys. Further motivation arising from the application of this system as a basis for many BMGs and ACC materials; the Cu-Zr system warrants this attention and offers great potential for the development of new materials. However, the prediction and control of microstructural evolution during devitrification remains challenging because of the complex devitrification behavior of the Cu-Zr binary alloy which is arising from the competition of metastable and stable phases and diversity of crystal structures. This dissertation details a systematic fundamental investigation into the mechanisms and kinetics of the various crystallization transformation processes involved in the overall devitrification response of Cu-Zr and Cu-Zr-Al glasses. Various isothermal and nonisothermal treatments are employed, and the structural response is characterized using bulk X-ray and thermal analysis methods as well as nanoscale microscopic analysis methods, revealing structural and chemical details down to the atomic-scale. By carefully combining techniques such as differential scanning calorimetry (DSC), in-situ synchrotron high energy X-ray diffraction (HEXRD), and transmission electron microscopy (TEM) to quantify the characterization transformations, this research has uncovered numerous details concerning the atomistic mechanisms of crystallization and has provided much new understanding related to the dominant phases, the overall reaction sequences, and the rate-controlling mechanisms. As such this work represents a substantial step forward in understanding these transformations and provides a clear framework for further progress toward ultimate application of controlled devitrification processing for the production of new materials with remarkable properties.

  5. Understanding the mechanical properties of DNA origami tiles and controlling the kinetics of their folding and unfolding reconfiguration.

    Science.gov (United States)

    Chen, Haorong; Weng, Te-Wei; Riccitelli, Molly M; Cui, Yi; Irudayaraj, Joseph; Choi, Jong Hyun

    2014-05-14

    DNA origami represents a class of highly programmable macromolecules that can go through conformational changes in response to external signals. Here we show that a two-dimensional origami rectangle can be effectively folded into a short, cylindrical tube by connecting the two opposite edges through the hybridization of linker strands and that this process can be efficiently reversed via toehold-mediated strand displacement. The reconfiguration kinetics was experimentally studied as a function of incubation temperature, initial origami concentration, missing staples, and origami geometry. A kinetic model was developed by introducing the j factor to describe the reaction rates in the cyclization process. We found that the cyclization efficiency (j factor) increases sharply with temperature and depends strongly on the structural flexibility and geometry. A simple mechanical model was used to correlate the observed cyclization efficiency with origami structure details. The mechanical analysis suggests two sources of the energy barrier for DNA origami folding: overcoming global twisting and bending the structure into a circular conformation. It also provides the first semiquantitative estimation of the rigidity of DNA interhelix crossovers, an essential element in structural DNA nanotechnology. This work demonstrates efficient DNA origami reconfiguration, advances our understanding of the dynamics and mechanical properties of self-assembled DNA structures, and should be valuable to the field of DNA nanotechnology.

  6. Kinetics and mechanism of oxidation of glycine by iron(III)

    Indian Academy of Sciences (India)

    Kinetics and mechanism of oxidation of glycine by iron(III)-1,10-phenanthroline complex has been studied in perchloric acid medium. The reaction is first order with respect to iron(III) and glycine. An increase in (phenanthroline) increases the rate, while increase in [H+] decreases the rate. Hence it can be inferred that the ...

  7. Experimental and detailed kinetic modeling study of PAH formation in laminar co-flow methane diffusion flames

    DEFF Research Database (Denmark)

    Cuoci, Alberto; Frassoldati, Alessio; Faravelli, Tiziano

    2013-01-01

    In the present paper, synchrotron VUV photoionization mass spectrometry is used to study the detailed chemistry of co-flow methane diffusion flames with different dilution ratios. The experimental results constitute a comprehensive characterization of species important for PAH and soot formation...

  8. Miniature free-piston homogeneous charge compression ignition engine-compressor concept - Part II: modeling HCCI combustion in small scales with detailed homogeneous gas phase chemical kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Aichlmayr, H.T.; Kittelson, D.B.; Zachariah, M.R. [The University of Minnesota, Minneapolis (United States). Departments of Mechanical Engineering and Chemistry

    2002-10-01

    Operational maps for crankshaft-equipped miniature homogeneous charge compression ignition engines are established using performance estimation, detailed chemical kinetics, and diffusion models for heat transfer and radical loss. In this study, radical loss was found to be insignificant. In contrast, heat transfer was found to be increasingly significant for 10, 1, and 0.1 W engines, respectively. Also, temperature-pressure trajectories and ignition delay time maps are used to explore relationships between engine operational parameters and HCCI. Lastly, effects of engine operating conditions and design on the indicated fuel conversion efficiency are investigated. (author)

  9. Oxidative Dehydrogenation on Nanocarbon: Insights into the Reaction Mechanism and Kinetics via in Situ Experimental Methods.

    Science.gov (United States)

    Qi, Wei; Yan, Pengqiang; Su, Dang Sheng

    2018-03-20

    Sustainable and environmentally benign catalytic processes are vital for the future to supply the world population with clean energy and industrial products. The replacement of conventional metal or metal oxide catalysts with earth abundant and renewable nonmetallic materials has attracted considerable research interests in the field of catalysis and material science. The stable and efficient catalytic performance of nanocarbon materials was discovered at the end of last century, and these materials are considered as potential alternatives for conventional metal-based catalysts. With its rapid development in the past 20 years, the research field of carbon catalysis has been experiencing a smooth transition from the discovery of novel nanocarbon materials or related new reaction systems to the atomistic-level mechanistic understanding on the catalytic process and the subsequent rational design of the practical catalytic reaction systems. In this Account, we summarize the recent progress in the kinetic and mechanistic studies on nanocarbon catalyzed alkane oxidative dehydrogenation (ODH) reactions. The paper attempts to extract general concepts and basic regularities for carbon catalytic process directing us on the way for rational design of novel efficient metal-free catalysts. The nature of the active sites for ODH reactions has been revealed through microcalorimetric analysis, ambient pressure X-ray photoelectron spectroscopy (XPS) measurement, and in situ chemical titration strategies. The detailed kinetic analysis and in situ catalyst structure characterization suggests that carbon catalyzed ODH reactions involve the redox cycles of the ketonic carbonyl-hydroxyl pairs, and the key physicochemical parameters (activation energy, reaction order, and rate/equilibrium constants, etc.) of the carbon catalytic systems are proposed and compared with conventional transition metal oxide catalysts. The proposal of the intrinsic catalytic activity (TOF) provides the

  10. The Kinetics and Mechanism for the Oxidation of Nicotinic Acid by Peroxomonosulfate in Acidic Aqueous Medium

    Energy Technology Data Exchange (ETDEWEB)

    Agrawal, Anju; Sailani, Riya; Gupta, Beena; Khandelwal, C. L.; Sharma, P. D. [Univ. of Rajasthan, Jaipur (India)

    2012-04-15

    The kinetics of oxidation of nicotinic acid by peroxomonosulfate (PMS) has been studied in acetate buffers. Stoichiometry of the reaction corresponds to the reaction of one mole of the oxidant with a mole of nicotinic acid. N→O product has been confirmed both by UV visible and IR spectroscopy. The reaction is second order viz. first order with respect to each reactant. Activation parameters have also been evaluated. A plausible reaction mechanism is mentioned and the derived kinetic rate law accounts for experimental observations.

  11. The Kinetics and Mechanism for the Oxidation of Nicotinic Acid by Peroxomonosulfate in Acidic Aqueous Medium

    International Nuclear Information System (INIS)

    Agrawal, Anju; Sailani, Riya; Gupta, Beena; Khandelwal, C. L.; Sharma, P. D.

    2012-01-01

    The kinetics of oxidation of nicotinic acid by peroxomonosulfate (PMS) has been studied in acetate buffers. Stoichiometry of the reaction corresponds to the reaction of one mole of the oxidant with a mole of nicotinic acid. N→O product has been confirmed both by UV visible and IR spectroscopy. The reaction is second order viz. first order with respect to each reactant. Activation parameters have also been evaluated. A plausible reaction mechanism is mentioned and the derived kinetic rate law accounts for experimental observations

  12. Kinetics and Mechanism of Oxidation of Benzyl Alcohol by Benzimidazolium Fluorochromate

    Directory of Open Access Journals (Sweden)

    J. Dharmaraja

    2008-01-01

    Full Text Available The kinetics of oxidation of benzyl alcohol (BzOH by benzimidazolium fluorochromate (BIFC has been studied in 50% aqueous acetic acid medium at 308 K. The reaction is first order with respect to [oxidant] and [benzyl alcohol]. The reaction is catalysed by hydrogen ions. The decrease in dielectric constant of the medium increases the rate of the reaction. Addition of sodium perchlorate increases the rate of the reaction appreciably. No polymerization with acrylonitrile. The reaction has been conducted at four different temperature and the activation parameters were calculated. From the observed kinetic results a suitable mechanism was proposed.

  13. Kinetics and Mechanism of Oxidation of Isoleucine by N-Bromophthalimide in Aqueous Perchloric Acid Medium

    Directory of Open Access Journals (Sweden)

    N. M. I. Alhaji

    2011-01-01

    Full Text Available The kinetics of oxidation of isoleucine with N-bromophthalimide has been studied in perchloric acid medium potentiometrically. The reaction is of first order each in [NBP] and [amino acid] and negative fractional order in [H+]. The rate is decreased by the addition of phthalimide. A decrease in the dielectric constant of the medium increases the rate. Addition of halide ions or acrylonitrile has no effect on the kinetics. Similarly, variation of ionic strength of the medium does not affect the reaction rate. The reaction rate has been determined at different temperatures and activation parameters have been calculated. A suitable mechanism involving hypobromous acid as reactive species has been proposed.

  14. Screw-vector bond graphs for kinetic-static modelling and analysis of mechanisms

    International Nuclear Information System (INIS)

    Bidard, Catherine

    1994-01-01

    This dissertation deals with the kinetic-static modelling and analysis of spatial mechanisms used in robotics systems. A framework is proposed, which embodies a geometrical and a network approach for kinetic-static modelling. For this purpose we use screw theory and bond graphs. A new form of bond graphs is introduced: the screw-vector bond graph, whose power variables are defined to be wrenches and twists expressed as intrinsic screw-vectors. The mechanism is then identified as a network, whose components are kinematic pairs and whose topology is described by a directed graph. A screw-vector Simple Junction Structure represents the topological constraints. Kinematic pairs are represented by one-port elements, defined by two reciprocal screw-vector spaces. Using dual bases of screw-vectors, a generic decomposition of kinematic pair elements is given. The reduction of kinetic-static models of series and parallel kinematic chains is used in order to derive kinetic-static functional models in geometric form. Thereupon, the computational causality assignment is adapted for the graphical analysis of the mobility and the functioning of spatial mechanisms, based on completely or incompletely specified models. (author) [fr

  15. A detailed analysis of adhesion mechanics between a compliant elastic coating and a spherical probe

    International Nuclear Information System (INIS)

    Sridhar, I; Zheng, Z W; Johnson, K L

    2004-01-01

    As length scales decrease, adhesive forces become increasingly important. These adhesive forces contribute to the normal load in experiments conducted on thin layered systems using micro-probe instruments such as the surface force apparatus (SFA) and the atomic force microscope (AFM). Adhesion between these thin-layer systems was analysed by Sridhar et al (1997 J. Phys. D: Appl. Phys. 30 1710) for the SFA geometry and Johnson and Sridhar (2001 J. Phys. D: Appl. Phys. 34 683) for AFM using a numerical SJF (Sridhar-Johnson-Fleck) version of the JKR (Johnson-Kendal-Roberts) theory. In this paper, adhesion mechanics between a compliant elastic coating and a spherical probe is investigated using the SJF model in detail. When the substrate is rigid, the non-dimensional pull-off force may differ from the JKR value of -0.5 by as much as 90%. Computations of the contact size at zero load and pull-off force are presented for a range of values of adhesion energy. Finally, empirical relations for the contact load and contact compliance as a function of contact radius were obtained from the numerical data for practical layer-substrate material systems

  16. Kinetics and mechanism of thermal processes of nonreversible decomposition of the system N2O4-NO

    International Nuclear Information System (INIS)

    Nesterenko, V.B.; Nichipor, G.V.

    1989-01-01

    Consideration is given to kinetics and mechanism of decomposition of nitrogen oxide in gaseous phase at devated pressures and temperature, decomposition of N 2 O 4 -NO system under flow conditions, as well as to kinetics and mechanism of formation of nitrons oxide. 37 refs.; 13 figs.; 13 tabs

  17. Characterization and kinetic study of Diels-Alder reaction: Detailed study on N-phenylmaleimide and furan based benzoxazine with potential self-healing application

    Directory of Open Access Journals (Sweden)

    Z. Stirn

    2016-07-01

    Full Text Available The Diels-Alder reaction between N-phenylmaleimide and benzoxazine bearing furan group was investigated for the purpose of successful appliance of self-healing in benzoxazine polymer networks. The reaction as a function of temperature/time was performed in molten state and in a solution, where also the kinetic study was performed. The Diels-Alder reaction leads to a mixture of two diastereomers: endo presented at lower cyclo-reversion temperature and exo at higher. Therefore, the conversion rates and exo/endo ratio were studied in detail for both systems. For instance, in molten state the Diels-Alder reaction was triggered by the temperature of the melting point at 60 °C with exo/endo ratio preferable to the endo adduct. The study of the kinetics in a solution revealed that the Diels-Alder reaction followed typical bimolecular reversible second-order reaction. The activation energies were close to the previous literature data; 48.4 and 51.9 kJ·mol–1 for Diels-Alder reaction, and 91.0 and 102.3 kJ·mol–1 for retro-Diels-Alder reaction, in acetonitrile and chloroform, respectively. The reaction equilibrium in a solution is much more affected by the retro-Diels-Alder reaction than in a molten state. This study shows detailed investigation of DA reaction and provides beneficial knowledge for further use in self-healing polymer networks.

  18. Thermo-kinetic mechanisms for grain boundary structure multiplicity, thermal instability and defect interactions

    International Nuclear Information System (INIS)

    Burbery, N.J.; Das, R.; Ferguson, W.G.

    2016-01-01

    Grain boundaries (GBs) provide a source and/or a sink for crystal defects and store elastic energy due to the non-uniform atomic bonding structure of the GB core. GB structures are thermodynamically driven to transition to the lowest energy configuration possible; however to date there has been little evidence to explain why specific GB structures have a low energy state. Furthermore, there is little quantitative demonstration of the significance of physical and GB structure characteristics on the GB energy, thermal stability, and the effect of temporary local GB structure transformations on defect interactions. This paper evaluates the defect interactions and structure stability of multiple Σ5(310) GB structures in bi-crystals of pure aluminium, and systematically investigates the features at 0 K to characterise multiple metastable structures. Structure stability is evaluated by utilising unstable vacancy defects to initiate GB transformations, and using nudged elastic band simulations to quantify this with the activation energy. The emission of stable vacancy defects from the ‘stable’ and metastable grain boundaries is also evaluated in the same manner. A detailed analysis of dislocation nucleation at the atomistic scale demonstrates that local transformations of GB structure between stable and metastable intermediates can provide a mechanism to accommodate the generation of crystal defects. Kinetic (time-dependent) effects that compete with energetic driving forces for structural transformations of GBs are shown to cause a significant effect on the activation properties that may exceed the influence of GB potential energy. The results demonstrate that GB structural multiplicity can be associated with the generation and absorption of dislocations and vacancies. This paper demonstrates the suitability of atomistic simulations coupled with nudged elastic band simulations to evaluate fundamental thermodynamic properties of pure FCC metals. Overall, this paper

  19. Thermo-kinetic mechanisms for grain boundary structure multiplicity, thermal instability and defect interactions

    Energy Technology Data Exchange (ETDEWEB)

    Burbery, N.J. [Department of Mechanical Engineering, University of Auckland, Auckland 1010 (New Zealand); Das, R., E-mail: r.das@auckland.ac.nz [Department of Mechanical Engineering, University of Auckland, Auckland 1010 (New Zealand); Ferguson, W.G. [Department of Chemical and Materials Engineering, University of Auckland, Auckland 1010 (New Zealand)

    2016-08-15

    Grain boundaries (GBs) provide a source and/or a sink for crystal defects and store elastic energy due to the non-uniform atomic bonding structure of the GB core. GB structures are thermodynamically driven to transition to the lowest energy configuration possible; however to date there has been little evidence to explain why specific GB structures have a low energy state. Furthermore, there is little quantitative demonstration of the significance of physical and GB structure characteristics on the GB energy, thermal stability, and the effect of temporary local GB structure transformations on defect interactions. This paper evaluates the defect interactions and structure stability of multiple Σ5(310) GB structures in bi-crystals of pure aluminium, and systematically investigates the features at 0 K to characterise multiple metastable structures. Structure stability is evaluated by utilising unstable vacancy defects to initiate GB transformations, and using nudged elastic band simulations to quantify this with the activation energy. The emission of stable vacancy defects from the ‘stable’ and metastable grain boundaries is also evaluated in the same manner. A detailed analysis of dislocation nucleation at the atomistic scale demonstrates that local transformations of GB structure between stable and metastable intermediates can provide a mechanism to accommodate the generation of crystal defects. Kinetic (time-dependent) effects that compete with energetic driving forces for structural transformations of GBs are shown to cause a significant effect on the activation properties that may exceed the influence of GB potential energy. The results demonstrate that GB structural multiplicity can be associated with the generation and absorption of dislocations and vacancies. This paper demonstrates the suitability of atomistic simulations coupled with nudged elastic band simulations to evaluate fundamental thermodynamic properties of pure FCC metals. Overall, this paper

  20. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation

    Directory of Open Access Journals (Sweden)

    Mohamad Irfan Fathurrohman

    2015-07-01

    Full Text Available The vulcanization kinetics of Ethylene-propylene diene monomer (EPDM rubber thermal insulation was studied by using rheometer under isothermal condition at different temperatures. The rheometry analysis was used to determining the cure kinetic parameters and predicting the cure time of EPDM thermal insulation. The experimental results revealed that the curing curves of EPDM thermal insulation were marching and the optimum curing time decreased with increasing the temperature. The kinetic parameters were determined from the autocatalytic model showed close fitting with the experimental results, indicating suitability of autocatalytic model in characterizing the cure kinetics. The activation energy was determined from the autocatalytic model is 46.3661 kJ mol-1. The cure time were predicted from autocatalytic model and the obtained kinetic parameter by using the relationship among degree of conversion, cure temperature, and cure time. The predictions of cure time provide information for the actual curing characteristic of EPDM thermal insulation. The mechanical properties of EPDM thermal insulation with different vulcanization temperatures showed the same hardness, tensile strength and modulus at 300%, except at temperature 70 °C, while the elongation at breaking point decreased with increasing temperature of vulcanization. © 2015 BCREC UNDIP. All rights reservedReceived: 8th April 2014; Revised: 7th January 2015; Accepted: 16th January 2015How to Cite: Fathurrohman, M.I., Maspanger, D.R., Sutrisno, S. (2015. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation. Bulletin of Chemi-cal Reaction Engineering & Catalysis, 10 (2, 104-110. (doi:10.9767/bcrec.10.2.6682.104-110Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.6682.104-110 

  1. Exact results in nonequilibrium statistical mechanics: Formalism and applications in chemical kinetics and single-molecule free energy estimation

    Science.gov (United States)

    Adib, Artur B.

    In the last two decades or so, a collection of results in nonequilibrium statistical mechanics that departs from the traditional near-equilibrium framework introduced by Lars Onsager in 1931 has been derived, yielding new fundamental insights into far-from-equilibrium processes in general. Apart from offering a more quantitative statement of the second law of thermodynamics, some of these results---typified by the so-called "Jarzynski equality"---have also offered novel means of estimating equilibrium quantities from nonequilibrium processes, such as free energy differences from single-molecule "pulling" experiments. This thesis contributes to such efforts by offering three novel results in nonequilibrium statistical mechanics: (a) The entropic analog of the Jarzynski equality; (b) A methodology for estimating free energies from "clamp-and-release" nonequilibrium processes; and (c) A directly measurable symmetry relation in chemical kinetics similar to (but more general than) chemical detailed balance. These results share in common the feature of remaining valid outside Onsager's near-equilibrium regime, and bear direct applicability in protein folding kinetics as well as in single-molecule free energy estimation.

  2. Mechanism and kinetics of the oxidation of synthetic alpha-NiS

    Directory of Open Access Journals (Sweden)

    BOYAN BOYANOV

    2008-02-01

    Full Text Available The results of an investigation of the mechanism and kinetics of the oxidation process of synthetic a-NiS are presented in this paper. The mechanism of a-NiS oxidation was investigated based on the comparative analysis of DTA–TG–DTG and XRD results, as well as the constructed phase stability diagrams (PSD for the Ni–S–O system. The kinetic investigations of the oxidation process were performed under isothermal conditions (temperature range 823–1073 K. The obtained degrees of desulfurization were used in the calculation process according to the Sharp model and the kinetic parameters, including the activation energies and the rate constants of the characteristic reactions, for the oxidation of a-NiS were determined. These results enabled the formulation of a kinetic equation for the desulfurization process: ‑ln(1−a = k1t = 27.89 exp(–9860/Tt, with an activation energy of 82±4 kJ mol-1, for the first stage of the process and –ln (1 − a = k2t = 1.177 exp(–4810/Tt, with an activation energy of 40±2 kJ mol-1, for the second stage.

  3. Training-induced acceleration of oxygen uptake kinetics in skeletal muscle: the underlying mechanisms.

    Science.gov (United States)

    Zoladz, J A; Korzeniewski, B; Grassi, B

    2006-11-01

    It is well known that the oxygen uptake kinetics during rest-to-work transition (V(O2) on-kinetics) in trained subjects is significantly faster than in untrained individuals. It was recently postulated that the main system variable that determines the transition time (t(1/2)) of the V(O2) on-kinetics in skeletal muscle, at a given moderate ATP usage/work intensity, and under the assumption that creatine kinase reaction works near thermodynamic equilibrium, is the absolute (in mM) decrease in [PCr] during rest-to-work transition. Therefore we postulate that the training-induced acceleration of the V(O2) on-kinetics is a marker of an improvement of absolute metabolic stability in skeletal muscles. The most frequently postulated factor responsible for enhancement of muscle metabolic stability is the training-induced increase in mitochondrial proteins. However, the mechanism proposed by Gollnick and Saltin (1982) can improve absolute metabolic stability only if training leads to a decrease in resting [ADP(free)]. This effect is not observed in many examples of training causing an acceleration of the V(O2) on-kinetics, especially in early stages of training. Additionally, this mechanism cannot account for the significant training-induced increase in the relative (expressed in % or as multiples of the resting values) metabolic stability at low work intensities, condition in which oxidative phosphorylation is not saturated with [ADP(free)]. Finally, it was reported that in the early stage of training, acceleration in the V(O2) on-kinetics and enhancement of muscle metabolic stability may precede adaptive responses in mitochondrial enzymes activities or mitochondria content. We postulate that the training-induced acceleration in the V(O2) on-kinetics and the improvement of the metabolite stability during moderate intensity exercise in the early stage of training is mostly caused by an intensification of the "parallel activation" of ATP consumption and ATP supply pathways

  4. Biofilm Formation Mechanisms of Pseudomonas aeruginosa Predicted via Genome-Scale Kinetic Models of Bacterial Metabolism

    Science.gov (United States)

    2016-03-15

    RESEARCH ARTICLE Biofilm Formation Mechanisms of Pseudomonas aeruginosa Predicted via Genome-Scale Kinetic Models of Bacterial Metabolism Francisco G...jaques.reifman.civ@mail.mil Abstract A hallmark of Pseudomonas aeruginosa is its ability to establish biofilm -based infections that are difficult to...eradicate. Biofilms are less susceptible to host inflammatory and immune responses and have higher antibiotic tolerance than free-living planktonic

  5. Heterogeneous reaction mechanisms and kinetics relevant to the CVD of semiconductor materials

    Energy Technology Data Exchange (ETDEWEB)

    Creighton, J.R.; Coltrin, M.E.

    1994-03-01

    This report documents the state of the art in experimental and theoretical techniques for determining reaction mechanisms and chemical kinetics of heterogeneous reactions relevant to the chemical vapor deposition of semiconductor materials. It summarizes the most common ultra-high vacuum experimental techniques that are used and the types of rate information available from each. Several case studies of specific chemical systems relevant to the microelectronics industry are described. Theoretical methods for calculating heterogeneous reaction rate constants are also summarized.

  6. Kinetics and mechanism of the gas phase reaction of Cl atoms with iodobenzene

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Ponomarev, DA; Nielsen, OJ

    2001-01-01

    Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms with iodobenzene (C6H5I) in 20-700 Torr of N-2, air, or O-2 diluent at 296 K. The reaction proceeds with a rate constant k(Cl + QH(5)I) = (3.3 +/- 0.7) x 10(-11) cm(3) molecule(-1) s(-1) to give...

  7. Microscopic Mechanism of Doping-Induced Kinetically Constrained Crystallization in Phase-Change Materials.

    Science.gov (United States)

    Lee, Tae Hoon; Loke, Desmond; Elliott, Stephen R

    2015-10-07

    A comprehensive microscopic mechanism of doping-induced kinetically constrained crystallization in phase-change materials is provided by investigating structural and dynamical dopant characteristics via ab initio molecular dynamics simulations. The information gained from this study may provide a basis for a fast screening of dopant species for electronic memory devices, or for understanding the general physics involved in the crystallization of doped glasses. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Lithium and rubidium extraction from zinnwaldite by alkali digestion process: Sintering mechanism and leaching kinetics

    Czech Academy of Sciences Publication Activity Database

    Vu, H.; Bernardi, J.; Jandová, J.; Vaculíková, Lenka; Goliáš, V.

    2013-01-01

    Roč. 123, č. 1 (2013), s. 9-17 ISSN 0301-7516 R&D Projects: GA MŠk ED2.1.00/03.0082 Institutional support: RVO:68145535 Keywords : zinnwaldite * lithium * rubidium * sintering mechanism * leaching kinetics Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 1.461, year: 2013 http://www.sciencedirect.com/science/article/pii/S0301751613001087

  9. Recent Insight into the Kinetic Mechanisms and Conformational Dynamics of Y-Family DNA Polymerases

    OpenAIRE

    Maxwell, Brian A.; Suo, Zucai

    2014-01-01

    The kinetic mechanisms by which DNA polymerases catalyze DNA replication and repair have long been areas of active research. Recently discovered Y-family DNA polymerases catalyze the bypass of damaged DNA bases that would otherwise block replicative DNA polymerases and stall replication forks. Unlike DNA polymerases from the five other families, the Y-family DNA polymerases have flexible, solvent-accessible active sites that are able to tolerate various types of damaged template bases and all...

  10. Kinetic mix mechanisms in shock-driven inertial confinement fusion implosions

    Energy Technology Data Exchange (ETDEWEB)

    Rinderknecht, H. G.; Sio, H.; Li, C. K.; Zylstra, A. B.; Rosenberg, M. J.; Frenje, J. A.; Gatu Johnson, M.; Séguin, F. H.; Petrasso, R. D. [Plasma Science and Fusion Center, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Hoffman, N.; Kagan, G.; Molvig, K. [Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States); Betti, R.; Yu Glebov, V.; Meyerhofer, D. D.; Sangster, T. C.; Seka, W.; Stoeckl, C. [Laboratory for Laser Energetics, University of Rochester, Rochester, New York 14623 (United States); Bellei, C.; Amendt, P. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); and others

    2014-05-15

    Shock-driven implosions of thin-shell capsules, or “exploding pushers,” generate low-density, high-temperature plasmas in which hydrodynamic instability growth is negligible and kinetic effects can play an important role. Data from implosions of thin deuterated-plastic shells with hydroequivalent D{sup 3}He gas fills ranging from pure deuterium to pure {sup 3}He [H. G. Rinderknecht et al., Phys. Rev. Lett. 112, 135001 (2014)] were obtained to evaluate non-hydrodynamic fuel-shell mix mechanisms. Simulations of the experiments including reduced ion kinetic models support ion diffusion as an explanation for these data. Several additional kinetic mechanisms are investigated and compared to the data to determine which are important in the experiments. Shock acceleration of shell deuterons is estimated to introduce mix less than or comparable to the amount required to explain the data. Beam-target mechanisms are found to produce yields at most an order of magnitude less than the observations.

  11. CH4/air homogeneous autoignition: A comparison of two chemical kinetics mechanisms

    KAUST Repository

    Tingas, Efstathios Al.

    2018-03-11

    Reactions contributing to the generation of the explosive time scale that characterise autoignition of homogeneous stoichiometric CH4/air mixture are identified using two different chemical kinetics models; the well known GRI-3.0 mechanism (53/325 species/reactions with N-chemistry) and the AramcoMech mechanism from NUI Galway (113/710 species/reactions without N-chemistry; Combustion and Flame 162:315-330, 2015). Although the two mechanisms provide qualitatively similar results (regarding ignition delay and profiles of temperature, of mass fractions and of explosive time scale), the 113/710 mechanism was shown to reproduce the experimental data with higher accuracy than the 53/325 mechanism. The present analysis explores the origin of the improved accuracy provided by the more complex kinetics mechanism. It is shown that the reactions responsible for the generation of the explosive time scale differ significantly. This is reflected to differences in the length of the chemical and thermal runaways and in the set of the most influential species.

  12. RESEARCH OF KINETIC AND DIFFUSIVE MECHANISMS IN THE ADSORPTION OF Cu (II IN SUGAR CANE BAGASSE ASH

    Directory of Open Access Journals (Sweden)

    Julio Omar Prieto García

    2016-10-01

    Full Text Available In this paper a kinetic and diffusive study regarding adsorption of ions Cu (II on a sample of sugar cane bagasse ash is made. The results show that the second-order kinetic model better adjusts the experimental data than the Elovich and first-order kinetic model. The diffusive mechanism study shows that the diffusion in the liquid pellicle and in the micro-pores of the adsorbent prevail in the adsorption phenomenon.

  13. Mechanistic studies with solubilized rat liver steroid 5 alpha-reductase: Elucidation of the kinetic mechanism

    International Nuclear Information System (INIS)

    Levy, M.A.; Brandt, M.; Greway, A.T.

    1990-01-01

    A solubilized preparation of steroid 5 alpha-reductase from rat liver has been used in studies focused toward an understanding of the kinetic mechanism associated with enzyme catalysis. From the results of analyses with product and dead-end inhibitors, a preferentially ordered binding of substrates and release of products from the surface of the enzyme is proposed. The observations from these experiments were identical with those using the steroid 5 alpha-reductase activity associated with rat liver microsomes. The primary isotope effects on steady-state kinetic parameters when [4S-2H]NADPH was used also were consistent with an ordered kinetic mechanism. Normal isotope effects were observed for all three kinetic parameters (Vm/Km for both testosterone and NADPH and Vm) at all substrate concentrations used experimentally. Upon extrapolation to infinite concentration of testosterone, the isotope effect on Vm/Km for NADPH approached unity, indicating that the nicotinamide dinucleotide phosphate is the first substrate binding to and the second product released from the enzyme. The isotope effects on Vm/Km for testosterone at infinite concentration of cofactor and on Vm were 3.8 +/- 0.5 and 3.3 +/- 0.4, respectively. Data from the pH profiles of these three steady-state parameters and the inhibition constants (1/Ki) of competitive inhibitors versus both substrates indicate that the binding of nicotinamide dinucleotide phosphate involves coordination of its anionic 2'-phosphate to a protonated enzyme-associated base with an apparent pK near 8.0. From these results, relative limits have been placed on several of the internal rate constants used to describe the ordered mechanism of the rat liver steroid 5 alpha-reductase

  14. Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

    Science.gov (United States)

    Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

    2016-03-10

    Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

  15. Curing kinetics and mechanical behavior of natural rubber reinforced with pretreated carbon nanotubes

    International Nuclear Information System (INIS)

    Sui, G.; Zhong, W.H.; Yang, X.P.; Yu, Y.H.

    2008-01-01

    To significantly improve the performance of rubber materials, fundamental studies on rubber nanocomposites are necessary. The curing kinetics and vulcanizate properties of carbon nanotubes (CNTs)/natural rubber (NR) nanocomposites were analyzed in this paper. The pretreatment of CNTs was carried out by acid bath followed by ball milling with HRH bonding systems in experiments. The CNT/NR nanocomposites were prepared through solvent mixing on the basis of pretreatment of CNTs. The surface characteristic of CNTs and physical interaction between CNTs and NR macromolecules were analyzed by Fourier transform infrared spectroscopy (FT-IR). The vulcanization kinetics of CNT/NR nanocomposites were studied contrasting with the neat NR. The quality of the NR vulcanizates was assessed through static and dynamic mechanical property tests and scanning electron microscope (SEM). Curing kinetic parameters of the neat NR and CNT/NR nanocomposites were obtained from experiments; the results indicated that the presence of CNTs affects the curing process of the NR, and additional heating is required to cure CNT/NR nanocomposites due to its higher active energy. The dispersion of pretreated CNTs in the rubber matrix and interfacial adhesion between them were obviously improved. The physical and mechanical properties of the CNT/NR nanocomposites showed considerable increases by incorporation of the pretreated CNTs compared to the neat NR and untreated CNTs-filled NR nanocomposites

  16. Kinetics and mechanism of sphalerite leaching by sodium nitrate in sulphuric acid solution

    Directory of Open Access Journals (Sweden)

    Sokić M.

    2012-01-01

    Full Text Available Interest for application of hydrometallurgical processes in a processing of complex sulphide ores and concentrates has increased in recent years. Their application provides better metal recoveries and reduced emission of gaseous and toxic ageneses in the environment. The kinetics and mechanism of sphalerite leaching from complex sulphide concentrate with sulphuric acid and sodium nitrate solution at standard conditions was presented in this paper. The influences of temperature and time on the leaching degree of zinc were investigated and kinetic analysis of the process was accomplished. With temperature increasing from 60 to 90°C, the zinc leaching increased from 25.23% to 71.66% after 2 hours, i.e. from 59.40% to 99.83% after 4 hours. The selected kinetic model indicated that the diffusion through the product layer was the rate-controlling step during the sphalerite leaching. The activation energy was determined to be 55 kJ/mol in the temperature range 60-90°C. XRD, light microscopy and SEM/EDX analyses of the complex concentrate and leach residue confirmed formation of elemental sulphur and diffusion-controlled leaching mechanism.

  17. Curing kinetics and mechanical behavior of natural rubber reinforced with pretreated carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Sui, G. [Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029 (China); Department of Mechanical Engineering and Applied Mechanics, North Dakota State University, Fargo, ND 58105 (United States); Zhong, W.H. [Department of Mechanical Engineering and Applied Mechanics, North Dakota State University, Fargo, ND 58105 (United States)], E-mail: Katie.Zhong@ndsu.edu; Yang, X.P.; Yu, Y.H. [Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029 (China)

    2008-06-25

    To significantly improve the performance of rubber materials, fundamental studies on rubber nanocomposites are necessary. The curing kinetics and vulcanizate properties of carbon nanotubes (CNTs)/natural rubber (NR) nanocomposites were analyzed in this paper. The pretreatment of CNTs was carried out by acid bath followed by ball milling with HRH bonding systems in experiments. The CNT/NR nanocomposites were prepared through solvent mixing on the basis of pretreatment of CNTs. The surface characteristic of CNTs and physical interaction between CNTs and NR macromolecules were analyzed by Fourier transform infrared spectroscopy (FT-IR). The vulcanization kinetics of CNT/NR nanocomposites were studied contrasting with the neat NR. The quality of the NR vulcanizates was assessed through static and dynamic mechanical property tests and scanning electron microscope (SEM). Curing kinetic parameters of the neat NR and CNT/NR nanocomposites were obtained from experiments; the results indicated that the presence of CNTs affects the curing process of the NR, and additional heating is required to cure CNT/NR nanocomposites due to its higher active energy. The dispersion of pretreated CNTs in the rubber matrix and interfacial adhesion between them were obviously improved. The physical and mechanical properties of the CNT/NR nanocomposites showed considerable increases by incorporation of the pretreated CNTs compared to the neat NR and untreated CNTs-filled NR nanocomposites.

  18. Transport in semiconductor nanowire superlattices described by coupled quantum mechanical and kinetic models.

    Science.gov (United States)

    Alvaro, M; Bonilla, L L; Carretero, M; Melnik, R V N; Prabhakar, S

    2013-08-21

    In this paper we develop a kinetic model for the analysis of semiconductor superlattices, accounting for quantum effects. The model consists of a Boltzmann-Poisson type system of equations with simplified Bhatnagar-Gross-Krook collisions, obtained from the general time-dependent Schrödinger-Poisson model using Wigner functions. This system for superlattice transport is supplemented by the quantum mechanical part of the model based on the Ben-Daniel-Duke form of the Schrödinger equation for a cylindrical superlattice of finite radius. The resulting energy spectrum is used to characterize the Fermi-Dirac distribution that appears in the Bhatnagar-Gross-Krook collision, thereby coupling the quantum mechanical and kinetic parts of the model. The kinetic model uses the dispersion relation obtained by the generalized Kronig-Penney method, and allows us to estimate radii of quantum wire superlattices that have the same miniband widths as in experiments. It also allows us to determine more accurately the time-dependent characteristics of superlattices, in particular their current density. Results, for several experimentally grown superlattices, are discussed in the context of self-sustained coherent oscillations of the current density which are important in an increasing range of current and potential applications.

  19. Effect and kinetic mechanism of ultrasonic vibration on solidification of 7050 aluminum alloy

    Directory of Open Access Journals (Sweden)

    Ripeng Jiang

    2014-07-01

    Full Text Available The work described in this paper dealt with the effect of ultrasonic vibration on the solidification of 7050 aluminum alloy. Two experiments were carried out through introducing ultrasound into the semi-continuous direct-chill (DC casting of aluminum alloy and into alloy solidifying in a crucible, respectively. Results show that ultrasonic vibration can refine grains in the whole cross-section of a billet in the first experiment and is able to increase the cooling rate within the temperature range from 625 °C to 590 °C in the other one. The mechanism of particle resonance caused by ultrasonic vibration was illustrated on the basis of theoretical analysis of the kinetics and energy conversion during the solidification. It is demonstrated that the kinetic energy of resonant particles are mainly from the latent heat energy of solidification, which can shorten the cooling time, inhibit the crystal growth and then lead to the grain refinement.

  20. Kinetics and mechanism of the low-temperature yttrium-aluminium garnet synthesis

    International Nuclear Information System (INIS)

    Ivakin, Yu.D.; Danchevskaya, M.N.; Yanchenko, P.A.; Murav'eva, G.P.

    2000-01-01

    Kinetics and formation mechanism of finely crystalline yttrium-aluminium garnet (YAG) during hydrothermal and hot steam treatment of stoichiometric mixture of oxides in the range of temperature 200-400 Deg C and pressures of 1.5-26 MPa were studied. It is ascertained that formation of YAG occurs via intermediate stage of Y(OH) 3 structure formation, whereas the aluminia component is X-ray amorphous. Kinetics of YAG formation is described by the equation of solid phase transformation with the limiting stage of nucleation. The YAG formed contains 7-5 % of water, which corresponds to hydrogarnet structure. Unit cell parameters of the YAG samples synthesized are somewhat high and after heating up to 1200 Deg C they decrease [ru

  1. Understanding the Broad Substrate Repertoire of Nitroreductase Based on Its Kinetic Mechanism*

    Science.gov (United States)

    Pitsawong, Warintra; Hoben, John P.; Miller, Anne-Frances

    2014-01-01

    The oxygen-insensitive nitroreductase from Enterobacter cloacae (NR) catalyzes two-electron reduction of nitroaromatics to the corresponding nitroso compounds and, subsequently, to hydroxylamine products. NR has an unusually broad substrate repertoire, which may be related to protein dynamics (flexibility) and/or a simple non-selective kinetic mechanism. To investigate the possible role of mechanism in the broad substrate repertoire of NR, the kinetics of oxidation of NR by para-nitrobenzoic acid (p-NBA) were investigated using stopped-flow techniques at 4 °C. The results revealed a hyperbolic dependence on the p-NBA concentration with a limiting rate of 1.90 ± 0.09 s−1, indicating one-step binding before the flavin oxidation step. There is no evidence for a distinct binding step in which specificity might be enforced. The reduction of p-NBA is rate-limiting in steady-state turnover (1.7 ± 0.3 s−1). The pre-steady-state reduction kinetics of NR by NADH indicate that NADH reduces the enzyme with a rate constant of 700 ± 20 s−1 and a dissociation constant of 0.51 ± 0.04 mm. Thus, we demonstrate simple transient kinetics in both the reductive and oxidative half-reactions that help to explain the broad substrate repertoire of NR. Finally, we tested the ability of NR to reduce para-hydroxylaminobenzoic acid, demonstrating that the corresponding amine does not accumulate to significant levels even under anaerobic conditions. Thus E. cloacae NR is not a good candidate for enzymatic production of aromatic amines. PMID:24706760

  2. Midtarsal locking, the windlass mechanism, and running strike pattern: A kinematic and kinetic assessment.

    Science.gov (United States)

    Bruening, Dustin A; Pohl, Michael B; Takahashi, Kota Z; Barrios, Joaquin A

    2018-05-17

    Changes in running strike pattern affect ankle and knee mechanics, but little is known about the influence of strike pattern on the joints distal to the ankle. The purpose of this study was to explore the effects of forefoot strike (FFS) and rearfoot strike (RFS) running patterns on foot kinematics and kinetics, from the perspectives of the midtarsal locking theory and the windlass mechanism. Per the midtarsal locking theory, we hypothesized that the ankle would be more inverted in early stance when using a FFS, resulting in decreased midtarsal joint excursions and increased dynamic stiffness. Associated with a more engaged windlass mechanism, we hypothesized that a FFS would elicit increased metatarsophalangeal joint excursions and negative work in late stance. Eighteen healthy female runners ran overground with both FFS and RFS patterns. Instrumented motion capture and a validated multi-segment foot model were used to analyze midtarsal and metatarsophalangeal joint kinematics and kinetics. During early stance in FFS the ankle was more inverted, with concurrently decreased midtarsal eversion (p strike pattern during running. However, the windlass mechanism appeared to be engaged to a greater extent during FFS. Copyright © 2018 Elsevier Ltd. All rights reserved.

  3. Possible mechanisms underlying slow component of V̇O2 on-kinetics in skeletal muscle.

    Science.gov (United States)

    Korzeniewski, Bernard; Zoladz, Jerzy A

    2015-05-15

    A computer model of a skeletal muscle bioenergetic system is used to study the background of the slow component of oxygen consumption V̇O2 on-kinetics in skeletal muscle. Two possible mechanisms are analyzed: inhibition of ATP production by anaerobic glycolysis by progressive cytosol acidification (together with a slow decrease in ATP supply by creatine kinase) and gradual increase of ATP usage during exercise of constant power output. It is demonstrated that the former novel mechanism is potent to generate the slow component. The latter mechanism further increases the size of the slow component; it also moderately decreases metabolite stability and has a small impact on muscle pH. An increase in anaerobic glycolysis intensity increases the slow component, elevates cytosol acidification during exercise, and decreases phosphocreatine and Pi stability, although slightly increases ADP stability. A decrease in the P/O ratio (ATP molecules/O2 molecules) during exercise cannot also be excluded as a relevant mechanism, although this issue requires further study. It is postulated that both the progressive inhibition of anaerobic glycolysis by accumulating protons (together with a slow decrease of the net creatine kinase reaction rate) and gradual increase of ATP usage during exercise, and perhaps a decrease in P/O, contribute to the generation of the slow component of the V̇O2 on-kinetics in skeletal muscle. Copyright © 2015 the American Physiological Society.

  4. Details about Mechanism of Identification of Viruses by Microsoft Security Essentials (Microsoft Forefront Endpoint Protection

    Directory of Open Access Journals (Sweden)

    D. S. Silnov

    2012-12-01

    Full Text Available A special mechanism of signature method while detecting virus signatures in binary files is detected and researched. It has been found that antivirus Microsoft Secutiry Essentials does not detect viruses in digitally signed binary files.

  5. The kinetics and mechanism of bainite transformation in high strength steels

    International Nuclear Information System (INIS)

    Ali, A.; Bhadeshia, H.K.D.H.

    1993-01-01

    The kinetics and mechanism of bainite formation have been studied in high strength Fe-C-Si-Mn and Fe-C-Si-Ni steels using dilatometry, optical and transmission electron microscopy. In these silicon containing steels, carbide precipitation dies not accompany the growth of bainitic ferrite so that the mechanism of transformation can be readily interpreted. The work confirms that the volume fraction of bainite when the reaction stops, is far less that expected from equilibrium or para equilibrium considerations. In addition the bainite exhibits an invariant plane strain surface relief effect with a large shear component, and adopts a sheaf morphology. The results are demonstrated to be consistent with a displacive diffusion less transformation mechanism of bainite, in which the excess carbon is, subsequent to transformation, rejected into the residual austenite. (author)

  6. Kinetic and mechanism formation reaction of complex compound Cu with di-n-buthildithiocarbamate (dbdtc) ligand

    Science.gov (United States)

    Haryani, S.; Kurniawan, C.; Kasmui

    2018-04-01

    Synthesis of complex compound is one field of research which intensively studied. Metal-dithiocarbamate complexes find wide-ranging applications in nanomaterial and metal separation science, and have potential use as chemotherapeutic, pesticides, and as additives to lubricants. However, the information about is reaction kinetic and mechanism are very much lacking. The research and analyzes results show that reaction synthesis ligand DBDTC and complex compounds Cu-DBDTC. Optimum reaction condition of formation of complex compounds Cu with DBDTC at pH=3, [DBDTC] = 4.10-3 M, and the time of reaction 5 minutes. Based the analysis varian reaction of complex compounds at pH 3 and 4, diffrence significance at the other pH: 5; 5,5; 6; 6,5 ; 7; and 8. The various of mole with reactants comosition difference sigbificance, those the time reaction for 5 and 6 minutes diffrence by significance with the other time, it is 3,4,8, and 10 minutes. The great product to at condition pH 6, the time optimum at 5 minutes and molar ratio of logam: ligand = 1:2. The reaction kinetic equation of complex compound Cu with chelathing ligand DBDTC is V=0.917106 [Cu2+]0.87921 [DBDTC]2.03021. Based on the kinetic data, and formed complex compounds estimation, the mechanism explaining by 2 stages. In the first stage formation of [Cu(DBDTC)], and then [Cu(DBDTC)2] with the last structure geomethry planar rectangle. The result of this research will be more useful if an effort is being done in reaction mechanism by chemical computation method for obtain intermediate, and for constant “k” in same stage, k1.k2. and compound complex constanta (β).

  7. Thymidine kinase 2 enzyme kinetics elucidate the mechanism of thymidine-induced mitochondrial DNA depletion.

    Science.gov (United States)

    Sun, Ren; Wang, Liya

    2014-10-07

    Mitochondrial thymidine kinase 2 (TK2) is a nuclear gene-encoded protein, synthesized in the cytosol and subsequently translocated into the mitochondrial matrix, where it catalyzes the phosphorylation of thymidine (dT) and deoxycytidine (dC). The kinetics of dT phosphorylation exhibits negative cooperativity, but dC phosphorylation follows hyperbolic Michaelis-Menten kinetics. The two substrates compete with each other in that dT is a competitive inhibitor of dC phosphorylation, while dC acts as a noncompetitive inhibitor of dT phosphorylation. In addition, TK2 is feedback inhibited by dTTP and dCTP. TK2 also phosphorylates a number of pyrimidine nucleoside analogues used in antiviral and anticancer therapy and thus plays an important role in mitochondrial toxicities caused by nucleoside analogues. Deficiency in TK2 activity due to genetic alterations causes devastating mitochondrial diseases, which are characterized by mitochondrial DNA (mtDNA) depletion or multiple deletions in the affected tissues. Severe TK2 deficiency is associated with early-onset fatal mitochondrial DNA depletion syndrome, while less severe deficiencies result in late-onset phenotypes. In this review, studies of the enzyme kinetic behavior of TK2 enzyme variants are used to explain the mechanism of mtDNA depletion caused by TK2 mutations, thymidine overload due to thymidine phosphorylase deficiency, and mitochondrial toxicity caused by antiviral thymidine analogues.

  8. Kinetics and mechanism of thermal degradation of pentose- and hexose-based carbohydrate polymers.

    Science.gov (United States)

    Akbar, Jamshed; Iqbal, Mohammad S; Massey, Shazma; Masih, Rashid

    2012-10-15

    This work aims at study of thermal degradation kinetics and mechanism of pentose- and hexose-based carbohydrate polymers isolated from Plantago ovata (PO), Salvia aegyptiaca (SA) and Ocimum basilicum (OB). The analysis was performed by isoconversional method. The materials exhibited mainly two-stage degradation. The weight loss at ambient-115°C characterized by low activation energy corresponds to loss of moisture. The kinetic triplets consisting of E, A and g(α) model of the materials were determined. The major degradation stage represents a loss of high boiling volatile components. This stage is exothermic in nature. Above 340°C complete degradation takes place leaving a residue of 10-15%. The master plots of g(α) function clearly differentiated the degradation mechanism of hexose-based OB and SA polymers and pentose-based PO polymer. The pentose-based carbohydrate polymer showed D(4) type and the hexose-based polymers showed A(4) type degradation mechanism. Copyright © 2012 Elsevier Ltd. All rights reserved.

  9. Kinetic theory approach to modeling of cellular repair mechanisms under genome stress.

    Directory of Open Access Journals (Sweden)

    Jinpeng Qi

    Full Text Available Under acute perturbations from outer environment, a normal cell can trigger cellular self-defense mechanism in response to genome stress. To investigate the kinetics of cellular self-repair process at single cell level further, a model of DNA damage generating and repair is proposed under acute Ion Radiation (IR by using mathematical framework of kinetic theory of active particles (KTAP. Firstly, we focus on illustrating the profile of Cellular Repair System (CRS instituted by two sub-populations, each of which is made up of the active particles with different discrete states. Then, we implement the mathematical framework of cellular self-repair mechanism, and illustrate the dynamic processes of Double Strand Breaks (DSBs and Repair Protein (RP generating, DSB-protein complexes (DSBCs synthesizing, and toxins accumulating. Finally, we roughly analyze the capability of cellular self-repair mechanism, cellular activity of transferring DNA damage, and genome stability, especially the different fates of a certain cell before and after the time thresholds of IR perturbations that a cell can tolerate maximally under different IR perturbation circumstances.

  10. Kinetic theory approach to modeling of cellular repair mechanisms under genome stress.

    Science.gov (United States)

    Qi, Jinpeng; Ding, Yongsheng; Zhu, Ying; Wu, Yizhi

    2011-01-01

    Under acute perturbations from outer environment, a normal cell can trigger cellular self-defense mechanism in response to genome stress. To investigate the kinetics of cellular self-repair process at single cell level further, a model of DNA damage generating and repair is proposed under acute Ion Radiation (IR) by using mathematical framework of kinetic theory of active particles (KTAP). Firstly, we focus on illustrating the profile of Cellular Repair System (CRS) instituted by two sub-populations, each of which is made up of the active particles with different discrete states. Then, we implement the mathematical framework of cellular self-repair mechanism, and illustrate the dynamic processes of Double Strand Breaks (DSBs) and Repair Protein (RP) generating, DSB-protein complexes (DSBCs) synthesizing, and toxins accumulating. Finally, we roughly analyze the capability of cellular self-repair mechanism, cellular activity of transferring DNA damage, and genome stability, especially the different fates of a certain cell before and after the time thresholds of IR perturbations that a cell can tolerate maximally under different IR perturbation circumstances.

  11. Mechanism and Kinetics of the Formation and Transport of Aerosol Particles in the Lower Stratosphere

    Science.gov (United States)

    Aloyan, A. E.; Ermakov, A. N.; Arutyunyan, V. O.

    2018-03-01

    Field and laboratory observation data on aerosol particles in the lower stratosphere are considered. The microphysics of their formation, mechanisms of heterogeneous chemical reactions involving reservoir gases (e.g., HCl, ClONO2, etc.) and their kinetic characteristics are analyzed. A new model of global transport of gaseous and aerosol admixtures in the lower stratosphere is described. The preliminary results from a numerical simulation of the formation of sulfate particles of the Junge layer and particles of polar stratospheric clouds (PSCs, types Ia, Ib, and II) are presented, and their effect on the gas and aerosol composition is analyzed.

  12. Mechanisms and Kinetics of Organic Aging in High-Level Nuclear Wastes

    International Nuclear Information System (INIS)

    Camaioni, Donald M.; Autrey, S. Thomas; Linehan, John L.

    1999-01-01

    The goal of this project is to develop a fundamental understanding of organic aging and to assemble a model that describes and predicts the thermal and radiolytic aging of organic compounds in high-level wastes (HLW). To reach this goal, we will measure kinetics and elucidate products and mechanisms of organic reactions occurring under conditions of waste storage, retrieval, and processing. Initial emphasis will be placed on studying thermal effects, because organic reaction mechanisms and effects of varying conditions are uncertain, and because we benefit from collaborations with earlier Environmental Management Science Program (EMSP) projects that have worked on radiation effects. Organic complexants are of greatest concern regarding both safety and pretreatment because they have been found to degrade to gases, combust in dry wastes, and interfere with radionuclide separations. Therefore, efforts will focus on studying the reactions of these organic chemicals and associated degradation products. In preliminary work, the authors have used mechanistic kinetic modeling techniques to successfully model the radiolytic degradation of formate to carbonate in HLW simulants. The research will continue development of the model using an iterative process that measures degradation products and kinetics of increasingly complex molecules while adapting the model to reproduce the results each step of the way. Several mechanistic probe experiments have been designed to learn the fundamental mechanisms that operate during thermal degradations so that thermal and radiolytic processes may be integrated within the model. Key kinetic data and thermodynamic properties relating to thermal reactivity will also be acquired so that rate-controlling and product-forming reactions can be predicted. Thermochemical properties of key intermediates will be experimentally and/or theoretically determined to facilitate mechanism verification, structure/reactivity correlation, and prediction of

  13. Kinetics and Mechanism of the Pyridinolysis of Diisopropyl Chlorothiophosphate in Acetonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Hoque, Md. Ehtesham Ul; Lee, Hai Whang [Inha Univ., Incheon (Korea, Republic of)

    2012-10-15

    The nucleophilic substitution reactions of diisopropyl chlorothiophosphate with X-pyridines have been kinetically studied in MeCN at 35.0 .deg. C. The Hammett and Bronsted plots for the substituent X variations in the nucleophiles show biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 5 exhibits great negative deviation from the Taft plot. A concerted S{sub N}2 mechanism is proposed involving a change of the attacking direction of the X-pyridines from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines.

  14. Kinetics and mechanism of oxidation of acetanilide by quinquevalent vanadium in acid medium

    International Nuclear Information System (INIS)

    Gupta, R.

    1990-01-01

    The kinetics of the oxidation of acetanilide with vanadium(V) in sulphuric acid medium at constant ionic strength has been studied. The reaction is first order with oxidant. The order of reaction in acetanilide varies from one to zero. The reaction follows an acid catalyzed independent path, exhibiting square dependence in H + . A Bunnett plot indicates that the water acts as a nucleophile. The thermodynamic parameters have been computed. A probable reaction mechanism and rate law consistent with these data are given. (Author)

  15. Kinetics and mechanism of the selective oxidation of primary aliphatic alcohols under phase transfer catalysis

    Directory of Open Access Journals (Sweden)

    K. Bijudas

    2014-03-01

    Full Text Available Kinetics of the oxidation of primary aliphatic alcohols has been carried out using phase transferred monochromate in benzene. Tetrabutylammonium bromide (TBAB and tetrabutylphosphonium bromide (TBPB are used as phase transfer catalysts (PT catalyst. The reaction shows first order dependence on both [alcohol] and [monochromate ion]. The oxidation leads to the formation of corresponding aldehyde and no traces of carboxylic acid has been detected. The reaction mixture failed to induce the polymerization of added acrylonitrile which rules out the presence radical intermediates in the reaction. Various thermodynamic parameters have been evaluated and a suitable mechanism has been proposed.

  16. Effect of environmental factors on the kinetics of insulin fibril formation: elucidation of the molecular mechanism.

    Science.gov (United States)

    Nielsen, L; Khurana, R; Coats, A; Frokjaer, S; Brange, J; Vyas, S; Uversky, V N; Fink, A L

    2001-05-22

    In the search for the molecular mechanism of insulin fibrillation, the kinetics of insulin fibril formation were studied under different conditions using the fluorescent dye thioflavin T (ThT). The effect of insulin concentration, agitation, pH, ionic strength, anions, seeding, and addition of 1-anilinonaphthalene-8-sulfonic acid (ANS), urea, TMAO, sucrose, and ThT on the kinetics of fibrillation was investigated. The kinetics of the fibrillation process could be described by the lag time for formation of stable nuclei (nucleation) and the apparent rate constant for the growth of fibrils (elongation). The addition of seeds eliminated the lag phase. An increase in insulin concentration resulted in shorter lag times and faster growth of fibrils. Shorter lag times and faster growth of fibrils were seen at acidic pH versus neutral pH, whereas an increase in ionic strength resulted in shorter lag times and slower growth of fibrils. There was no clear correlation between the rate of fibril elongation and ionic strength. Agitation during fibril formation attenuated the effects of insulin concentration and ionic strength on both lag times and fibril growth. The addition of ANS increased the lag time and decreased the apparent growth rate for insulin fibril formation. The ANS-induced inhibition appears to reflect the formation of amorphous aggregates. The denaturant, urea, decreased the lag time, whereas the stabilizers, trimethylamine N-oxide dihydrate (TMAO) and sucrose, increased the lag times. The results indicated that both nucleation and fibril growth were controlled by hydrophobic and electrostatic interactions. A kinetic model, involving the association of monomeric partially folded intermediates, whose concentration is stimulated by the air-water interface, leading to formation of the critical nucleus and thence fibrils, is proposed.

  17. Kinetics and formation mechanism of amorphous Fe52Nb48 alloy powder fabricated by mechanical alloying

    International Nuclear Information System (INIS)

    El-Eskandarany, S.

    1999-01-01

    A single phase amorphous Fe 52 Nb 48 alloy has been synthesized through a solid state interdiffusion of pure polycrystalline Fe and Nb powders at room temperature, using a high-energy ball-milling technique. The mechanisms of metallic glass formation and competing crystallization processes in the mechanically deformed composite powders have been investigated by means of X-ray diffraction, Moessbauer spectroscopy, differential thermal analysis, scanning electron microscopy and transmission electron microscopy. The numerous intimate layered composite particles of the diffusion couples that formed during the first and intermediate stages of milling time (0-56 ks), are intermixed to form amorphous phase(s) upon heating to about 625 K by so-called thermally assisted solid state amorphization, TASSA. The amorphization heat of formation for binary system via the TASSA, ΔH a , was measured directly as a function of the milling time. Comparable with the TASSA, homogeneous amorphous alloys were fabricated directly without heating the composite multilayered particles upon milling these particles for longer milling time (86 ks-144 ks). The amorphization reaction here is attributed to the mechanical driven solid state amorphization. This single amorphous phase transforms into an order phase (μ phase) upon heating at 1088 K (crystallization temperature, T x ) with enthalpy change of crystallization, ΔH x , of -8.3 kJmol -1 . (orig.)

  18. Kinetics and mechanism of reduction of diazonium salts with hypophosphorous acid

    International Nuclear Information System (INIS)

    Levit, A.F.; Kiprianova, L.A.; Gragerov, I.P.

    1975-01-01

    A kinetic study has been made of reduction of a series of diazonium salts n-XC 6 H 4 N 2 + BF 4 - (X=OCH 3 , CH 3 , H, Cl, Br, NO 2 ) by subphosphorus acid using the NMR technique. The intensity of NMR signals has been used to measure the rate of formation of the reaction products-benzene or substituted benzenes. The reaction with phenyldiazonium has been studied in the most detailed way. Under conditions when propagation stages are suppressed (in the presence of benzoquinone) chemical polarization of nuclei is observed in benzene which is formed at the initiation stage. The polarization indicates the formation of C 6 H 5 radicals in this stage. It is interesting as the first observation of the chemical polarization of nuclei in the initiation stage of chain reactions

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

    Science.gov (United States)

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

    2010-12-14

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

  20. Mechanisms and kinetics of electrodeposition of alkali metals on solid and liquid mercury electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Wenzhe.

    1993-01-01

    Electroreduction of alkali metal ions at mercury is an important area in electrochemistry related to the battery industry. In this work, four major topics were considered: alkali metal/mercury interactions; electrosorption of alkali metal ions on solid mercury; electroreduction of alkali metal/crown ether complexes; and ammonium amalgam formation. The formation of alkali metal-mercury intermetallic compounds was studied on liquid and frozen thin layer mercury electrodes. The stoichiometry of the compounds produced under these conditions was determined using cyclic voltammetry. As expected, formation of a new phase was preceded by nucleation phenomena, which were particularly easy to monitor at solid Hg electrodes. The nucleation kinetics were studied using the chronoamperometric method. At very low temperatures, when the mobility of mercury atoms was restricted, the electrosorption of alkali metal ions on solid mercury electrodes was noted. Subsequent study allowed determination of the electrosorption parameters. The free energy of electrosorption is discussed in terms of interactions between alkali metals and mercury. The effect of crown ethers on the kinetics of alkali metal ion reduction was studied at both standard size and ultramicro-mercury electrodes in nonaqueous solutions using ultrafast cyclic voltammetry and ac voltammetry. The usefulness of ultrafast cyclic voltammetry with ultramicroelectrodes in measurements of the kinetics of amalgam formation was verified in a brief study of cadmium ion reduction. The mechanism of the complex reduction at mercury was analyzed based on the free energy changes before and after the activation state. In addition, the stoichiometry and formation constants of the crown ether/alkali metal complexes were determined using cyclic voltammetry. The mechanism of electroreduction of ammonium ions at mercury electrodes in non-aqueous media was analyzed.

  1. Cure kinetics and mechanical interfacial characteristics of zeolite/DGEBA composites

    International Nuclear Information System (INIS)

    Park, Soo Jin; Kim, Young Mi; Shin, Jae Sup

    2003-01-01

    In this work, the zeolite/diglycidylether of bisphenol A(DGEBA) systems were investigated in terms of the cure kinetics and mechanical interfacial properties of the composites. The 4, 4-Diamino Diphenyl Methane(DDM) was used as a curing agent for epoxy. Two types of zeolite(PZ) were prepared with 15 and 35 wt% KOH treatments(15-BZ and 35-BZ, respectively) for 24 h, and their surface characteristics were studied by X-ray Photoelectron Spectroscopy (XPS) and X-Ray Diffraction (XRD). Cure kinetics of the composites were examined in the context of Differential Scanning Calorimetry(DSC), and mechanical interfacial properties were investigated in critical stress intensity factor(K IC ) and critical strain energy release rate(G IC ). In the results of XPS and XRD, sodium ion(Na) of zeolite was exchanged for potassium ion(K), resulting from the treatment of KOH. Also, Si 2p /A1 2p composition ratios of the treated zeolite were increased, which could be attributed to the weakening of A1-O bond in framework. Cure activation energy(E a ) of 15-BZ composites was decreased, whereas K IC and G IC were increased, compared with those of the pure zeolite/DGEBA composites. It was probably accounted that the acidity of zeolite was increased by surface treatments and the cure reaction between zeolite and epoxy was influenced on the increased acidity of zeolite

  2. Physical organogels: mechanism and kinetics of evaporation of the solvents entrapped within network scaffolding

    International Nuclear Information System (INIS)

    Markovic, Nov; Dutta, Naba K.

    2005-01-01

    A series of hydrocarbon gels (based on leaded petrol and decalin) using physically crosslinked networks have been prepared using Al-salt of fatty acid as the physical gelling agent. The effects of gel network scaffolding on the mechanism and kinetics of evaporation of the solvents from the gels were investigated using conventional, isothermal and modulated thermogravimetric analysis. It has been clearly observed that the evaporation of solvent from gels followed a complex evaporation pattern compared to the pure solvent. It appears that with increase in network scaffolding the maximum rate of evaporation of the solvent decreases and its distribution become broader. The activation energy of evaporation for these solvents was found not to be dramatically dependent on the concentration of the gelator and tightness of the network scaffolding. Amongst different methods employed, isothermal measurements provided reliable information about the mechanism of evaporation. Modulated thermogravimetric analysis proved to be an efficient method to achieve kinetic parameters of evaporation from a single dynamic experiment. Scanning electron microscopy was used to probe for both dry gelator and gel network after evaporation of the solvents for evaluation of their surface morphology

  3. Kinetics and Mechanism of Oxidation of Diethyl Ether by Chloramine-T in Acidic Medium

    Directory of Open Access Journals (Sweden)

    Y. I. Hassan

    2012-01-01

    Full Text Available The kinetics of oxidation of diethyl ether (DE with sodium N-chloro-p-toluenesulphonamide (CAT in hydrochloric acid solution has been studied at (313°K.The reaction rate show a first order dependence on [CAT] and fractional order dependence on each [DE] and [H+] .The variation of ionic strength of the medium has no significant effect on the reaction rate , addition of p-toluenesulphonamide (p-TSA affects the reaction rate marginally the rate increased with decreasing dielectric constant of the medium , the stochiometry of the reaction was found to be 1:2 and oxidation products were identified , A Michaelis – Menten type mechanism has been suggested to explain the results.The equilibrium and the decomposition constants of CAT – diethyl ether complex have been evaluated. Thermodynamic parameters were computed by studying reaction at temperatures range ( 308 – 323°K for the rate limiting step and for the observed first order constants by the linear Arrhenius plot. The mechanism proposed and the derived rate law are consistent with observed kinetics.

  4. Kinetics and Mechanism of Radiation-Induced Synthesis of Substituted Chloroolefins

    Energy Technology Data Exchange (ETDEWEB)

    Horowitz, A.; Rajbenbach, L. A. [Soreq Nuclear Research Centre, Yavne (Israel)

    1969-12-15

    The mechanism and kinetic aspects of eight irradiation-initiated syntheses of alkyl substituted chloroethylenes were studied at 210 Degree-Sign C. G-values of condensation products of the order of ten thousands were found upon irradiation of solutions of trans C{sub 2}Cl{sub 2}H{sub 2}, C{sub 2}Cl{sub 3}H and C{sub 2}Cl{sub 4} in cyclohexane. These condensation products represent compounds in which one chlorine atom in the chloroethylene solutes has been replaced by a cyclohexyl radical. The condensation reaction was found to proceed via a free-radical chain mechanism, the radiolytical formation of cyclohexyl radicals representing the chain initiation step. In the chain propagation step the cyclohexyl radicals add to the olefins followed by chlorine atom elimination from the newly formed radicals, subsequent reaction of chlorine atoms with cyclohexane resulting in the regeneration of the cyclohexyl radicals. Kinetic expressions relating the yield-of condensation products with chloroolefins concentration were derived; The effect of experimental parameters such as temperature, solute concentration, dose rate and total dose in the condensation products yields are discussed. (author)

  5. Kinetics and mechanism for degradation of dichlorvos by permanganate in drinking water treatment.

    Science.gov (United States)

    Liu, Chao; Qiang, Zhimin; Adams, Craig; Tian, Fang; Zhang, Tao

    2009-08-01

    The degradation kinetics and mechanism of dichlorvos by permanganate during drinking water treatment were investigated. The reaction of dichlorvos with permanganate was of second-order overall with negligible pH dependence and an activation energy of 29.5 kJ x mol(-1). At pH 7.0 and 25 degrees C, the rate constant was 25.2+/-0.4M(-1)s(-1). Dichlorvos was first degraded to trimethyl phosphate (TMP) and dimethyl phosphate (DMP) simultaneously which approximately accounted for or=95% with respect to phosphorus mass, respectively. Further oxidation of DMP generated a final byproduct, monomethyl phosphate (MMP). MMP was for the first time identified as a major byproduct in chemical oxidation of dichlorvos. The kinetic model based on degradation mechanism and determined reaction rate constants allowed us to predict the evolution of dichlorvos and its byproduct concentrations during permanganate pre-oxidation process at water treatment plants. These results suggest that even though the dichlorvos concentration in surface water complies with the surface water quality standards of China (50 microg L(-1)), its concentration after conventional water treatment will most probably exceed the drinking water quality standards (1 microg L(-1)). Moreover, luminescent bacteria test shows that the acute toxicity of dichlorvos solution evidently increased after permanganate oxidation.

  6. Curing kinetics, mechanism and chemorheological behavior of methanol etherified amino/novolac epoxy systems

    Directory of Open Access Journals (Sweden)

    S. F. Zhao

    2014-02-01

    Full Text Available The curing kinetics and mechanism of epoxy novolac resin (DEN and modified epoxy novolac resin (MDEN with methanol etherified amino resin were studied by means of differential scanning calorimetry (DSC, Fourier transforminfrared (FT-IR spectroscopy and chemorheological analysis. Their kinetics parameters and models of the curing were examined utilizing isoconversional methods, Flynn-Wall-Ozawa and Friedman methods. For the DEN mixture, its average activation energy (Ea was 71.05 kJ/mol and the autocatalytic model was established to describe the curing reaction. The MDEN mixture exhibited three dominant curing processes, termed as reaction 1, reaction 2 and reaction 3; and their Ea were 70.05, 106.55 and 101.91 kJ/mol, respectively. Besides, Ea of reaction 1 was similar to that of DEN mixture, while Ea of reactions 2 and 3 corresponded to that of the etherification reaction between hydroxyl and epoxide group. Moreover, these three dominant reactions were nth order in nature. Furthermore, their curing mechanisms were proposed from the results of DSC and FTIR. The chemorheological behavior was also investigated to obtain better plastics products via optimizing the processing schedules.

  7. ELECTROCHEMICAL STUDIES OF URANIUM METAL CORROSION MECHANISM AND KINETICS IN WATER

    International Nuclear Information System (INIS)

    Boudanova, Natalya; Maslennikov, Alexander; Peretroukhine, Vladimir F.; Delegard, Calvin H.

    2006-01-01

    During long-term underwater storage of low burn-up uranium metal fuel, a corrosion product sludge forms containing uranium metal grains, uranium dioxide, uranates and, in some cases, uranium peroxide. Literature data on the corrosion of non-irradiated uranium metal and its alloys do not allow unequivocal prediction of the paragenesis of irradiated uranium in water. The goal of the present work conducted under the program 'CORROSION OF IRRADIATED URANIUM ALLOYS FUEL IN WATER' is to study the corrosion of uranium and uranium alloys and the paragenesis of the corrosion products during long-term underwater storage of uranium alloy fuel irradiated at the Hanford Site. The elucidation of the physico-chemical nature of the corrosion of irradiated uranium alloys in comparison with non-irradiated uranium metal and its alloys is one of the most important aspects of this work. Electrochemical methods are being used to study uranium metal corrosion mechanism and kinetics. The present part of work aims to examine and revise, where appropriate, the understanding of uranium metal corrosion mechanism and kinetics in water

  8. Kinetics exoelectron emission phenomena confirmed mechanism of vacancy diffusion through dislocation

    International Nuclear Information System (INIS)

    Dus-Sitek, M.; Szymura, S.; Pisarek, J.

    1998-01-01

    On the basis on the data obtained during experiments regarding the kinetics of exoelectron emission phenomenon in deformed metal, a hypothesis concerning the dislocation mechanism of vacancies transport was confirmed. The nature and character of the exoelectron emission phenomenon accompanying a plastic deformation of thermally or mechanically prepared metals showed distinct relations between the exoelectron emission phenomenon and the defects of a crystalline structure produced during processing. On the basic of the result obtained for the Ni and stainless steels has been concluded that exoelectron emission intensity accompanying an uniaxial deformation appears at the yield strain ε 0 on the stress-strain curve, and that the sharp 'destruction' emission peak is associated with the sample failure strain ε f

  9. Elucidation of reaction mechanism for m -cresol hydrodeoxygenation over Fe based catalysts: A kinetic study

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Yongchun; Wang, Yong

    2017-09-01

    Fe based catalysts are promising for hydrodeoxygenation (HDO) of lignin derived phenolics due to their high selectivity for aromatics. In this work, the reaction mechanism of m-cresol HDO on Fe catalysts and the kinetic consequence with Pd addition were elucidated by examining the effect of H2, H2O and m-cresol pressures on toluene formation rate on Fe and PdFe catalysts. A direct CO bond cleavage mechanism is proposed for HDO catalysis on both Fe and PdFe catalysts, while Pd provides a facilitated reaction pathway at the PdFe interface and therefore promotes the catalysis on Fe without changing the high selectivity towards aromatics.

  10. Reduced chemical kinetic mechanisms for NOx emission prediction in biomass combustion

    DEFF Research Database (Denmark)

    Houshfar, Ehsan; Skreiberg, Øyvind; Glarborg, Peter

    2012-01-01

    Because of the complex composition of biomass, the chemical mechanism contains many different species and therefore a large number of reactions. Although biomass gas‐phase combustion is fairly well researched and understood, the proposed mechanisms are still complex and need very long computational...... time and powerful hardware resources. A reduction of the mechanism for biomass volatile oxidation has therefore been performed to avoid these difficulties. The selected detailed mechanism in this study contains 81 species and 703 elementary reactions. Necessity analysis is used to determine which...... reactions and chemical species, that is, 35 species and 198 reactions, corresponding to 72% reduction in the number of reactions and, therefore, improving the computational time considerably. Yet, the model based on the reduced mechanism predicts correctly concentrations of NOx and CO that are essentially...

  11. Kinetics and mechanism of jack bean urease inhibition by Hg2+

    Directory of Open Access Journals (Sweden)

    Du Nana

    2012-12-01

    Full Text Available Abstract Background Jack bean urease (EC 3.5.1.5 is a metalloenzyme, which catalyzes the hydrolysis of urea to produce ammonia and carbon dioxide. The heavy metal ions are common inhibitors to control the rate of the enzymatic urea hydrolysis, which take the Hg2+ as the representative. Hg2+ affects the enzyme activity causing loss of the biological function of the enzyme, which threatens the survival of many microorganism and plants. However, inhibitory kinetics of urease by the low concentration Hg2+ has not been explored fully. In this study, the inhibitory effect of the low concentration Hg2+ on jack bean urease was investigated in order to elucidate the mechanism of Hg2+ inhibition. Results According to the kinetic parameters for the enzyme obtained from Lineweaver–Burk plot, it is shown that the Km is equal to 4.6±0.3 mM and Vm is equal to 29.8±1.7 μmol NH3/min mg. The results show that the inhibition of jack bean urease by Hg2+ at low concentration is a reversible reaction. Equilibrium constants have been determined for Hg2+ binding with the enzyme or the enzyme-substrate complexes (Ki =0.012 μM. The results show that the Hg2+ is a noncompetitive inhibitor. In addition, the kinetics of enzyme inhibition by the low concentration Hg2+ has been studied using the kinetic method of the substrate reaction. The results suggest that the enzyme first reversibly and quickly binds Hg2+ and then undergoes a slow reversible course to inactivation. Furthermore, the rate constant of the forward reactions (k+0 is much larger than the rate constant of the reverse reactions (k-0. By combining with the fact that the enzyme activity is almost completely lost at high concentration, the enzyme is completely inactivated when the Hg2+ concentration is high enough. Conclusions These results suggest that Hg2+ has great impacts on the urease activity and the established inhibition kinetics model is suitable.

  12. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Jorge, Nelly Lidia [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain); Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Romero, Jorge Marcelo [Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Grand, Andre [INAC, SCIB, Laboratoire ' Lesions des Acides Nucleiques' , UMR CEA-UJF E3, CEA-Grenoble, 17 Rue des Martyrs, 38054 Grenoble cedex 9 (France); Hernandez-Laguna, Alfonso, E-mail: ahlaguna@ugr.es [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain)

    2012-01-17

    Highlights: Black-Right-Pointing-Pointer Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. Black-Right-Pointing-Pointer Gas chromatography and computational potential energy surfaces were performed. Black-Right-Pointing-Pointer A mechanism in steps looked like the most probable mechanism. Black-Right-Pointing-Pointer A spin-orbit coupling appeared at the singlet and triple diradical open structures. Black-Right-Pointing-Pointer A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463-503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 {+-} 0.8 kcal/mol and 5.2 Multiplication-Sign 10{sup 13} s{sup -1}, respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G{sup Asterisk-Operator Asterisk-Operator} level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin-orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

  13. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    International Nuclear Information System (INIS)

    Jorge, Nelly Lidia; Romero, Jorge Marcelo; Grand, André; Hernández-Laguna, Alfonso

    2012-01-01

    Highlights: ► Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. ► Gas chromatography and computational potential energy surfaces were performed. ► A mechanism in steps looked like the most probable mechanism. ► A spin–orbit coupling appeared at the singlet and triple diradical open structures. ► A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463–503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 ± 0.8 kcal/mol and 5.2 × 10 13 s −1 , respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G ∗∗ level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin–orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

  14. The Spliced Leader Trans-Splicing Mechanism in Different Organisms: Molecular Details and Possible Biological Roles

    Directory of Open Access Journals (Sweden)

    Mainá eBitar

    2013-10-01

    Full Text Available The spliced leader (SL is a gene that generates a functional ncRNA that is composed of two regions: an intronic region of unknown function (SLi and an exonic region (SLe, which is transferred to the 5’ end of independent transcripts yielding mature mRNAs, in a process known as spliced leader trans-splicing (SLTS. The best described function for SLTS is to solve polycistronic transcripts into monocistronic units, specifically in Trypanosomatids. In other metazoans, it is speculated that the SLe addition could lead to increased mRNA stability, differential recruitment of the translational machinery, modification of the 5' region or a combination of these effects. Although important aspects of this mechanism have been revealed, several features remain to be elucidated. We have analyzed 157 SLe sequences from 148 species from 7 phyla and found a high degree of conservation among the sequences of species from the same phylum, although no considerable similarity seems to exist between sequences of species from different phyla. When analyzing case studies, we found evidence that a given SLe will always be related to a given set of transcripts in different species from the same phylum, and therefore, different SLe sequences from the same species would regulate different sets of transcripts. In addition, we have observed distinct transcript categories to be preferential targets for the SLe addition in different phyla. This work sheds light into crucial and controversial aspects of the SLTS mechanism. It represents a comprehensive study concerning various species and different characteristics of this important post-transcriptional regulatory mechanism.

  15. The combustion chemistry of a fuel tracer: Measured flame speeds and ignition delays and a detailed chemical kinetic model for the oxidation of acetone

    Energy Technology Data Exchange (ETDEWEB)

    Pichon, S.; Black, G.; Simmie, J.M.; Curran, H.J. [Combustion Chemistry Centre, National University of Ireland, Galway (Ireland); Chaumeix, N.; Yahyaoui, M. [Institut de Combustion Aerothermique Reactivite et Environnement, CNRS, Orleans (France); Donohue, R. [Information Technology, National University of Ireland, Galway (Ireland)

    2009-02-15

    Acetone ignition delay and stretch-free laminar flame speed measurements have been carried out and a kinetic model has been developed to simulate these and literature data for acetone and for ketene, which was found to be an important intermediate in its oxidation. The mechanism has been based on one originally devised for dimethyl ether and modified through validation of the hydrogen, carbon monoxide and methane sub-mechanisms. Acetone oxidation in argon was studied behind reflected shock waves in the temperature range 1340-1930 K, at 1 atm and at equivalence ratios of 0.5, 1 and 2; it is also shown that the addition of up to 15% acetone to a stoichiometric n-heptane mixture has no effect on the measured ignition delay times. Flame speeds at 298 K and 1 atm of pure acetone in air were measured in a spherical bomb; a maximum flame speed of {proportional_to}35 cm s{sup -1} at {phi}=1.15 is indicated. (author)

  16. In vitro kinetic studies on the mechanism of oxygen-dependent cellular uptake of copper radiopharmaceuticals

    Energy Technology Data Exchange (ETDEWEB)

    Holland, Jason P; Bell, Stephen G; Wong, Luet-Lok; Dilworth, Jonathan R [Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA (United Kingdom); Giansiracusa, Jeffrey H [Department of Mathematics, Mathematical Institute, University of Oxford, 24-29 St Giles' , Oxford, OX1 3LB (United Kingdom)], E-mail: hollanj3@mskcc.org, E-mail: jasonpholland@gmail.com

    2009-04-07

    The development of hypoxia-selective radiopharmaceuticals for use as therapeutic and/or imaging agents is of vital importance for both early identification and treatment of cancer and in the design of new drugs. Radiotracers based on copper for use in positron emission tomography have received great attention due to the successful application of copper(II) bis(thiosemicarbazonato) complexes, such as [{sup 60/62/64}Cu(II)ATSM] and [{sup 60/62/64}Cu(II)PTSM], as markers for tumour hypoxia and blood perfusion, respectively. Recent work has led to the proposal of a revised mechanism of hypoxia-selective cellular uptake and retention of [Cu(II)ATSM]. The work presented here describes non-steady-state kinetic simulations in which the reported pO{sub 2}-dependent in vitro cellular uptake and retention of [{sup 64}Cu(II)ATSM] in EMT6 murine carcinoma cells has been modelled by using the revised mechanistic scheme. Non-steady-state (NSS) kinetic analysis reveals that the model is in very good agreement with the reported experimental data with a root-mean-squared error of less than 6% between the simulated and experimental cellular uptake profiles. Estimated rate constants are derived for the cellular uptake and washout (k{sub 1} = 9.8 {+-} 0.59 x 10{sup -4} s{sup -1} and k{sub 2} = 2.9 {+-} 0.17 x 10{sup -3} s{sup -1}), intracellular reduction (k{sub 3} = 5.2 {+-} 0.31 x 10{sup -2} s{sup -1}), reoxidation (k{sub 4} = 2.2 {+-} 0.13 mol{sup -1} dm{sup 3} s{sup -1}) and proton-mediated ligand dissociation (k{sub 5} = 9.0 {+-} 0.54 x 10{sup -5} s{sup -1}). Previous mechanisms focused on the reduction and reoxidation steps. However, the data suggest that the origins of hypoxia-selective retention may reside with the stability of the copper(I) anion with respect to protonation and ligand dissociation. In vitro kinetic studies using the nicotimamide adenine dinucleotide (NADH)-dependent ferredoxin reductase enzyme PuR isolated from the bacterium Rhodopseudomonas palustris have

  17. Ground-state kinetics of bistable redox-active donor-acceptor mechanically interlocked molecules.

    Science.gov (United States)

    Fahrenbach, Albert C; Bruns, Carson J; Li, Hao; Trabolsi, Ali; Coskun, Ali; Stoddart, J Fraser

    2014-02-18

    The ability to design and confer control over the kinetics of theprocesses involved in the mechanisms of artificial molecular machines is at the heart of the challenge to create ones that can carry out useful work on their environment, just as Nature is wont to do. As one of the more promising forerunners of prototypical artificial molecular machines, chemists have developed bistable redox-active donor-acceptor mechanically interlocked molecules (MIMs) over the past couple of decades. These bistable MIMs generally come in the form of [2]rotaxanes, molecular compounds that constitute a ring mechanically interlocked around a dumbbell-shaped component, or [2]catenanes, which are composed of two mechanically interlocked rings. As a result of their interlocked nature, bistable MIMs possess the inherent propensity to express controllable intramolecular, large-amplitude, and reversible motions in response to redox stimuli. In this Account, we rationalize the kinetic behavior in the ground state for a large assortment of these types of bistable MIMs, including both rotaxanes and catenanes. These structures have proven useful in a variety of applications ranging from drug delivery to molecular electronic devices. These bistable donor-acceptor MIMs can switch between two different isomeric states. The favored isomer, known as the ground-state co-conformation (GSCC) is in equilibrium with the less favored metastable state co-conformation (MSCC). The forward (kf) and backward (kb) rate constants associated with this ground-state equilibrium are intimately connected to each other through the ground-state distribution constant, KGS. Knowing the rate constants that govern the kinetics and bring about the equilibration between the MSCC and GSCC, allows researchers to understand the operation of these bistable MIMs in a device setting and apply them toward the construction of artificial molecular machines. The three biggest influences on the ground-state rate constants arise from

  18. A detailed examination of laser-ion acceleration mechanisms in the relativistic transparency regime using tracers

    Science.gov (United States)

    Stark, David J.; Yin, Lin; Albright, Brian J.; Nystrom, William; Bird, Robert

    2018-04-01

    We present a particle-in-cell study of linearly polarized laser-ion acceleration systems, in which we use both two-dimensional (2D) and three-dimensional (3D) simulations to characterize the ion acceleration mechanisms in targets which become transparent to the laser pulse during irradiation. First, we perform a target length scan to optimize the peak ion energies in both 2D and 3D, and the predictive capabilities of 2D simulations are discussed. Tracer analysis allows us to isolate the acceleration into stages of target normal sheath acceleration (TNSA), hole boring (HB), and break-out afterburner (BOA) acceleration, which vary in effectiveness based on the simulation parameters. The thinnest targets reveal that enhanced TNSA is responsible for accelerating the most energetic ions, whereas the thickest targets have ions undergoing successive phases of HB and TNSA (in 2D) or BOA and TNSA (in 3D); HB is not observed to be a dominant acceleration mechanism in the 3D simulations. It is in the intermediate optimal regime, both when the laser breaks through the target with appreciable amplitude and when there is enough plasma to form a sustained high density flow, that BOA is most effective and is responsible for the most energetic ions. Eliminating the transverse laser spot size effects by performing a plane wave simulation, we can isolate with greater confidence the underlying physics behind the ion dynamics we observe. Specifically, supplemented by wavelet and FFT analyses, we match the post-transparency BOA acceleration with a wave-particle resonance with a high-amplitude low-frequency electrostatic wave of increasing phase velocity, consistent with that predicted by the Buneman instability.

  19. Detailed monitoring of two biogas plants and mechanical solid-liquid separation of fermentation residues.

    Science.gov (United States)

    Bauer, Alexander; Mayr, Herwig; Hopfner-Sixt, Katharina; Amon, Thomas

    2009-06-01

    The Austrian "green electricity act" (Okostromgesetz) has led to an increase in biogas power plant size and consequently to an increased use of biomass. A biogas power plant with a generating capacity of 500 kW(el) consumes up to 38,000 kg of biomass per day. 260 ha of cropland is required to produce this mass. The high water content of biomass necessitates a high transport volume for energy crops and fermentation residues. The transport and application of fermentation residues to farmland is the last step in this logistic chain. The use of fermentation residues as fertilizer closes the nutrient cycle and is a central element in the efficient use of biomass for power production. Treatment of fermentation residues by separation into liquid and solid phases may be a solution to the transport problem. This paper presents detailed results from the monitoring of two biogas plants and from the analysis of the separation of fermentation residues. Furthermore, two different separator technologies for the separation of fermentation residues of biogas plants were analyzed. The examined biogas plants correspond to the current technological state of the art and have designs developed specifically for the utilization of energy crops. The hydraulic retention time ranged between 45.0 and 83.7 days. The specific methane yields were 0.40-0.43 m(3)N CH(4) per kg VS. The volume loads ranged between 3.69 and 4.00 kg VS/m(3). The degree of degradation was between 77.3% and 82.14%. The screw extractor separator was better suited for biogas slurry separation than the rotary screen separator. The screw extractor separator exhibited a high throughput and good separation efficiency. The efficiency of slurry separation depended on the dry matter content of the fermentation residue. The higher the dry matter content, the higher the proportion of solid phase after separation. In this project, we found that the fermentation residues could be divided into 79.2% fluid phase with a dry matter

  20. Kinetics and fracture resistance of lithiated silicon nanostructure pairs controlled by their mechanical interaction

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Seok Woo; /Stanford U., Geballe Lab.; Lee, Hyun-Wook; /Stanford U., Materials Sci. Dept.; Ryu, Ill; /Brown U.; Nix, William D.; /Stanford U., Materials Sci. Dept.; Gao, Huajian; /Brown U.; Cui, Yi; /Stanford U., Materials Sci. Dept. /SLAC

    2015-06-01

    Following an explosion of studies of silicon as a negative electrode for Li-ion batteries, the anomalous volumetric changes and fracture of lithiated single Si particles have attracted significant attention in various fields, including mechanics. However, in real batteries, lithiation occurs simultaneously in clusters of Si in a confined medium. Hence, understanding how the individual Si structures interact during lithiation in a closed space is necessary. Herein, we demonstrate physical/mechanical interactions of swelling Si structures during lithiation using well-defined Si nanopillar pairs. Ex situ SEM and in situ TEM studies reveal that compressive stresses change the reaction kinetics so that preferential lithiation occurs at free surfaces when the pillars are mechanically clamped. Such mechanical interactions enhance the fracture resistance of This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under Contract No. DE-AC02-76SF00515. SLAC-PUB-16300 2 lithiated Si by lessening the tensile stress concentrations in Si structures. This study will contribute to improved design of Si structures at the electrode level for high performance Li-ion batteries.

  1. Kinetics of Domain Switching by Mechanical and Electrical Stimulation in Relaxor-Based Ferroelectrics

    Science.gov (United States)

    Chen, Zibin; Hong, Liang; Wang, Feifei; An, Xianghai; Wang, Xiaolin; Ringer, Simon; Chen, Long-Qing; Luo, Haosu; Liao, Xiaozhou

    2017-12-01

    Ferroelectric materials have been extensively explored for applications in high-density nonvolatile memory devices because of their ferroelectric-ferroelastic domain-switching behavior under electric loading or mechanical stress. However, the existence of ferroelectric and ferroelastic backswitching would cause significant data loss, which affects the reliability of data storage. Here, we apply in situ transmission electron microscopy and phase-field modeling to explore the unique ferroelastic domain-switching kinetics and the origin of this in relaxor-based Pb (Mg1 /3Nb2 /3)O3-33 % PbTiO3 single-crystal pillars under electrical and mechanical stimulations. Results showed that the electric-mechanical hysteresis loop shifted for relaxor-based single-crystal pillars because of the low energy levels of domains in the material and the constraint on the pillars, resulting in various mechanically reversible and irreversible domain-switching states. The phenomenon can potentially be used for advanced bit writing and reading in nonvolatile memories, which effectively overcomes the backswitching problem and broadens the types of ferroelectric materials for nonvolatile memory applications.

  2. Application potential of grapefruit peel as dye sorbent: Kinetics, equilibrium and mechanism of crystal violet adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Saeed, Asma, E-mail: asmadr@wol.net.pk [Environmental Biotechnology Group, Biotechnology and Food Research Centre, PCSIR Laboratories Complex, Ferozepur Road, Lahore 54600 (Pakistan); Sharif, Mehwish [School of Biological Sciences, University of the Punjab, Lahore 54590 (Pakistan); Iqbal, Muhammad [Environmental Biotechnology Group, Biotechnology and Food Research Centre, PCSIR Laboratories Complex, Ferozepur Road, Lahore 54600 (Pakistan)

    2010-07-15

    This study reports the sorption of crystal violet (CV) dye by grapefruit peel (GFP), which has application potential in the remediation of dye-contaminated wastewaters using a solid waste generated by the citrus fruit juice industry. Batch adsorption of CV was conducted to evaluate the effect of initial pH, contact time, temperature, initial dye concentration, GFP adsorbent dose, and removal of the adsorbate CV dye from aqueous solution to understand the mechanism of sorption involved. Sorption equilibrium reached rapidly with 96% CV removal in 60 min. Fit of the sorption experimental data was tested on the pseudo-first and pseudo-second-order kinetics mathematical equations, which was noted to follow the pseudo-second-order kinetics better, with coefficient of correlation {>=}0.992. The equilibrium process was well described by the Langmuir isotherm model, with maximum sorption capacity of 254.16 mg g{sup -1}. The GFP was regenerated using 1 M NaOH, with up to 98.25% recovery of CV and could be reused as a dye sorbent in repeated cycles. GFP was also shown to be highly effective in removing CV from aqueous solution in continuous-flow fixed-bed column reactors. The study shows that GFP has the potential of application as an efficient sorbent for the removal of CV from aqueous solutions.

  3. Application potential of grapefruit peel as dye sorbent: Kinetics, equilibrium and mechanism of crystal violet adsorption

    International Nuclear Information System (INIS)

    Saeed, Asma; Sharif, Mehwish; Iqbal, Muhammad

    2010-01-01

    This study reports the sorption of crystal violet (CV) dye by grapefruit peel (GFP), which has application potential in the remediation of dye-contaminated wastewaters using a solid waste generated by the citrus fruit juice industry. Batch adsorption of CV was conducted to evaluate the effect of initial pH, contact time, temperature, initial dye concentration, GFP adsorbent dose, and removal of the adsorbate CV dye from aqueous solution to understand the mechanism of sorption involved. Sorption equilibrium reached rapidly with 96% CV removal in 60 min. Fit of the sorption experimental data was tested on the pseudo-first and pseudo-second-order kinetics mathematical equations, which was noted to follow the pseudo-second-order kinetics better, with coefficient of correlation ≥0.992. The equilibrium process was well described by the Langmuir isotherm model, with maximum sorption capacity of 254.16 mg g -1 . The GFP was regenerated using 1 M NaOH, with up to 98.25% recovery of CV and could be reused as a dye sorbent in repeated cycles. GFP was also shown to be highly effective in removing CV from aqueous solution in continuous-flow fixed-bed column reactors. The study shows that GFP has the potential of application as an efficient sorbent for the removal of CV from aqueous solutions.

  4. Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathways.

    Science.gov (United States)

    Bu, Lingjun; Zhou, Shiqing; Shi, Zhou; Deng, Lin; Li, Guangchao; Yi, Qihang; Gao, Naiyun

    2016-02-01

    The degradation kinetics and mechanism of the antiepileptic drug oxcarbazepine (OXC) by UV-activated persulfate oxidation were investigated in this study. Results showed that UV/persulfate (UV/PS) process appeared to be more effective in degrading OXC than UV or PS alone. The OXC degradation exhibited a pseudo-first order kinetics pattern and the degradation rate constants (k obs) were affected by initial OXC concentration, PS dosage, initial pH, and humic acid concentration to different degrees. It was found that low initial OXC concentration, high persulfate dosage, and initial pH enhanced the OXC degradation. Additionally, the presence of humic acid in the solution could greatly inhibit the degradation of OXC. Moreover, hydroxyl radical (OH•) and sulfate radical (SO4 (-)••) were identified to be responsible for OXC degradation and SO4 (-)• made the predominant contribution in this study. Finally, major intermediate products were identified and a preliminary degradation pathway was proposed. Results demonstrated that UV/PS system is a potential technology to control the water pollution caused by emerging contaminants such as OXC.

  5. Application potential of grapefruit peel as dye sorbent: kinetics, equilibrium and mechanism of crystal violet adsorption.

    Science.gov (United States)

    Saeed, Asma; Sharif, Mehwish; Iqbal, Muhammad

    2010-07-15

    This study reports the sorption of crystal violet (CV) dye by grapefruit peel (GFP), which has application potential in the remediation of dye-contaminated wastewaters using a solid waste generated by the citrus fruit juice industry. Batch adsorption of CV was conducted to evaluate the effect of initial pH, contact time, temperature, initial dye concentration, GFP adsorbent dose, and removal of the adsorbate CV dye from aqueous solution to understand the mechanism of sorption involved. Sorption equilibrium reached rapidly with 96% CV removal in 60 min. Fit of the sorption experimental data was tested on the pseudo-first and pseudo-second-order kinetics mathematical equations, which was noted to follow the pseudo-second-order kinetics better, with coefficient of correlation > or = 0.992. The equilibrium process was well described by the Langmuir isotherm model, with maximum sorption capacity of 254.16 mg g(-1). The GFP was regenerated using 1 M NaOH, with up to 98.25% recovery of CV and could be reused as a dye sorbent in repeated cycles. GFP was also shown to be highly effective in removing CV from aqueous solution in continuous-flow fixed-bed column reactors. The study shows that GFP has the potential of application as an efficient sorbent for the removal of CV from aqueous solutions. 2010 Elsevier B.V. All rights reserved.

  6. Kinetic mechanism of V-shaped twinning in 3C/4H-SiC heteroepitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Xin, Bin; Zhang, Yu-Ming; Jia, Ren-Xu, E-mail: rxjia@mail.xidian.edu.cn [School of Microelectronics, Xidian University, Key Laboratory of Wide Band-Gap Semiconductor Materials and Devices, Xi' an 710071 (China); Wu, Hong-Ming [Graduate Institute of Electronics Engineering, National Taiwan University, 10617 Taipei, Taiwan (China); Feng, Zhe Chuan [Graduate Institute of Photonics and Optoelectronics, National Taiwan University, 10617 Taipei, Taiwan and Laboratory of Optoelectronic Materials and Detection Technology, Guangxi Key Laboratory for the Relativistic Astrophysics, College of Physics Science and Technology, Guangxi University, Nanning 530004 (China); Lin, Hao-Hsiung [Graduate Institute of Electronics Engineering, National Taiwan University, 10617 Taipei, Taiwan and Graduate Institute of Photonics and Optoelectronics, National Taiwan University, 10617 Taipei, Taiwan (China)

    2016-05-15

    The authors investigated the kinetic mechanism of V-shaped twinning in 3C/4H-SiC heteroepitaxy. A fourfold V-shaped twinning complex was found, and its interface was measured with high-resolution transmission electron microscopy (HRTEM). Two linear coherent boundaries and a nonlinear incoherent boundary (also called the double-position boundary) were observed. On the basis of the HRTEM results, the authors proposed an adatom migration growth model, in which the activation barrier at the coherent boundary is much lower than that at the incoherent boundary. From a kinetic perspective, adatoms are prone to migrate to the side of the boundary with the lower potential energy if they have sufficient thermal energy to overcome the activation barrier. In the case of a coherent boundary, the growth rates of the domains either side of the boundary can be balanced through the intermigration of adatoms, leading to a linear boundary. Conversely, it is difficult for adatoms to migrate across an incoherent boundary, which results in asynchronous growth rates and a nonlinear boundary.

  7. Adsorption isotherm, kinetic and mechanism of expanded graphite for sulfadiazine antibiotics removal from aqueous solutions.

    Science.gov (United States)

    Zhang, Ling; Wang, Yong; Jin, SuWan; Lu, QunZan; Ji, Jiang

    2017-10-01

    The adsorption of sulfadiazine from water by expanded graphite (EG), a low cost and environmental-friendly adsorbent, was investigated. Several adsorption parameters (including the initial sulfadiazine concentration, contact time, pH of solution, ionic strength and temperature) were studied. Results of equilibrium experiments indicated that adsorption of sulfadiazine onto EG were better described by the Langmuir and Tempkin models than by the Freundlich model. The maximum adsorption capacity is calculated to be 16.586 mg/g at 298 K. The kinetic data were analyzed by pseudo-first-order, pseudo-second-order and intraparticle models. The results indicated that the adsorption process followed pseudo-second-order kinetics and may be controlled by two steps. Moreover, the pH significantly influenced the adsorption process, with the relatively high adsorption capacity at pH 2-10. The electrostatic and hydrophobic interactions are manifested to be two main mechanisms for sulfadiazine adsorption of EG. Meanwhile, the ionic concentration of Cl - slightly impacted the removal of sulfadiazine. Results of thermodynamics analysis showed spontaneous and exothermic nature of sulfadiazine adsorption on EG. In addition, regeneration experiments imply that the saturated EG could be reused for sulfadiazine removal by immersing sodium hydroxide.

  8. Desorption Kinetics and Mechanisms of CO2 on Amine-Based Mesoporous Silica Materials

    Directory of Open Access Journals (Sweden)

    Yang Teng

    2017-01-01

    Full Text Available Tetraethylenepentamine (TEPA-based mesoporous MCM-41 is used as the adsorbent to determine the CO2 desorption kinetics of amine-modified materials after adsorption. The experimental data of CO2 desorption as a function of time are derived by zero-length column at different temperatures (35, 50, and 70 °C and analyzed by Avrami’s fractional-order kinetic model. A new method is used to distinguish the physical desorption and chemical desorption performance of surface-modified mesoporous MCM-41. The activation energy Ea of CO2 physical desorption and chemical desorption calculated from Arrhenius equation are 15.86 kJ/mol and 57.15 kJ/mol, respectively. Furthermore, intraparticle diffusion and Boyd’s film models are selected to investigate the mechanism of CO2 desorption from MCM-41 and surface-modified MCM-41. For MCM-41, there are three rate-limiting steps during the desorption process. Film diffusion is more prominent for the CO2 desorption rates at low temperatures, and pore diffusion mainly governs the rate-limiting process under higher temperatures. Besides the surface reaction, the desorption process contains four rate-limiting steps on surface-modified MCM-41.

  9. Adsorption of Ag (I) from aqueous solution by waste yeast: kinetic, equilibrium and mechanism studies.

    Science.gov (United States)

    Zhao, Yufeng; Wang, Dongfang; Xie, Hezhen; Won, Sung Wook; Cui, Longzhe; Wu, Guiping

    2015-01-01

    One type of biosorbents, brewer fermentation industry waste yeast, was developed to adsorb the Ag (I) in aqueous solution. The result of FTIR analysis of waste yeast indicated that the ion exchange, chelating and reduction were the main binding mechanisms between the silver ions and the binding sites on the surface of the biomass. Furthermore, TEM, XRD and XPS results suggested that Ag(0) nanoparticles were deposited on the surface of yeast. The kinetic experiments revealed that sorption equilibrium could reach within 60 min, and the removal efficiency of Ag (I) could be still over 93 % when the initial concentration of Ag (I) was below 100 mg/L. Thermodynamic parameters of the adsorption process (ΔG, ΔH and ΔS) identified that the adsorption was a spontaneous and exothermic process. The waste yeast, playing a significant role in the adsorption of the silver ions, is useful to fast adsorb Ag (I) from low concentration.

  10. Spectral methods in chemistry and physics applications to kinetic theory and quantum mechanics

    CERN Document Server

    Shizgal, Bernard

    2015-01-01

    This book is a pedagogical presentation of the application of spectral and pseudospectral methods to kinetic theory and quantum mechanics. There are additional applications to astrophysics, engineering, biology and many other fields. The main objective of this book is to provide the basic concepts to enable the use of spectral and pseudospectral methods to solve problems in diverse fields of interest and to a wide audience. While spectral methods are generally based on Fourier Series or Chebychev polynomials, non-classical polynomials and associated quadratures are used for many of the applications presented in the book. Fourier series methods are summarized with a discussion of the resolution of the Gibbs phenomenon. Classical and non-classical quadratures are used for the evaluation of integrals in reaction dynamics including nuclear fusion, radial integrals in density functional theory, in elastic scattering theory and other applications. The subject matter includes the calculation of transport coefficient...

  11. Kinetics and mechanism of azo dye destruction in advanced oxidation processes

    International Nuclear Information System (INIS)

    Wojnarovits, L.; Palfi, T.; Takacs, E.

    2007-01-01

    The kinetics and mechanism of dye destruction in advanced oxidation processes is discussed on the example of Apollofix Red (Ar-28) radiolysis in aqueous solution. When the reactive intermediate reacts with the color bearing part of the molecule causing with nearly 100% efficiency destruction of the conjugation, the dose dependence, or time dependence of color disappearance is linear. In this case, spectrophotometry can be used to follow-up dye decomposition. Linear dependence was observed when hydrated electrons or hydrogen atoms reacted with the dye. In hydroxyl radical reactions some colored products form with spectra similar to those of the starting dye molecules. For that reason, spectrophotometry gives false result about the intact dye molecule concentration. Analysis by the HPLC reveals logarithmic time dependence in agreement with a theoretical model developed

  12. Kinetics and Mechanism of Oxidation of Aromatic Aldehydes by Imidazolium Dichromate in Aqueous Acetic Acid Medium

    Directory of Open Access Journals (Sweden)

    S. Sheik Mansoor

    2009-01-01

    Full Text Available The kinetics of oxidation of benzaldehyde (BA and para-substituted benzaldehydes by imidazolium dichromate (IDC has been studied in aqueous acetic acid medium in the presence of perchloric acid. The reaction is first order each in [IDC], [Substrate] and [H+]. The reaction rates have been determined at different temperatures and the activation parameters calculated. Electron withdrawing substituents are found to increase the reaction and electron releasing substituents are found to retard the rate of the reaction and the rate data obey the Hammett relationship. The products of the oxidation are the corresponding acids. The rate decreases with the increase in the water content of the medium. A suitable mechanism is proposed.

  13. Enhanced charging kinetics of porous electrodes: surface conduction as a short-circuit mechanism.

    Science.gov (United States)

    Mirzadeh, Mohammad; Gibou, Frederic; Squires, Todd M

    2014-08-29

    We use direct numerical simulations of the Poisson-Nernst-Planck equations to study the charging kinetics of porous electrodes and to evaluate the predictive capabilities of effective circuit models, both linear and nonlinear. The classic transmission line theory of de Levie holds for general electrode morphologies, but only at low applied potentials. Charging dynamics are slowed appreciably at high potentials, yet not as significantly as predicted by the nonlinear transmission line model of Biesheuvel and Bazant. We identify surface conduction as a mechanism which can effectively "short circuit" the high-resistance electrolyte in the bulk of the pores, thus accelerating the charging dynamics and boosting power densities. Notably, the boost in power density holds only for electrode morphologies with continuous conducting surfaces in the charging direction.

  14. Kinetics and mechanisms of interactions of nitrogen and carbon monoxide with liquid niobium

    International Nuclear Information System (INIS)

    Park, H.G.

    1990-01-01

    The kinetics and mechanisms of interactions of N 2 and CO with liquid niobium were investigated in the temperature range of 2,700 to 3,000 K in samples levitated in N 2 /Ar and CO/Ar streams. The nitrogen absorption and desorption processes were found to be second-order with respect to nitrogen concentration, indicating that the rate controlling step is either the adsorption of nitrogen molecules on the liquid surface or dissociation of absorbed nitrogen molecules into adsorbed atoms. The carbon and oxygen dissolution in liquid niobium from CO gas is an exothermic process and the solubilities of carbon and oxygen (C Ce , C Oe in at%) are related to the temperature and the partial pressure of CO. The reaction CO → [C] + [O] along with the evaporation of niobium oxide takes place during C and O dissolution, whereas C and O desorption occurs via CO evolution only

  15. Mechanisms and kinetic profiles of superoxide-stimulated nitrosative processes in cells using a diaminofluorescein probe.

    Science.gov (United States)

    Damasceno, Fernando Cruvinel; Facci, Rômulo Rodrigues; da Silva, Thalita Marques; Toledo, José Carlos

    2014-12-01

    In this study, we examined the mechanisms and kinetic profiles of intracellular nitrosative processes using diaminofluorescein (DAF-2) as a target in RAW 264.7 cells. The intracellular formation of the fluorescent, nitrosated product diaminofluorescein triazol (DAFT) from both endogenous and exogenous nitric oxide (NO) was prevented by deoxygenation and by cell membrane-permeable superoxide (O2(-)) scavengers but not by extracellular bovine Cu,Zn-SOD. In addition, the DAFT formation rate decreased in the presence of cell membrane-permeable Mn porphyrins that are known to scavenge peroxynitrite (ONOO(-)) but was enhanced by HCO3(-)/CO2. Together, these results indicate that nitrosative processes in RAW 264.7 cells depend on endogenous intracellular O2(-) and are stimulated by ONOO(-)/CO2-derived radical oxidants. The N2O3 scavenger sodium azide (NaN3) only partially attenuated the DAFT formation rate and only with high NO (>120 nM), suggesting that DAFT formation occurs by nitrosation (azide-susceptible DAFT formation) and predominantly by oxidative nitrosylation (azide-resistant DAFT formation). Interestingly, the DAFT formation rate increased linearly with NO concentrations of up to 120-140 nM but thereafter underwent a sharp transition and became insensitive to NO. This behavior indicates the sudden exhaustion of an endogenous cell substrate that reacts rapidly with NO and induces nitrosative processes, consistent with the involvement of intracellular O2(-). On the other hand, intracellular DAFT formation stimulated by a fixed flux of xanthine oxidase-derived extracellular O2(-) that also occurs by nitrosation and oxidative nitrosylation increased, peaked, and then decreased with increasing NO, as previously observed. Thus, our findings complementarily show that intra- and extracellular O2(-)-dependent nitrosative processes occurring by the same chemical mechanisms do not necessarily depend on NO concentration and exhibit different unusual kinetic profiles with

  16. Kinetics and mechanism of oxygen reduction reaction at CoPd system synthesized on XC72

    International Nuclear Information System (INIS)

    Tarasevich, M.R.; Chalykh, A.E.; Bogdanovskaya, V.A.; Kuznetsova, L.N.; Kapustina, N.A.; Efremov, B.N.; Ehrenburg, M.R.; Reznikova, L.A.

    2006-01-01

    Studies are presented of the kinetics and mechanism of oxygen electroreduction reaction on CoPd catalysts synthesized on carbon black XC72. As shown both in model conditions and in the tests within the cathodes of hydrogen-oxygen fuel cells with proton conducting electrolyte, CoPd/C system features a higher activity, as compared to Co/C. The highest activity in the oxygen reduction reaction is demonstrated by the catalysts with the Pd:Co atomic ratio being 7:3 and 4:1. The structural studies (XPS and XRD, and also the data of CO desorption measurements) evidence the CoPd alloy formation, which is reflected in the negative shift of the bonding energy maximum as compared to Pd/C and in the appearance of the additional CO desorption maximums on the voltammograms. It is found by means of structural research that CoPd alloy is formed in the course of the catalyst synthesis which features a higher catalytic activity of the binary systems. Besides, CoPd/C catalyst is more stable in respect to corrosion than Pd supported on carbon black. The measurements on the rotating disc electrode and rotating ring-disc electrode evidence that CoPd/C system provides the predominant oxygen reduction to water in the practically important range of potentials (E > 0.7 V). The proximity of kinetic parameters of the oxygen reduction reaction on CoPd/C and Pt/C catalysts points to the similar reaction mechanism. The slow step of the reaction is the addition of the first electron to the adsorbed and previously protonated O 2 molecule. The assumptions are offered about the reasons causing the higher activity and selectivity of the binary catalyst towards oxygen reduction to water, as compared to Co/C. The studies of the most active catalysts within the fuel cell cathodes are performed

  17. Kinetics and mechanical stability of the fibril state control fibril formation time of polypeptide chains: A computational study

    Science.gov (United States)

    Kouza, Maksim; Co, Nguyen Truong; Li, Mai Suan; Kmiecik, Sebastian; Kolinski, Andrzej; Kloczkowski, Andrzej; Buhimschi, Irina Alexandra

    2018-06-01

    Fibril formation resulting from protein misfolding and aggregation is a hallmark of several neurodegenerative diseases such as Alzheimer's and Parkinson's diseases. Despite much progress in the understanding of the protein aggregation process, the factors governing fibril formation rates and fibril stability have not been fully understood. Using lattice models, we have shown that the fibril formation time is controlled by the kinetic stability of the fibril state but not by its energy. Having performed all-atom explicit solvent molecular dynamics simulations with the GROMOS43a1 force field for full-length amyloid beta peptides Aβ40 and Aβ42 and truncated peptides, we demonstrated that kinetic stability can be accessed via mechanical stability in such a way that the higher the mechanical stability or the kinetic stability, the faster the fibril formation. This result opens up a new way for predicting fibril formation rates based on mechanical stability that may be easily estimated by steered molecular dynamics.

  18. Atomistic detailed mechanism and weak cation-conducting activity of HIV-1 Vpu revealed by free energy calculations.

    Directory of Open Access Journals (Sweden)

    Siladitya Padhi

    Full Text Available The viral protein U (Vpu encoded by HIV-1 has been shown to assist in the detachment of virion particles from infected cells. Vpu forms cation-specific ion channels in host cells, and has been proposed as a potential drug target. An understanding of the mechanism of ion transport through Vpu is desirable, but remains limited because of the unavailability of an experimental structure of the channel. Using a structure of the pentameric form of Vpu--modeled and validated based on available experimental data--umbrella sampling molecular dynamics simulations (cumulative simulation time of more than 0.4 µs were employed to elucidate the energetics and the molecular mechanism of ion transport in Vpu. Free energy profiles corresponding to the permeation of Na+ and K+ were found to be similar to each other indicating lack of ion selection, consistent with previous experimental studies. The Ser23 residue is shown to enhance ion transport via two mechanisms: creating a weak binding site, and increasing the effective hydrophilic length of the channel, both of which have previously been hypothesized in experiments. A two-dimensional free energy landscape has been computed to model multiple ion permeation, based on which a mechanism for ion conduction is proposed. It is shown that only one ion can pass through the channel at a time. This, along with a stretch of hydrophobic residues in the transmembrane domain of Vpu, explains the slow kinetics of ion conduction. The results are consistent with previous conductance studies that showed Vpu to be a weakly conducting ion channel.

  19. Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

    Science.gov (United States)

    Hynes, A. J.; Wine, P. H.

    1997-01-01

    scheme to extract kinetic information about the adduct reations with O2 and branching ratios for OH regeneration. A plausible mechanism for OH regeneration in (2) involves OH addition to the nitrogen atom followed by O2 addition to the cyano carbon atom, isomeriazation and decomposition to D2CO + DOCN + OH. Our results suggest that the OH + CH3CN reaction occurs via a complex mechanism involving both bimolecular and termolecular pathways, analogous to the mechanisms for the the important atmospheric reactions of OH with CO and HNO3.

  20. PAH growth initiated by propargyl addition: Mechanism development and computational kinetics

    KAUST Repository

    Raj, Abhijeet Dhayal

    2014-04-24

    Polycyclic aromatic hydrocarbon (PAH) growth is known to be the principal pathway to soot formation during fuel combustion, as such, a physical understanding of the PAH growth mechanism is needed to effectively assess, predict, and control soot formation in flames. Although the hydrogen abstraction C2H2 addition (HACA) mechanism is believed to be the main contributor to PAH growth, it has been shown to under-predict some of the experimental data on PAHs and soot concentrations in flames. This article presents a submechanism of PAH growth that is initiated by propargyl (C 3H3) addition onto naphthalene (A2) and the naphthyl radical. C3H3 has been chosen since it is known to be a precursor of benzene in combustion and has appreciable concentrations in flames. This mechanism has been developed up to the formation of pyrene (A4), and the temperature-dependent kinetics of each elementary reaction has been determined using density functional theory (DFT) computations at the B3LYP/6-311++G(d,p) level of theory and transition state theory (TST). H-abstraction, H-addition, H-migration, β-scission, and intramolecular addition reactions have been taken into account. The energy barriers of the two main pathways (H-abstraction and H-addition) were found to be relatively small if not negative, whereas the energy barriers of the other pathways were in the range of (6-89 kcal·mol-1). The rates reported in this study may be extrapolated to larger PAH molecules that have a zigzag site similar to that in naphthalene, and the mechanism presented herein may be used as a complement to the HACA mechanism to improve prediction of PAH and soot formation. © 2014 American Chemical Society.

  1. Development of Detailed and Reduced Kinetics Mechanisms for Surrogates of Petroleum-Derived and Synthetic Jet Fuels

    Science.gov (United States)

    2014-12-04

    flexible energy conversion and design) needs of air-breathing propulsion are addressed. The research efforts of the completed program are directly...particle riser to tune the seeding particle density for the particle image velocimetry (PIV) measurements. To reach approximately ambient air temperature

  2. Kinetic calorimetry in the study of the mechanism of low-temperature chemical reactions

    Science.gov (United States)

    Barkalov, I. M.; Kiryukhin, D. P.

    Chemical reactions are always followed by a change in the reacting system enthalpy, hence, calorimetry as a method of enthalpy and heat capacity measuring is a universal and, sometimes, even the only possible way of studying chemical reaction kinetics. Throughout its long history, the calorimeter, having preserved the positions of the main method of thermodynamic studies, has conquered a new field of application: that of kinetic study of chemical reactions. The advantages and disadvantages of the kinetic calorimeter are now obvious. First, the advantages are: (1) the possibility of measuring the rate of a chemical reaction without any special requirements being imposed on the reaction medium (solid, viscous, multicomponent systems); (2) the high efficiency: a large volume of kinetic information in one experiment and a non-destructive character of changes; (3) the possibility of measuring directly in the field of ionizing radiation (γ-radiation, accelerated electrons) and light; and (4) recording of the chemical conversion directly at the time of its occurrence. The disadvantages of this method are: (1) the high inertia of standard calorimeter systems (τC⋍102-103S), which restricts the possibilities of studying fast processes; and (2) the complexity of the correct organization of the calorimeter experiment when the parameters of the process are changed (overheating in the sample, conversion of the process to explosive and auto wave regimens). One of the oldest and most universal methods of studying the mechanism of chemical reactions, calorimetry, is now passing through a period of turbulent development due to the advances in electronics and computerization. The wide variety of types of calorimeter set-ups and the large assortment of measurement schemes in the currently described methods complicate the experimental selection of the necessary instrument rather than facilitate it. The basic principles of the method, the types of calorimeters, and the measuring

  3. Corrosion mechanisms of zirconium alloys - study of the initial oxidation kinetics and of the mechanical behaviour of the metal/oxide system

    International Nuclear Information System (INIS)

    Parise, M.

    1996-12-01

    Nuclear fuel claddings are made of zirconium alloys. The conditions of use lead the cladding oxidize outside. The so-formed layers behaves like a thermal barrier and prevents from using oxidized claddings with an oxide thickness larger than 100 μm. The oxidation kinetic is approximately cubic for oxide thicknesses smaller than about 2μm, linear beyond. A kinetic model has been proposed which estimates the post-transition growth rate from the kinetic parameters of the pre-transition state and morphological features of post-transition layers. This work aims at providing the necessary elements to validate this model and studying the layers around the kinetic transition, in order to determine whether the oxidation mechanisms before and after the transition are similar. Thicknesses of the 50 - 500 nm range of the oxide layers are measured by an optical method; pre-transition kinetics are thus precisely determined. The effect of the composition, the thermal treatment and the presence of oxygen in solid solution is studied. The morphological and crystallographic study of the layers show that they exhibit a lot of similarities before and after the kinetic transition. The results concerning the kinetic aspects and the morphology of the post-transition layers point out that the proposed model leads to realistic post-transition growth rates. Furthermore, the kinetic transition corresponds to the appearance of cracks in the oxide layer. The mechanical behaviour of the metal/oxide system has been modelled at different scales. When the specific behaviours of the metal and the oxide are taken into account together with the interface geometry, radial stresses appear, which are high enough to locally open cracks. The appearance and localization of cracks depend on both the interface geometry and the stress distribution in the metal/oxide system. (author)

  4. Large variation in the Rubisco kinetics of diatoms reveals diversity among their carbon-concentrating mechanisms

    Science.gov (United States)

    Young, Jodi N.; Heureux, Ana M.C.; Sharwood, Robert E.; Rickaby, Rosalind E.M.; Morel, François M.M.; Whitney, Spencer M.

    2016-01-01

    While marine phytoplankton rival plants in their contribution to global primary productivity, our understanding of their photosynthesis remains rudimentary. In particular, the kinetic diversity of the CO2-fixing enzyme, Rubisco, in phytoplankton remains unknown. Here we quantify the maximum rates of carboxylation (k cat c), oxygenation (k cat o), Michaelis constants (K m) for CO2 (K C) and O2 (K O), and specificity for CO2 over O2 (SC/O) for Form I Rubisco from 11 diatom species. Diatom Rubisco shows greater variation in K C (23–68 µM), SC/O (57–116mol mol−1), and K O (413–2032 µM) relative to plant and algal Rubisco. The broad range of K C values mostly exceed those of C4 plant Rubisco, suggesting that the strength of the carbon-concentrating mechanism (CCM) in diatoms is more diverse, and more effective than previously predicted. The measured k cat c for each diatom Rubisco showed less variation (2.1–3.7s−1), thus averting the canonical trade-off typically observed between K C and k cat c for plant Form I Rubisco. Uniquely, a negative relationship between K C and cellular Rubisco content was found, suggesting variation among diatom species in how they allocate their limited cellular resources between Rubisco synthesis and their CCM. The activation status of Rubisco in each diatom was low, indicating a requirement for Rubisco activase. This work highlights the need to better understand the correlative natural diversity between the Rubisco kinetics and CCM of diatoms and the underpinning mechanistic differences in catalytic chemistry among the Form I Rubisco superfamily. PMID:27129950

  5. Kinetic and Structural Insights into the Mechanism of AMPylation by VopS Fic Domain*

    Science.gov (United States)

    Luong, Phi; Kinch, Lisa N.; Brautigam, Chad A.; Grishin, Nick V.; Tomchick, Diana R.; Orth, Kim

    2010-01-01

    The bacterial pathogen Vibrio parahemeolyticus manipulates host signaling pathways during infections by injecting type III effectors into the cytoplasm of the target cell. One of these effectors, VopS, blocks actin assembly by AMPylation of a conserved threonine residue in the switch 1 region of Rho GTPases. The modified GTPases are no longer able to interact with downstream effectors due to steric hindrance by the covalently linked AMP moiety. Herein we analyze the structure of VopS and its evolutionarily conserved catalytic residues. Steady-state analysis of VopS mutants provides kinetic understanding on the functional role of each residue for AMPylation activity by the Fic domain. Further mechanistic analysis of VopS with its two substrates, ATP and Cdc42, demonstrates that VopS utilizes a sequential mechanism to AMPylate Rho GTPases. Discovery of a ternary reaction mechanism along with structural insight provides critical groundwork for future studies for the family of AMPylators that modify hydroxyl-containing residues with AMP. PMID:20410310

  6. Kinetic and Structural Insights into the Mechanism of AMPylation by VopS Fic Domain

    Energy Technology Data Exchange (ETDEWEB)

    Luong, Phi; Kinch, Lisa N.; Brautigam, Chad A.; Grishin, Nick V.; Tomchick, Diana R.; Orth, Kim (UTSMC)

    2010-07-19

    The bacterial pathogen Vibrio parahemeolyticus manipulates host signaling pathways during infections by injecting type III effectors into the cytoplasm of the target cell. One of these effectors, VopS, blocks actin assembly by AMPylation of a conserved threonine residue in the switch 1 region of Rho GTPases. The modified GTPases are no longer able to interact with downstream effectors due to steric hindrance by the covalently linked AMP moiety. Herein we analyze the structure of VopS and its evolutionarily conserved catalytic residues. Steady-state analysis of VopS mutants provides kinetic understanding on the functional role of each residue for AMPylation activity by the Fic domain. Further mechanistic analysis of VopS with its two substrates, ATP and Cdc42, demonstrates that VopS utilizes a sequential mechanism to AMPylate Rho GTPases. Discovery of a ternary reaction mechanism along with structural insight provides critical groundwork for future studies for the family of AMPylators that modify hydroxyl-containing residues with AMP.

  7. The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite.

    Science.gov (United States)

    Rodriguez-Blanco, Juan Diego; Shaw, Samuel; Benning, Liane G

    2011-01-01

    The kinetics and mechanisms of nanoparticulate amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite, were studied at a range of environmentally relevant temperatures (7.5-25 °C) using synchrotron-based in situ time-resolved Energy Dispersive X-ray Diffraction (ED-XRD) in conjunction with high-resolution electron microscopy, ex situ X-ray diffraction and infrared spectroscopy. The crystallization process occurs in two stages; firstly, the particles of ACC rapidly dehydrate and crystallize to form individual particles of vaterite; secondly, the vaterite transforms to calcite via a dissolution and reprecipitation mechanism with the reaction rate controlled by the surface area of calcite. The second stage of the reaction is approximately 10 times slower than the first. Activation energies of calcite nucleation and crystallization are 73±10 and 66±2 kJ mol(-1), respectively. A model to calculate the degree of calcite crystallization from ACC at environmentally relevant temperatures (7.5-40 °C) is also presented.

  8. Experimental studies on the mechanism of leukemogenesis following the hemopoietic stem cell kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Bessho, Masami; Hirashima, Kunitake (National Inst. of Radiological Sciences, Chiba (Japan))

    1982-12-01

    The mechanism of radiation-induced myeloid leukemogenesis was studied experimentally following the hemopoietic stem cell kinetics. Pluripotent stem cells (CFU-S) regarded as target cells to Friend virus (FV) were highly susceptible to leukemic cell transformation by FV during the regeneration period after irradiation. Experimental studies using RFM mice revealed that (1) the period of leukemic transformation closely corresponded to the prolonged suppressive period of CFU-C after irradiation, when significantly increased fraction of CFU-C is in S-phase, (2) the leukemic cell transformation after irradiation occurred earlier and more frequently than the overt leukemia, (3) some unknown host factors except cellular immunity played an important role in the establishment of overt leukemia, (4) lipopolysaccharide administrated after irradiation increased the incidence of myeloid leukemia whereas urethane decreased it. Another experimental systems using C3H/He mice bearing CSF-producing tumor revealed that the incidence of myeloid leukemia after a low-dose irradiation increased when CFU-S and CFU-C were proliferating and differentiating actively by the stimulus of CSF produced by the tumor. The mechanism of this phenomenon can be regarded as the activation of leukemia virus in irradiated bodies.

  9. Biodegradation mechanisms and kinetics of azo dye 4BS by a microbial consortium.

    Science.gov (United States)

    He, Fang; Hu, Wenrong; Li, Yuezhong

    2004-10-01

    A microbial consortium consisting of a white-rot fungus 8-4* and a Pseudomonas 1-10 was isolated from wastewater treatment facilities of a local dyeing house by enrichment, using azo dye Direct Fast Scarlet 4BS as the sole source of carbon and energy, which had a high capacity for rapid decolorization of 4BS. To elucidate the decolorization mechanisms, decolorization of 4BS was compared between individual strains and the microbial consortium under different treatment processes. The microbial consortium showed a significant improvement on dye decolorization rates under either static or shaking culture, which might be attributed to the synergetic reaction of single strains. From the curve of COD values and the UV-visible spectra of 4BS solutions before and after decolorization cultivation with the microbial consortium, it was found that 4BS could be mineralized completely, and the results had been used for presuming the degrading pathway of 4BS. This study also examined the kinetics of 4BS decolorization by immobilized microbial consortium. The results demonstrated that the optimal decolorization activity was observed in pH range between four and 9, temperature range between 20 and 40 degrees C and the maximal specific decolorization rate occurred at 1,000 mg l(-1) of 4BS. The proliferation and distribution of microbial consortium were also microscopically observed, which further confirmed the decolorization mechanisms of 4BS.

  10. Kinetics and mechanism of the pyridinolysis of phenacyl bromides in acetonitrile

    Science.gov (United States)

    Koh; Han; Lee; Lee

    2000-07-28

    Kinetic studies of the reactions of substituted phenacyl bromides (YC6H4COCH2Br) with pyridines (XC5H4N) are carried out in acetonitrile at 45.0 degrees C. A biphasic Bronsted plot is obtained with a change in slope from a large (betaX approximately equals 0.65-0.80) to a small (betaX approximately 0.36-0.40) value at pKa = 3.2-3.6, which can be attributed to a change in the rate-determining step from breakdown to formation of a tetrahedral intermediate in the reaction path as the basicity of the pyridine nucleophile increases. This mechanism is supported by the faster rates with pyridines than with anilines and the change of cross-interaction constant rhoXY from a large positive (rhoXY = +1.4) to a small positive (rhoXY approximately +0.1) value. The large magnitude of Hammett rhoX (= -5.5 to -6.9) values for the pyridines with electron-withdrawing substituents and positive deviations of the pi-acceptors, p-CH3CO and p-CN, are quite similar to those for the pyridinium ion formation equilibria. The activation parameters are also in line with the proposed mechanism.

  11. Kinetics and mechanism of the formation and etching of particle tracks in polyethylene-terephthalate

    International Nuclear Information System (INIS)

    Lueck, H.B.

    1982-05-01

    The physical and chemical processes initiated by a particle passing through a polymer are reviewed. Particular attention is devoted to the processes in PETP. The influence of the material parameters and environmental effects on the subsequent reactions in PETP is discussed. Models of the mechanism and kinetics of the alkaline degradation on the surface and in the etch channel are presented. The character and the effect of the relevant species has been taken into consideration. The mechanism of the photo-oxidative sensitivity enhancement is discussed. The models mentioned above are taken as a basis to interpret the empirical response function. It is shown, that the response function can be applied to bulk-irradiated polymers as well. Treeing in electrically stressed particle tracks assisted by an etchant can be attributed to the electrostatic pressure. However, the differences in the behaviour of the structures give evidence, that the formation of craze structures and bubbles in the presence of a nonetching electrolyte is the result of the electroosmotic pressure. (author)

  12. Direct laser sintering of metal powders: Mechanism, kinetics and microstructural features

    International Nuclear Information System (INIS)

    Simchi, A.

    2006-01-01

    In the present work, the densification and microstructural evolution during direct laser sintering of metal powders were studied. Various ferrous powders including Fe, Fe-C, Fe-Cu, Fe-C-Cu-P, 316L stainless steel, and M2 high-speed steel were used. The empirical sintering rate data was related to the energy input of the laser beam according to the first order kinetics equation to establish a simple sintering model. The equation calculates the densification of metal powders during direct laser sintering process as a function of operating parameters including laser power, scan rate, layer thickness and scan line spacing. It was found that when melting/solidification approach is the mechanism of sintering, the densification of metals powders (D) can be expressed as an exponential function of laser specific energy input (ψ) as ln(1 - D) = -Kψ. The coefficient K is designated as 'densification coefficient'; a material dependent parameter that varies with chemical composition, powder particle size, and oxygen content of the powder material. The mechanism of particle bonding and microstructural features of the laser sintered powders are addressed

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

    NARCIS (Netherlands)

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

    1976-01-01

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

  14. Kinetics and mechanisms of the oxide film growth on the surface of α-Fe in transitional domains

    International Nuclear Information System (INIS)

    Mukhambetov, D.G.; Berber, N.N.; Kargin, D.B.; Chalaya, O.V.

    2003-01-01

    The object of this work was to study the kinetics of the α-Fe surface oxidation with prevailing cubic texture at temperatures of 450-500 deg. C. The basic conformity to natural laws and mechanisms of the two-phase thin oxide films grows are determined. (author)

  15. Andrographolide sodium bisulphite-induced inactivation of urease: inhibitory potency, kinetics and mechanism.

    Science.gov (United States)

    Mo, Zhi-Zhun; Wang, Xiu-Fen; Zhang, Xie; Su, Ji-Yan; Chen, Hai-Ming; Liu, Yu-Hong; Zhang, Zhen-Biao; Xie, Jian-Hui; Su, Zi-Ren

    2015-07-16

    The inhibitory effect of andrographolide sodium bisulphite (ASB) on jack bean urease (JBU) and Helicobacter pylori urease (HPU) was performed to elucidate the inhibitory potency, kinetics and mechanism of inhibition in 20 mM phosphate buffer, pH 7.0, 2 mM EDTA, 25 °C. The ammonia formations, indicator of urease activity, were examined using modified spectrophotometric Berthelot (phenol-hypochlorite) method. The inhibitory effect of ASB was characterized with IC50 values. Lineweaver-Burk and Dixon plots for JBU inhibition of ASB was constructed from the kinetic data. SH-blocking reagents and competitive active site Ni2+ binding inhibitors were employed for mechanism study. Molecular docking technique was used to provide some information on binding conformations as well as confirm the inhibition mode. The IC50 of ASB against JBU and HPU was 3.28±0.13 mM and 3.17±0.34 mM, respectively. The inhibition proved to be competitive and concentration- dependent in a slow-binding progress. The rapid formation of initial ASB-JBU complex with an inhibition constant of Ki=2.86×10(-3) mM was followed by a slow isomerization into the final complex with an overall inhibition constant of Ki*=1.33×10(-4) mM. The protective experiment proved that the urease active site is involved in the binding of ASB. Thiol reagents (L-cysteine and dithiothreithol) strongly protect the enzyme from the loss of enzymatic activity, while boric acid and fluoride show weaker protection, indicating that the active-site sulfhydryl group of JBU was potentially involved in the blocking process. Moreover, inhibition of ASB proved to be reversible since ASB-inactivated JBU could be reactivated by dithiothreitol application. Molecular docking assay suggested that ASB made contacts with the important sulfhydryl group Cys-592 residue and restricted the mobility of the active-site flap. ASB was a competitive inhibitor targeting thiol groups of urease in a slow-binding manner both reversibly and concentration

  16. Kinetics and Mechanism of Calcium Hydroxide Conversion into Calcium Alkoxides: Implications in Heritage Conservation Using Nanolimes.

    Science.gov (United States)

    Rodriguez-Navarro, Carlos; Vettori, Irene; Ruiz-Agudo, Encarnacion

    2016-05-24

    Nanolimes are alcohol dispersions of Ca(OH)2 nanoparticles used in the conservation of cultural heritage. Although it was believed that Ca(OH)2 particles were inert when dispersed in short-chain alcohols, it has been recently shown that they can undergo transformation into calcium alkoxides. Little is known, however, about the mechanism and kinetics of such a phase transformation as well as its effect on the performance of nanolimes. Here we show that Ca(OH)2 particles formed after lime slaking react with ethanol and isopropanol and partially transform (fractional conversion, α up to 0.08) into calcium ethoxide and isopropoxide, respectively. The transformation shows Arrhenius behavior, with apparent activation energy Ea of 29 ± 4 and 37 ± 6 kJ mol(-1) for Ca-ethoxide and Ca-isopropoxide conversion, respectively. High resolution transmission electron microscopy analyses of reactant and product phases show that the alkoxides replace the crystalline structure of Ca(OH)2 along specific [hkl] directions, preserving the external hexagonal (platelike) morphology of the parent phase. Textural and kinetic results reveal that this pseudomorphic replacement involves a 3D diffusion-controlled deceleratory advancement of the reaction front. The results are consistent with an interface-coupled dissolution-precipitation replacement mechanism. Analysis of the carbonation of Ca(OH)2 particles with different degree of conversion into Ca-ethoxide (α up to 0.08) and Ca-isopropoxide (α up to 0.04) exposed to air (20 °C, 80% relative humidity) reveals that Ca-alkoxides significantly reduce the rate of transformation into cementing CaCO3 and induce the formation of metastable vaterite, as opposed to stable calcite which forms in untransformed Ca(OH)2 samples. Similar effects are obtained when a commercial nanolime partially transformed into Ca-ethoxide is subjected to carbonation. Such effects may hamper/delay the strengthening or consolidation effects of nanolimes, thus having

  17. Anti-Inflammatory Applications of Melittin, a Major Component of Bee Venom: Detailed Mechanism of Action and Adverse Effects

    Directory of Open Access Journals (Sweden)

    Gihyun Lee

    2016-05-01

    Full Text Available Inflammation is a pervasive phenomenon triggered by the innate and adaptive immune systems to maintain homeostasis. The phenomenon normally leads to recovery from infection and healing, but when not properly phased, inflammation may cause immune disorders. Bee venom is a toxin that bees use for their protection from enemies. However, for centuries it has been used in the Orient as an anti-inflammatory medicine for the treatment of chronic inflammatory diseases. Bee venom and its major component, melittin, are potential means of reducing excessive immune responses and provide new alternatives for the control of inflammatory diseases. Recent experimental studies show that the biological functions of melittin could be applied for therapeutic use in vitro and in vivo. Reports verifying the therapeutic effects of melittin are accumulating in the literature, but the cellular mechanism(s of the anti-inflammatory effects of melittin are not fully elucidated. In the present study, we review the current knowledge on the therapeutic effects of melittin and its detailed mechanisms of action against several inflammatory diseases including skin inflammation, neuroinflammation, atherosclerosis, arthritis and liver inflammation, its adverse effects as well as future prospects regarding the use of melittin.

  18. Anti-Inflammatory Applications of Melittin, a Major Component of Bee Venom: Detailed Mechanism of Action and Adverse Effects.

    Science.gov (United States)

    Lee, Gihyun; Bae, Hyunsu

    2016-05-11

    Inflammation is a pervasive phenomenon triggered by the innate and adaptive immune systems to maintain homeostasis. The phenomenon normally leads to recovery from infection and healing, but when not properly phased, inflammation may cause immune disorders. Bee venom is a toxin that bees use for their protection from enemies. However, for centuries it has been used in the Orient as an anti-inflammatory medicine for the treatment of chronic inflammatory diseases. Bee venom and its major component, melittin, are potential means of reducing excessive immune responses and provide new alternatives for the control of inflammatory diseases. Recent experimental studies show that the biological functions of melittin could be applied for therapeutic use in vitro and in vivo. Reports verifying the therapeutic effects of melittin are accumulating in the literature, but the cellular mechanism(s) of the anti-inflammatory effects of melittin are not fully elucidated. In the present study, we review the current knowledge on the therapeutic effects of melittin and its detailed mechanisms of action against several inflammatory diseases including skin inflammation, neuroinflammation, atherosclerosis, arthritis and liver inflammation, its adverse effects as well as future prospects regarding the use of melittin.

  19. Online quench-flow electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry for elucidating kinetic and chemical enzymatic reaction mechanisms.

    Science.gov (United States)

    Clarke, David J; Stokes, Adam A; Langridge-Smith, Pat; Mackay, C Logan

    2010-03-01

    We have developed an automated quench-flow microreactor which interfaces directly to an electrospray ionization (ESI) mass spectrometer. We have used this device in conjunction with ESI Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) to demonstrate the potential of this approach for studying the mechanistic details of enzyme reactions. For the model system chosen to test this device, namely, the pre-steady-state hydrolysis of p-nitrophenyl acetate by the enzyme chymotrypsin, the kinetic parameters obtained are in good agreement with those in the literature. To our knowledge, this is the first reported use of online quench-flow coupled with FTICR MS. Furthermore, we have exploited the power of FTICR MS to interrogate the quenched covalently bound enzyme intermediate using top-down fragmentation. The accurate mass capabilities of FTICR MS permitted the nature of the intermediate to be assigned with high confidence. Electron capture dissociation (ECD) fragmentation allowed us to locate the intermediate to a five amino acid section of the protein--which includes the known catalytic residue, Ser(195). This experimental approach, which uniquely can provide both kinetic and chemical details of enzyme mechanisms, is a potentially powerful tool for studies of enzyme catalysis.

  20. Electrochemical mechanism and kinetics studies of haloperidol and its assay in commercial formulations

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, Francisco W.P. [Departamento de Quimica Analitica e Fisico-Quimica, Centro de Ciencias, Universidade Federal do Ceara, Bloco 940 Campus do Pici 60455-970, Fortaleza, CE (Brazil); Soares, Janete E.S. [Departamento de Farmacia, Faculdade de Farmacia, Odontologia e Enfermagem, Universidade Federal do Ceara, Rua Capitao Francisco Pedro, 1210 Rodolfo Teofilo 60430-370, Fortaleza, CE (Brazil); Becker, Helena; De Souza, Djenaine; Lima-Neto, Pedro de [Departamento de Quimica Analitica e Fisico-Quimica, Centro de Ciencias, Universidade Federal do Ceara, Bloco 940 Campus do Pici 60455-970, Fortaleza, CE (Brazil); Correia, Adriana N., E-mail: adriana@ufc.b [Departamento de Quimica Analitica e Fisico-Quimica, Centro de Ciencias, Universidade Federal do Ceara, Bloco 940 Campus do Pici 60455-970, Fortaleza, CE (Brazil)

    2011-02-01

    The kinetics and mechanism for electrochemical reduction of haloperidol, a psychotherapeutic drug used in the treatment of schizophrenia, were studied using square wave and cyclic voltammetries allied to a hanging mercury drop electrode. The experimental and voltammetric parameters were optimized at 0.04 mol L{sup -1} Brinton-Robinson buffer (pH 10), with a pulse potential frequency of 100 s{sup -1}, a pulse amplitude of 30 mV and scan increment of 2 mV. Two well-defined peaks were observed, which exhibited properties of fast electron transfer with a strong adsorption process of reactants and products on the electrode surface. The first peak was related to a fast and reversible anion-radical formation originating from the reduction of the carbonyl group, and the second was related to the irreversible reduction of the anion-radical previously formed. Analytical parameters such as: linearity range, equation of the analytical curves, correlation coefficients, detection and quantification limits, recovery efficiency, and relative standard deviation for intraday and interday were compared to similar results obtained by use of the UV-vis spectrophotometry technique, and the analytical results obtained in commercial formulations show that the voltammetric procedure using a hanging mercury drop electrode is suitable for analyzing haloperidol in complex commercial formulation samples.

  1. Conversion of glucose into 5-hydroxymethylfurfural in different solvents and catalysts: Reaction kinetics and mechanism

    Directory of Open Access Journals (Sweden)

    Cunshan Zhou

    2017-06-01

    Full Text Available Synthesis of 5-hydroxymethylfurfural (HMF from glucose was done in H2O, dimethylsulfoxide (DMSO and 1-butyl-3-methylimidazolium chloride ([Bmim]Cl catalyzed by metal (III chloride (FeCl3·6H2O, CrCl3·6H2O and AlCl3. The effects of solvent/catalyst system and temperature/time on the performance of the reaction are studied. HMF yield in the different solvents follows a decreasing order as DMSO > [Bmim]Cl > H2O. The highest HMF yield is achieved by CrCl3·6H2O, followed by AlCl3 and then FeCl3·6H2O. An optimal temperature/time is found at 393 K or 403 K and a time between 30 min and 480 min. Under the optimal reaction conditions, HMF yields of 54.43% and 52.86% are obtained in DMSO with CrCl3·6H2O at 403 K and 480 min and AlCl3 at 393 K and 240 min, respectively. The mechanism of the halide chlorides catalyzed glucose conversion reaction is proposed. The kinetic model is established to describe the HMF formation and the experimental data conform to the model.

  2. Interaction between bacterial outer membrane proteins and periplasmic quality control factors: a kinetic partitioning mechanism.

    Science.gov (United States)

    Wu, Si; Ge, Xi; Lv, Zhixin; Zhi, Zeyong; Chang, Zengyi; Zhao, Xin Sheng

    2011-09-15

    The OMPs (outer membrane proteins) of Gram-negative bacteria have to be translocated through the periplasmic space before reaching their final destination. The aqueous environment of the periplasmic space and high permeability of the outer membrane engender such a translocation process inevitably challenging. In Escherichia coli, although SurA, Skp and DegP have been identified to function in translocating OMPs across the periplasm, their precise roles and their relationship remain to be elucidated. In the present paper, by using fluorescence resonance energy transfer and single-molecule detection, we have studied the interaction between the OMP OmpC and these periplasmic quality control factors. The results of the present study reveal that the binding rate of OmpC to SurA or Skp is much faster than that to DegP, which may lead to sequential interaction between OMPs and different quality control factors. Such a kinetic partitioning mechanism for the chaperone-substrate interaction may be essential for the quality control of the biogenesis of OMPs.

  3. [Adsorption kinetics and mechanism of lead (II) on polyamine-functionalized mesoporous activated carbon].

    Science.gov (United States)

    Li, Kun-Quan; Wang, Yan-Jin; Yang, Mei-Rong; Zhu, Zhi-Qiang; Zheng, Zheng

    2014-08-01

    Bagasse mesoporous carbon was prepared by microwave assisted H3 PO4 activation. Amido and imido groups were modified with ethanediamine on the channels' surface of mesoporous carbon through nitric oxidation and amide reaction. The influence of Pb(II) concentration, adsorption time on Pb(II) adsorption on the ethanediamine-modified mesoporous carbon (AC-EDA) was investigated. The adsorption kinetics and mechanism were also discussed. The results showed that AC-EDA had a great performance for Pb(II) adsorption, and more than 70% of Pb(II) was adsorbed in 5 minutes. The adsorption amount of Pb(II) on the carbon increased with the increase of solution pH in acidic conditions. It was found that AC-EDA had different binding energies on different adsorption sites for Pb(II) separation. The Pb(II) adsorption process on AC-EDA was controlled by intra-particle diffusion in the first 3 min, and then film diffusion played the important pole on the adsorption. The adsorption amount increased with the increase of temperature, indicating the adsorption was an endothermic reaction. The high adsorption energy (> 11 kJ x mol(-1)) implied that the) adsorption was a chemical adsorption. The XPS of AC-EDA before and after Pb(II) adsorption showed that the polyamine group was involved in the adsorption, and should be a main factor of the high efficient adsorption.

  4. NMR of α-synuclein–polyamine complexes elucidates the mechanism and kinetics of induced aggregation

    Science.gov (United States)

    Fernández, Claudio O; Hoyer, Wolfgang; Zweckstetter, Markus; Jares-Erijman, Elizabeth A; Subramaniam, Vinod; Griesinger, Christian; Jovin, Thomas M

    2004-01-01

    The aggregation of α-synuclein is characteristic of Parkinson's disease (PD) and other neurodegenerative synucleinopathies. The 140-aa protein is natively unstructured; thus, ligands binding to the monomeric form are of therapeutic interest. Biogenic polyamines promote the aggregation of α-synuclein and may constitute endogenous agents modulating the pathogenesis of PD. We characterized the complexes of natural and synthetic polyamines with α-synuclein by NMR and assigned the binding site to C-terminal residues 109–140. Dissociation constants were derived from chemical shift perturbations. Greater polyamine charge (+2 → +5) correlated with increased affinity and enhancement of fibrillation, for which we propose a simple kinetic mechanism involving a dimeric nucleation center. According to the analysis, polyamines increase the extent of nucleation by ∼104 and the rate of monomer addition ∼40-fold. Significant secondary structure is not induced in monomeric α-synuclein by polyamines at 15°C. Instead, NMR reveals changes in a region (aa 22–93) far removed from the polyamine binding site and presumed to adopt the β-sheet conformation characteristic of fibrillar α-synuclein. We conclude that the C-terminal domain acts as a regulator of α-synuclein aggregation. PMID:15103328

  5. Electro-oxidation of diclofenac at boron doped diamond: Kinetics and mechanism

    International Nuclear Information System (INIS)

    Zhao Xu; Hou Yining; Liu Huijuan; Qiang Zhimin; Qu Jiuhui

    2009-01-01

    Diclofenac is a common anti-inflammatory drug. Its electrochemical degradation at boron doped diamond electrode was investigated in aqueous solution. The degradation kinetics and the intermediate products were studied. Results showed that electro-oxidation was effective in inducing the degradation of diclofenac with 30 mg/L initial concentration, ensuring a mineralization degree of 72% after a 4 h treatment with the applied bias potential of 4.0 V. The effects of applied bias potential and addition of NaCl on diclofenac degradation were investigated. Different degradation mechanisms of diclofenac were involved at various applied bias potentials. With the addition of NaCl, some chlorination intermediates including dichlorodiclofenac were identified, which lead to the total organic carbon increase compared with the electrolysis process without NaCl addition at the reaction initial period. The main intermediates including 2,6-dichlorobenzenamine, 2,5-dihydroxybenzyl alcohol, and benzoic acid are identified at the time of 2 h. 1-(2,6-Dichlorocyclohexa-2,4-dienyl)indolin-2-one were also identified. These intermediates disappeared gradually with the extension of reaction time. Small molecular acids were identified finally. Based on these results, a degradation pathway of diclofenac was proposed.

  6. Electro-oxidation of diclofenac at boron doped diamond: Kinetics and mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Xu; Hou Yining; Liu Huijuan; Qiang Zhimin [State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085 (China); Qu Jiuhui [State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085 (China)], E-Mail: jhqu@mail.rcees.ac.cn

    2009-07-01

    Diclofenac is a common anti-inflammatory drug. Its electrochemical degradation at boron doped diamond electrode was investigated in aqueous solution. The degradation kinetics and the intermediate products were studied. Results showed that electro-oxidation was effective in inducing the degradation of diclofenac with 30 mg/L initial concentration, ensuring a mineralization degree of 72% after a 4 h treatment with the applied bias potential of 4.0 V. The effects of applied bias potential and addition of NaCl on diclofenac degradation were investigated. Different degradation mechanisms of diclofenac were involved at various applied bias potentials. With the addition of NaCl, some chlorination intermediates including dichlorodiclofenac were identified, which lead to the total organic carbon increase compared with the electrolysis process without NaCl addition at the reaction initial period. The main intermediates including 2,6-dichlorobenzenamine, 2,5-dihydroxybenzyl alcohol, and benzoic acid are identified at the time of 2 h. 1-(2,6-Dichlorocyclohexa-2,4-dienyl)indolin-2-one were also identified. These intermediates disappeared gradually with the extension of reaction time. Small molecular acids were identified finally. Based on these results, a degradation pathway of diclofenac was proposed.

  7. Electrochemical mechanism and kinetics studies of haloperidol and its assay in commercial formulations

    International Nuclear Information System (INIS)

    Ribeiro, Francisco W.P.; Soares, Janete E.S.; Becker, Helena; De Souza, Djenaine; Lima-Neto, Pedro de; Correia, Adriana N.

    2011-01-01

    The kinetics and mechanism for electrochemical reduction of haloperidol, a psychotherapeutic drug used in the treatment of schizophrenia, were studied using square wave and cyclic voltammetries allied to a hanging mercury drop electrode. The experimental and voltammetric parameters were optimized at 0.04 mol L -1 Brinton-Robinson buffer (pH 10), with a pulse potential frequency of 100 s -1 , a pulse amplitude of 30 mV and scan increment of 2 mV. Two well-defined peaks were observed, which exhibited properties of fast electron transfer with a strong adsorption process of reactants and products on the electrode surface. The first peak was related to a fast and reversible anion-radical formation originating from the reduction of the carbonyl group, and the second was related to the irreversible reduction of the anion-radical previously formed. Analytical parameters such as: linearity range, equation of the analytical curves, correlation coefficients, detection and quantification limits, recovery efficiency, and relative standard deviation for intraday and interday were compared to similar results obtained by use of the UV-vis spectrophotometry technique, and the analytical results obtained in commercial formulations show that the voltammetric procedure using a hanging mercury drop electrode is suitable for analyzing haloperidol in complex commercial formulation samples.

  8. An Engineered Kinetic Amplification Mechanism for Single Nucleotide Variant Discrimination by DNA Hybridization Probes.

    Science.gov (United States)

    Chen, Sherry Xi; Seelig, Georg

    2016-04-20

    Even a single-nucleotide difference between the sequences of two otherwise identical biological nucleic acids can have dramatic functional consequences. Here, we use model-guided reaction pathway engineering to quantitatively improve the performance of selective hybridization probes in recognizing single nucleotide variants (SNVs). Specifically, we build a detection system that combines discrimination by competition with DNA strand displacement-based catalytic amplification. We show, both mathematically and experimentally, that the single nucleotide selectivity of such a system in binding to single-stranded DNA and RNA is quadratically better than discrimination due to competitive hybridization alone. As an additional benefit the integrated circuit inherits the property of amplification and provides at least 10-fold better sensitivity than standard hybridization probes. Moreover, we demonstrate how the detection mechanism can be tuned such that the detection reaction is agnostic to the position of the SNV within the target sequence. in contrast, prior strand displacement-based probes designed for kinetic discrimination are highly sensitive to position effects. We apply our system to reliably discriminate between different members of the let-7 microRNA family that differ in only a single base position. Our results demonstrate the power of systematic reaction network design to quantitatively improve biotechnology.

  9. Reaction kinetics and mechanisms of organosilicon fungicide flusilazole with sulfate and hydroxyl radicals.

    Science.gov (United States)

    Mercado, D Fabio; Bracco, Larisa L B; Arques, Antonio; Gonzalez, Mónica C; Caregnato, Paula

    2018-01-01

    Flusilazole is an organosilane fungicide used for treatments in agriculture and horticulture for control of diseases. The reaction kinetics and mechanism of flusilazole with sulfate and hydroxyl radicals were studied. The rate constant of the radicals with the fungicide were determined by laser flash photolysis of peroxodisulfate and hydrogen peroxide. The results were 2.0 × 10 9 s -1 M -1 for the reaction of the fungicide with HO and 4.6 × 10 8  s -1  M -1 for the same reaction with SO 4 - radicals. The absorption spectra of organic intermediates detected by laser flash photolysis of S 2 O 8 2- with flusilazole, were identified as α-aminoalkyl and siloxyl radicals and agree very well with those estimated employing the time-dependent density functional theory with explicit account for bulk solvent effects. In the continuous photolysis experiments, performed by photo-Fenton reaction of the fungicide, the main degradation products were: (bis(4-fluorophenyl)-hydroxy-methylsilane) and the non-toxic silicic acid, diethyl bis(trimethylsilyl) ester, in ten and twenty minutes of reaction, respectively. Copyright © 2017. Published by Elsevier Ltd.

  10. KINETICS AND MECHANISM OF PHOTOINDUCED POLYMERIZATION BY α,α-DIMETHOXY-α-PHENYL ACETOPHENONE

    Institute of Scientific and Technical Information of China (English)

    WANG Xiuzhi; LI Miaozhen; CHANG Zhiying; WANG Erjian

    1993-01-01

    α,α- dimethoxy- α-phenyl acetophenone (DMPA) is an efficient and thermally stable photoinitiator.Here its spectral characteristics in the transient state were shown. The transient species were identified as a benzoyl radical and a dimethoxyl benzyl radical that played a primary initiation role in polymerization. The kinetics and mechanism of the bulk polymerization of MMA were investigated. The exponent of DMPA concentration and κp/κt1/2 value were found to be 0.5 and 0.066 mol-1/2l1/2 s-1/2 , respectively. The existence of oxygen led to obtain the polymer with higher molecular weight, which can be attributed to the occurrence of the subsequent polymerization induced by active polymer end group. In the photocrosslinking reaction, the dependence of DMPA content on initial rate has been found. A principal reason is that the sample contained higher percentage of DMPA has higher light-absorbed efficiency. In solid film, higher concentration of DMPA is permitted to be used because there is little excited state self-quenching effect in the rigid medium.

  11. Hydrolysis mechanism of BH4- in moist acetonitrile. III. Kinetic isotope effects

    International Nuclear Information System (INIS)

    Meeks, B.S. Jr.; Kreevoy, M.M.

    1979-01-01

    The present work and a concurrent paper show that, in the presence of acetic acid, BH 4 - in acetonitrile is rapidly converted to BH 3 OCOCH 3 - and that previous kinetic studies of the hydrolysis of BH 4 - in such solutions actually referred to the hydrolysis of BH 3 OCOCH 3 - . As previously shown, the substrate (now shown to be BH 3 OCOCH 3 - ) complexes with acetic acid, with a complexing constant of about 160. That complex hydrolyzes by spontaneous and water-catalyzed paths. The present paper shows that the latter reaction is accelerated 15 to 40% by the substitution of D for H on boron. The rate is reduced, by a factor of approx. 1.75, by replacing all the hydroxylic hydrogen with deuterium. These results are consistent with BH 3 OC(CH 3 )O . HOCOCH 3 as the acetic acid-substrate complex. The displacement of the incipient biacetate ion by water is rate determining in this process. Isotopic substitution at either position reduces the rate of the spontaneous process. Its mechanism is uncertain. 2 figures, 3 tables

  12. Kinetic mechanism and isotope effects of Pseudomonas cepacia 3-hydroxybenzoate-t-hydroxylase

    International Nuclear Information System (INIS)

    Wang, L.H.; Yu, Y.; Hamzah, R.Y.; Tu, S.C.

    1986-01-01

    The kinetic mechanism of Pseudomonas cepacia 3-hydroxybenzoate-6-hydroxylase has been delineated. Double reciprocal plots of initial rate versus m-hydroxybenzoate concentration at a constant level of oxygen and several fixed concentrations of NADH yielded a set of converging lines. Similar reciprocal plots of velocity versus NADH concentration at a constant oxygen level and several fixed m-hydroxybenzoate concentrations also showed converging lines. In contrast, double reciprocal plots of initial rate versus NADH concentration at a fixed m-hydroxybenzoate level and several oxygen concentrations showed a series of parallel lines. Parallel lines were also obtained from double reciprocal plots of initial rate versus m-hydroxybenzoate concentration at a fixed NADH level and varying oxygen concentrations. These results suggest a sequential binding of m-hydroxybenzoate and NADH by the hydroxylase. The enzyme-bound FAD is reduced and NAD is released. The reduced enzyme subsequently reacts with oxygen leading to the formation of other products. This hydroxylase exhibited a primary isotope effect of /sup D/V = 3.5 for (4R)-[4- 2 H] NADH but no isotope effect was observed with (4S)-[4- 2 H]NADH. An isotope effect of /sup T/V/K = 5.0 was also observed using (4R)-[4- 3 H]NADH. This tritium isotope effect was apparently independent of m-hydroxybenzoate concentration

  13. Studies on adsorption, reaction mechanisms and kinetics for photocatalytic degradation of CHD, a pharmaceutical waste.

    Science.gov (United States)

    Sarkar, Santanu; Bhattacharjee, Chiranjib; Curcio, Stefano

    2015-11-01

    The photocatalytic degradation of chlorhexidine digluconate (CHD), a disinfectant and topical antiseptic and adsorption of CHD catalyst surface in dark condition has been studied. Moreover, the value of kinetic parameters has been measured and the effect of adsorption on photocatalysis has been investigated here. Substantial removal was observed during the photocatalysis process, whereas 40% removal was possible through the adsorption route on TiO2 surface. The parametric variation has shown that alkaline pH, ambient temperature, low initial substrate concentration, high TiO2 loading were favourable, though at a certain concentration of TiO2 loading, photocatalytic degradation efficiency was found to be maximum. The adsorption study has shown good confirmation with Langmuir isotherm and during the reaction at initial stage, it followed pseudo-first-order reaction, after that Langmuir Hinshelwood model was found to be appropriate in describing the system. The present study also confirmed that there is a significant effect of adsorption on photocatalytic degradation. The possible mechanism for adsorption and photocatalysis has been shown here and process controlling step has been identified. The influences of pH and temperature have been explained with the help of surface charge distribution of reacting particles and thermodynamic point of view respectively. Copyright © 2015 Elsevier Inc. All rights reserved.

  14. Mechanism of seasonal eddy kinetic energy variability in the eastern equatorial Pacific Ocean

    Science.gov (United States)

    Wang, Minyang; Du, Yan; Qiu, Bo; Cheng, Xuhua; Luo, Yiyong; Chen, Xiao; Feng, Ming

    2017-04-01

    Enhanced mesoscale eddy activities or tropical instability waves (TIWs) exist along the northern front of the cold tongue in the eastern equatorial Pacific Ocean. In this study, we investigate seasonal variability of eddy kinetic energy (EKE) over this region and its associated dynamic mechanism using a global, eddy-resolving ocean general circulation model (OGCM) simulation, the equatorial mooring data, and satellite altimeter observations. The seasonal-varying enhanced EKE signals are found to expand westward from 100°W in June to 180°W in December between 0°N and 6°N. This westward expansion in EKE is closely connected to the barotropically-baroclinically unstable zonal flows that are in thermal-wind balance with the seasonal-varying thermocline trough along 4°N. By adopting an 1½-layer reduced-gravity model, we confirm that the seasonal perturbation of the thermocline trough is dominated by the anticyclonic wind stress curl forcing, which develops due to southerly winds along 4°N from June to December.

  15. Kinetic evidence for a two-stage mechanism of protein denaturation by guanidinium chloride.

    Science.gov (United States)

    Jha, Santosh Kumar; Marqusee, Susan

    2014-04-01

    Dry molten globular (DMG) intermediates, an expanded form of the native protein with a dry core, have been observed during denaturant-induced unfolding of many proteins. These observations are counterintuitive because traditional models of chemical denaturation rely on changes in solvent-accessible surface area, and there is no notable change in solvent-accessible surface area during the formation of the DMG. Here we show, using multisite fluorescence resonance energy transfer, far-UV CD, and kinetic thiol-labeling experiments, that the guanidinium chloride (GdmCl)-induced unfolding of RNase H also begins with the formation of the DMG. Population of the DMG occurs within the 5-ms dead time of our measurements. We observe that the size and/or population of the DMG is linearly dependent on [GdmCl], although not as strongly as the second and major step of unfolding, which is accompanied by core solvation and global unfolding. This rapid GdmCl-dependent population of the DMG indicates that GdmCl can interact with the protein before disrupting the hydrophobic core. These results imply that the effect of chemical denaturants cannot be interpreted solely as a disruption of the hydrophobic effect and strongly support recent computational studies, which hypothesize that chemical denaturants first interact directly with the protein surface before completely unfolding the protein in the second step (direct interaction mechanism).

  16. [Removal Kinetics and Mechanism of Aniline by Manganese-oxide-modified Diatomite].

    Science.gov (United States)

    Xiao, Shao-dan; Liu, Lu; Jiang, Li-ying; Chen, Jian-meng

    2015-06-01

    A novel rapid green one-step method was developed for the preparation of manganese modified diatomite (Mn-D) by treating roasted diatomite with an acidic permanganate solution. The effects of calcination temperature and mass ratio of KMnO4 and diatomite (p) on aniline removal efficiency of Mn-D were investigated. The removal kinetics and mechanism of aniline by Mn-D were also discussed. The results showed that when the optimal calcination temperature was 450 degrees C, p was 1.6, and the loading amounts of δ-MnO2 was 0.82 g x g(-1), Mn-D had a great performance for aniline removal, and more than 80% of aniline was adsorbed within 10 minutes, accompanied with the release of Mn2+. In acidic conditions, the adsorption process on Mn-D followed pseudo-second-order and was mainly controlled by intra-particle diffusion. The best fitting of the experimental adsorption data was given by the Freundlich equation. Gas chromatograph-mass spectrometer was applied to identify the reaction intermediates at different times, and azobenzene was found to be the main reaction intermediate in the degradation system. Based on the above observations, the possible degradation pathway of aniline by Mn-D was proposed.

  17. Investigation of the kinetics and mechanism of the glycerol chlorination reaction using gas chromatography–mass spectrometry

    Directory of Open Access Journals (Sweden)

    JUN WANG

    2010-01-01

    Full Text Available As a primary by-product in biodiesel production, glycerol can be used to prepare an important fine chemical, epichlorohydrin, by the glycerol chlorination reaction. Although this process has been applied in industrial production, unfortunately, less attention has been paid to the analysis and separation of the compounds in the glycerol chlorination products. In this study, a convenient and accurate method to determine the products in glycerol chlorination reaction was established and based on the results the kinetic mechanism of the reaction was investigated. The structure of main products, including 1,3--dichloropropan-2-ol, 2,3-dichloropropan-1-ol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol and glycerol was ascertained by gas chromatography–mass spectrometry and the isomers of the products were distinguished. Apidic acid was considered as the best catalyst because of its excellent catalytic effect and high boiling point. The mechanism of the glycerol chlorination reaction was proposed and a new kinetic model was developed. Kinetic equations of the process in the experimental range were obtained by data fitting and the activation energies of each tandem reaction were 30.7, 41.8, 29.4 and 49.5 kJ mol-1, respectively. This study revealed the process and mechanism of the kinetics and provides the theoretical basis for engineering problems.

  18. Kinetic mechanism of Toxoplasma gondii adenosine kinase and the highly efficient utilization of adenosine

    Science.gov (United States)

    Naguib, Fardos N. M.; Rais, Reem H.; Al Safarjalani, Omar N.; el Kouni, Mahmoud H.

    2015-01-01

    Toxoplasma gondii has an extraordinarily ability to utilize adenosine (Ado) as the primary source of all necessary purines in this parasite which lacks de novo purine biosynthesis. The activity of T. gondii adenosine kinase (TgAK, EC 2.7.1.20) is responsible for this efficient salvage of Ado in T. gondii. To fully understand this remarkable efficiency of TgAK in the utilization of Ado, complete kinetic parameters of this enzyme are necessary. Initial velocity and product inhibition studies of TgAK demonstrated that the basic mechanism of this enzyme is a hybrid random bi-uni ping-pong uni-bi. Initial velocity studies showed an intersecting pattern, consistent with substrate-enzyme-co-substrate complex formation and a binding pattern indicating that binding of the substrate interferes with the binding of the co-substrate and vice versa. Estimated kinetic parameters were KAdo = 0.002 ± 0.0002 mM, KATP = 0.05 ± 0.008 mM, and Vmax = 920 ± 35 μmol/min/mg protein. Ado exhibited substrate inhibition suggesting the presence of more than one binding site for Ado on the enzyme. ATP relieved substrate inhibition by Ado. Thus, Ado also binds to the ATP binding site. AMP was competitive with ATP, inferring that AMP binds to the same site as ATP. AMP, ADP and ATP were non-competitive with Ado, therefore, none of these nucleotides binds to the Ado binding site. Combining ATP with ADP was additive. Therefore, the binding of either ATP or ADP does not interfere with the binding of the other. It is concluded that for every ATP consumed, TgAK generates three new AMPs. These findings along with the fact that a wide range of nucleoside 5′-mono, di, and triphosphates could substitute for ATP as phosphate donors in this reaction may explain the efficient and central role played by TgAK in the utilization of Ado as the major source from which all other purines can be synthesized in T. gondii. PMID:26112826

  19. SENSITIVITY ANALYSIS OF KINETIC CONSTANTS AS A TOOL FOR ELUCIDATING THE POLYMERIZATION MECHANISM OF ACRYL-FURANIC COMPOUNDS

    Directory of Open Access Journals (Sweden)

    Jurgen Lange

    2013-12-01

    Full Text Available By means of the sensitivity analysis of kinetics constants in a proposed mechanism for radical polymerization of acrylfuranic compounds [Furfuryl Acrylate (FA and Methacrylate (FM],it is elucidated which elementary steps are relevant in the phenomenology. In this analysis, the application of Come's methodology allows to classify the elementary steps of a mechanism in three categories: Non-sensible, Non-determinant, Sensible. The results obtained with this tool in modeling of experimental data in free radical polymerization of FA and FM suggest that kinetic mechanism consists mainly on five elementary steps: 1 Primary initiation, 2 propagation, 3 degradative transfers (which include intermolecular and primary, 4 re-initiation and 5 cross-termination. Thus, taking into account these elementary steps in mathematical modeling, the polymerization of FA and FM in different experimental conditions was successfully simulated.

  20. Investigation of the enzymatic mechanism of yeast orotidine-5'-monophosphate decarboxylase using 13C kinetic isotope effects

    International Nuclear Information System (INIS)

    Smiley, J.A.; Bell, J.B.; Jones, M.E.; Paneth, P.; O'Leary, M.H.

    1991-01-01

    Orotidine-5'-monophosphate decarboxylase (ODCase) from Saccharomyces cerevisiae displays an observed 13 C kinetic isotope effect of 1.0247 ± 0.0008 at 25 C, pH 6.8. The observed isotope effect is sensitive to changes in the reaction medium, such as pH, temperature, or glycerol content. The value of 1.0494 ± 0.0006 measured at pH 4.0, 25 C, is not altered significantly by temperature or glycerol, and thus the intrinsic isotope effect for the reaction is apparently being observed under these conditions and decarboxylation is almost entirely rate-determining. These data require a catalytic mechanism with freely reversible binding and one in which a very limited contribution to the overall rate is made by chemical steps preceding decarboxylation; the zwitterion mechanism of Beak and Siegel, which involves only protonation of the pyrimidine ring, is such a mechanism. With use of an intrinsic isotope effect of 1.05, a partitioning factor of less than unity is calculated for ODCase at pH 6.0, 25 C. A quantitative kinetic analysis using this result excludes the possibility of an enzymatic mechanism involving covalent attachment of an enzyme nucleophile to C-5 of the pyrimidine ring. These data fit a kinetic model in which an enzyme proton necessary for catalysis is titrated at high pH, thus providing evidence for the catalytic mechanism of Beak and Siegal

  1. Kinetics and mechanism of permanganate oxidation of iota- and lambda-carrageenan polysaccharides as sulfated carbohydrates in acid perchlorate solutions.

    Science.gov (United States)

    Hassan, Refat M; Fawzy, Ahmed; Ahmed, Gamal A; Zaafarany, Ishaq A; Asghar, Basim H; Takagi, Hideo D; Ikeda, Yasuhisa

    2011-10-18

    The kinetics of oxidation of iota- and lambda-carrageenan as sulfated carbohydrates by permanganate ion in aqueous perchlorate solutions at a constant ionic strength of 2.0 mol dm(-3) have been investigated spectrophotometrically. The pseudo-first-order plots were found to be of inverted S-shape throughout the entire courses of reactions. The initial rates were found to be relatively slow in the early stages, followed by an increase in the oxidation rates over longer time periods. The experimental observations showed first-order dependences in permanganate and fractional first-order kinetics with respect to both carrageenans concentration for both the induction and autoacceleration periods. The results obtained at various hydrogen ion concentrations showed that the oxidation processes in these redox systems are acid-catalyzed throughout the two stages of oxidation reactions. The added salts lead to the prediction that Mn(III) is the reactive species throughout the autoacceleration periods. Kinetic evidence for the formation of 1:1 intermediate complexes was revealed. The kinetic parameters have been evaluated and tentative reaction mechanisms in good agreement with the kinetic results are discussed. Copyright © 2011 Elsevier Ltd. All rights reserved.

  2. Kinetics and mechanisms of iron redox reactions in silicate melts: The effects of temperature and alkali cations

    Energy Technology Data Exchange (ETDEWEB)

    Magnien, V.; Pinet, O. [CEA VALRHO, SCDV/LEBV, F-30207 Bagnols Sur Ceze, (France); Magnien, V.; Neuville, D. R.; Roux, J.; Richet, P. [IPGP, CNRS, Physique des Mineraux et Magmas, F-75252 Paris 05, (France); Cormier, L. [Univ Paris 06, IMPMC, F-75015 Paris, (France); Hazemann, J. L. [CNRS, Inst Neel, F-38043 Grenoble, (France); De Ligny, D. [Univ Lyon 1, LMLC, CNRS, UMR 5620, F-69622 Villeurbanne, (France); Pascarelli, S. [European Synchrotron Radiat Facil, F-38043 Grenoble, (France); Vickridge, I. [Univ Paris 06, INSP, F-75015 Paris, (France)

    2008-07-01

    The kinetics and the mechanisms of iron redox reactions in molten Fe-bearing pyroxene compositions have been investigated by Raman spectroscopy and X-ray absorption Near Edge Structure (XANES) experiments at the iron K-edge. The former experiments have been made only near the glass transition whereas the latter have also been performed from about 1300 to 2100 K. The same kinetics are observed with both techniques. They are described by characteristic times that depend primarily on temperature and not on the initial redox state. At high temperatures, where both kinds of reactions could be investigated, these times are similar for oxidation and reduction. From these characteristic times we have calculated as a function of temperature and composition a parameter termed effective redox diffusivity. For a given melt, the diffusivities follow two distinct Arrhenius laws, which indicate that the mechanisms of the redox reaction are not the same near the glass transition and at high temperatures. As is now well established, diffusion of divalent cations is the dominant mechanism at low temperatures but the enhanced kinetics observed for alkali-bearing melts indicate that Li{sup +} and Na{sup +} also participate in ionic transport. At super-liquidus temperatures, in contrast, diffusion of oxygen represents the dominant mechanism. (authors)

  3. A detailed kinetic study of the direct ring opening of cyclohexane and methylcyclohexane over monofunctional Ir/Al{sub 2}O{sub 3} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Hui; Gutierrez, O.Y.; Lercher, J.A. [Technische Univ. Muenchen (Germany). Catalysis Research Center

    2011-07-01

    The present study analyses a series of Al{sub 2}O{sub 3}-supported iridium catalysts with different pretreatments and addresses the kinetic features and structural requirements of direct ring opening of cyclohexane and methylcyclohexane catalyzed by Ir in absence of acid-catalyzed ring contraction. Mild reaction conditions and high H{sub 2}/hydrocarbon ratios (200-1000) were used to improve accuracy of kinetic measurements and to negate deactivation. Isomerization and dehydrogenation pathways were suppressed to low extents (1-5%) over the weakly acidic catalysts under the reaction conditions applied. Three main observations are shown: 1) initial selectivity to ring opening products (ROPs) increases with iridium dispersion; 2) optimal H{sub 2} pressures differ not only between primary and secondary products, but also among ROPs and fragments; 3) the air-calcination step before catalyst reduction imposes a significant impact on both activity and product distribution. (orig.)

  4. Debromination of polybrominated diphenyl ethers by Ni/Fe bimetallic nanoparticles: Influencing factors, kinetics, and mechanism

    International Nuclear Information System (INIS)

    Fang Zhanqiang; Qiu Xinhong; Chen Jinhong; Qiu Xiuqi

    2011-01-01

    Polybrominated diphenyl ethers have been identified as a new class of organic pollutants with ecological risk due to their toxicity, bioaccumulation, and global distribution. Proper remediation technologies are needed to remove them from the environment. In this paper, Ni/Fe bimetallic nanoparticles were synthesized by chemical deposition and used to degrade decabromodiphenyl ether (BDE209). The characteristics of Ni/Fe nanoparticles were analyzed by transmission electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, and Brunnaer-Emmett-Teller surface area analysis. Ni/Fe bimetallic nanoparticles with diameters in the order of 20-50 nm could effectively degrade BDE209 in the solvent (tetrahydrofuran/water). Influence factors, such as Ni/Fe nanoparticle dosage, initial BDE209 concentration, and Ni loading, on the removal of BDE209 were studied. The results indicated that the degradation of BDE209 followed pseudo-first-order kinetics, and the degradation rate of BDE209 increased with increasing the amount of nano Ni/Fe particles, Ni/Fe ratio, and decreasing the initial concentration of BDE209. Through analyzed the mass balance of the BDE209 removal, degradation was the main process of BDE209 removal. The mechanism of debromination was deduced by analyzing the reaction products using gas chromatography-mass spectrometry, the bromide ion in the solution and varying the solvent conditions. Stepwise hydrogen reduction is the main process of debromination, and the hydrion play an important role in the reaction. Moreover, the experiment of long term performance and leaching of Ni were also carried out to test the stability and durability of Ni/Fe nanoparticles in BDE209 degradation.

  5. Kinetics and Mechanism Study of Competitive Inhibition of Jack-Bean Urease by Baicalin

    Science.gov (United States)

    Tan, Lirong; Su, Jiyan; Wu, Dianwei; Yu, Xiaodan; Su, Zuqing; Wu, Xiaoli; Kong, Songzhi; Lai, Xiaoping; Lin, Ji; Su, Ziren

    2013-01-01

    Baicalin (BA) is the principal component of Radix Scutellariae responsible for its pharmacological activity. In this study, kinetics and mechanism of inhibition by BA against jack-bean urease were investigated for its therapeutic potential. It was revealed that the IC50 of BA against jack-bean urease was 2.74 ± 0.51 mM, which was proved to be a competitive and concentration-dependent inhibition with slow-binding progress curves. The rapid formation of initial BA-urease complex with an inhibition constant of K i = 3.89 × 10−3 mM was followed by a slow isomerization into the final complex with an overall inhibition constant of K i* = 1.47 × 10−4 mM. High effectiveness of thiol protectors against BA inhibition indicated that the strategic role of the active-site sulfhydryl group of the urease was involved in the blocking process. Moreover, the inhibition of BA was proved to be reversible due to the fact that urease could be reactivated by dithiothreitol but not reactant dilution. Molecular docking assay suggested that BA made contacts with the important activating sulfhydryl group Cys-592 residues and restricted the mobility of the active-site flap. Taken together, it could be deduced that BA was a competitive inhibitor targeting thiol groups of urease in a slow-binding manner both reversibly and concentration-dependently, serving as a promising urease inhibitor for treatments on urease-related diseases. PMID:24198731

  6. Reaction mechanisms and kinetics of the iminovinylidene radical with NO: Ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Hsiao, Ming-Kai; Chung, Yi-Hua; Hung, Yu-Ming; Chen, Hui-Lung, E-mail: chl3@faculty.pccu.edu.tw [Department of Chemistry and Institute of Applied Chemistry, Chinese Culture University, Taipei 111, Taiwan (China)

    2014-05-28

    The nitric oxide (NO) is a notorious compound for polluting environment. Recent year, removing nitric oxide from the atmosphere becomes a focus of the investigation. In our work, we study the iminovinylidene (HNCC) radical reacted with NO molecule. The mechanism and kinetic for reaction of the HNCC radical with the NO molecule is investigated via considering the possible channels of the N and O atoms of NO attacking the N and C atoms of the HNCC based on the high level ab initio molecular orbital calculations in conjunction with variational TST and RRKM calculations. The species involved have been optimized at the B3LYP/6-311++G(3df,2p) level and their single-point energies are refined by the CCSD(T)/aug-cc-PVQZ//B3LYP/6-311++G(3df,2p) method. The calculated potential energy surfaces indicated that energetically the most favorable channel for the HNCC + NO reaction was predicted to be the formation of HNC+CNO (P8) product via the addition reaction of the C atom of HNCC radical and the N atom of NO with the head to head orientation. To rationalize the scenario of the calculated results, we also employ the Fukui functions and HSAB theory to seek for a possible explanation. In addition, the reaction rate constants were calculated using VariFlex code, and the results show that the total rate coefficient, k{sub total}, at Ar pressure 760 Torr can be represented with an equation: k{sub total} = 6.433 × 10{sup −11} T {sup 0.100} exp(0.275 kcal mol{sup −1}/RT) at T = 298–3000 K, in units of cm{sup 3} molecule{sup −1} s{sup −1}.

  7. A kinetic study of the mechanism of radiation induced agglomeration of ovalbumin in aqueous solution

    International Nuclear Information System (INIS)

    Tuce, Zorana; Janata, Eberhard; Radojcic, Marija; Milosavljevic, B.H.

    2001-01-01

    The effect of concentration on the protein radiolytic damage resulting in a change in molecular mass was measured in the concentration range from 0.2 to 2 mmolxdm -3 ovalbumin in phosphate buffered solutions saturated with N 2 O. The electrophoretic analysis of samples on discontinuous SDS-polyacrylamide gels in the presence or absence of 5% β-mercaptoethanol showed an expected result, i.e. that the protein scission did not take place in the absence of oxygen. Only ovalbumin agglomerates, bonded by covalent bonds other than S-S bridges, were observed. The G-value for the formation of ovalbumin agglomerates increased linearly from 1.1 to 2.4 by increasing the ovalbumin concentration from 0.2 to 2 mmolxdm -3 . The result is interpreted as to be owing to the competition between ovalbumin agglomeration and some intramolecular reactions which did not lead to the change in the molecular mass. It was also found that the G-value is independent of irradiation dose rate. The result was rationalized as a kinetic evidence that the agglomeration is not a cross-linking process, i.e. it does not occur via recombination of the protein radicals produced in the interaction of ovalbumin and · OH radical. The result suggested that the agglomeration takes place via the process of grafting, i.e. it occurs in the reaction of ovalbumin radical and an intact ovalbumin molecule. The time-resolved light scattering experiments provided an additional proof, supporting the reaction scheme of radiation-induced protein agglomeration. The biological consequences of the proposed mechanism of protein agglomeration are also discussed

  8. Kinetics and mechanism of ligand-exchange reactions of Cd(II) chelates

    Energy Technology Data Exchange (ETDEWEB)

    Nivorozhkin, L.E.; Kalabin, G.A.; Nivorozhkin, A.L.; Valeev, R.B.; Minkin, V.I.

    1987-03-01

    Tetrahedral Cd(II) bis(5-thio(or seleno)pyrazole-4-carboxaldiminates) of types II and III have been synthesized for the first time. The kinetics of the degenerate ligand exchange and enantiomerization of the complexes obtained have been studied by dynamic /sup 111/Cd, /sup 77/Se, and /sup 1/H (s = 1/2) NMR. The rate of intramolecular enantiomerization (k = 1/tau) is more than an order of magnitude greater than the corresponding values for processes of degenerate ligand exchange (a second-order reaction) determined from the dynamics of the averaging of the /sup 111/Cd-/sup 77/Se and /sup 111/Cd-N=CH spin-spin coupling constants. The cleavage and formation processes of the Cd-Se and Cd-N bonds are isoenergetic (..delta.. G/sub 298//sup not equal to/ = 14.4 kcal/mole for chelate II with X = Se and R = CH/sub 2/C/sub 6/H/sub 5/). The free energies of activation of degenerate ligand exchange determined form the dynamics of the averaging of the /sup 111/Cd N=CH spin-spin coupling constant increase from 12.7 to 17.9 kcal/mole along the following series for R: C/sub 2/H/sub 5/ < Ar < CH/sub 2/C/sub 6/H/sub 5/ < t-C/sub 4/H/sub 9/ < cyclo-C/sub 6/H/sub 11/. Replacement of the sulfur atom in the chelate ring by selenium results in increases in the rates of ligand exchange. A mechanism of degenerate ligand exchange has been proposed.

  9. Kinetic characterization of Vibrio cholerae ApbE: Substrate specificity and regulatory mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Xuan; Liang, Pingdong; Raba, Daniel Alexander; Rosas-Lemus, Mónica; Chakravarthy, Srinivas; Tuz, Karina; Juárez, Oscar; Permyakov, Eugene A.

    2017-10-24

    ApbE is a member of a novel family of flavin transferases that incorporates flavin mononucleotide (FMN) to subunits of diverse respiratory complexes, which fulfill important homeostatic functions. In this work a detailed characterization of Vibrio cholerae ApbE physiologic activity, substrate specificity and pH dependency was carried out. The data obtained show novel characteristics of the regulation and function of this family. For instance, our experiments indicate that divalent cations are essential for ApbE function, and that the selectivity depends largely on size and the coordination sphere of the cation. Our data also show that ApbE regulation by pH, ADP and potassium is an important mechanism that enhances the adaptation, survival and colonization of V. cholerae in the small intestine. Moreover, studies of the pH-dependency of the activity show that the reaction is favored under alkaline conditions, with a pKa of 8.4. These studies, together with sequence and structure analysis allowed us to identify His257, which is absolutely conserved in the family, as a candidate for the residue whose deprotonation controls the activity. Remarkably, the mutant H257G abolished the flavin transfer activity, strongly indicating that this residue plays an important role in the catalytic mechanism of ApbE.

  10. Research cooperation project on environmentally friendly technology for highly efficient mineral resources extraction and treatment. Detail design for pilot plant (Mechanical fabrication)

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-03-01

    The paper prepared plans of the mechanical equipment in the detailed design of a pilot plant in the joint research project on the environmental protection technology for highly efficient mineral resource extraction and treatment. (NEDO)

  11. Study of kinetics and mechanism of diazo compound reactions using nuclear chemical polarization

    International Nuclear Information System (INIS)

    Gragerov, I.P.; Levit, A.F.; Kiprianova, L.A.; Buchachenko, A.L.; Sterleva, T.G.

    1975-01-01

    It has been established that at the rate-determining steps of the radical reactions in which aniline interacts with isoamyl nitrite and substituted diazo salts interact with sodium methylate, tertiary fatty amines, or phosphinic acid, no transfer of a single electron occurs. The processes of single electron transfer do not seem to play a decisive role in the kinetics of most transformations of diazo compounds. Chemical nuclear polarization is shown to be suitable for kinetic studies of fast radical processes

  12. Polycaprolactone/maltodextrin nanocarrier for intracellular drug delivery: formulation, uptake mechanism, internalization kinetics, and subcellular localization.

    Science.gov (United States)

    Korang-Yeboah, Maxwell; Gorantla, Yamini; Paulos, Simon A; Sharma, Pankaj; Chaudhary, Jaideep; Palaniappan, Ravi

    2015-01-01

    Prostate cancer (PCa) disease progression is associated with significant changes in intracellular and extracellular proteins, intracellular signaling mechanism, and cancer cell phenotype. These changes may have direct impact on the cellular interactions with nanocarriers; hence, there is the need for a much-detailed understanding, as nanocarrier cellular internalization and intracellular sorting mechanism correlate directly with bioavailability and clinical efficacy. In this study, we report the differences in the rate and mechanism of cellular internalization of a biocompatible polycaprolactone (PCL)/maltodextrin (MD) nanocarrier system for intracellular drug delivery in LNCaP, PC3, and DU145 PCa cell lines. PCL/MD nanocarriers were designed and characterized. PCL/MD nanocarriers significantly increased the intracellular concentration of coumarin-6 and fluorescein isothiocyanate-labeled bovine serum albumin, a model hydrophobic and large molecule, respectively. Fluorescence microscopy and flow cytometry analysis revealed rapid internalization of the nanocarrier. The extent of nanocarrier cellular internalization correlated directly with cell line aggressiveness. PCL/MD internalization was highest in PC3 followed by DU145 and LNCaP, respectively. Uptake in all PCa cell lines was metabolically dependent. Extraction of endogenous cholesterol by methyl-β-cyclodextrin reduced uptake by 75%±4.53% in PC3, 64%±6.01% in LNCaP, and 50%±4.50% in DU145, indicating the involvement of endogenous cholesterol in cellular internalization. Internalization of the nanocarrier in LNCaP was mediated mainly by macropinocytosis and clathrin-independent pathways, while internalization in PC3 and DU145 involved clathrin-mediated endocytosis, clathrin-independent pathways, and macropinocytosis. Fluorescence microscopy showed a very diffused and non-compartmentalized subcellular localization of the PCL/MD nanocarriers with possible intranuclear localization and minor colocalization in

  13. Kinetics modeling and reaction mechanism of ferrate(VI) oxidation of benzotriazoles.

    Science.gov (United States)

    Yang, Bin; Ying, Guang-Guo; Zhang, Li-Juan; Zhou, Li-Jun; Liu, Shan; Fang, Yi-Xiang

    2011-03-01

    Benzotriazoles (BTs) are high production volume chemicals with broad application in various industrial processes and in households, and have been found to be omnipresent in aquatic environments. We investigated oxidation of five benzotriazoles (BT: 1H-benzotriazole; 5MBT: 5-methyl-1H-benzotriazole; DMBT: 5,6-dimethyl-1H-benzotriazole hydrate; 5CBT: 5-chloro-1H-benzotriazole; HBT: 1-hydroxybenzotriazole) by aqueous ferrate (Fe(VI)) to determine reaction kinetics as a function of pH (6.0-10.0), and interpreted the reaction mechanism of Fe(VI) with BTs by using a linear free-energy relationship. The pK(a) values of BT and DMBT were also determined using UV-Visible spectroscopic method in order to calculate the species-specific rate constants, and they were 8.37 ± 0.0 and 8.98 ± 0.08 respectively. Each of BTs reacted moderately with Fe(VI) with the k(app) ranged from 7.2 to 103.8 M(-1)s(-1) at pH 7.0 and 24 ± 1 °C. When the molar ratio of Fe(VI) and BTs increased up to 30:1, the removal rate of BTs reached about >95% in buffered milli-Q water or secondary wastewater effluent. The electrophilic oxidation mechanism of the above reaction was illustrated by using a linear free-energy relationship between pH-dependence of species-specific rate constants and substituent effects (σ(p)). Fe(VI) reacts initially with BTs by electrophilic attack at the 1,2,3-triazole moiety of BT, 5MBT, DMBT and 5CBT, and at the N-OH bond of HBT. Moreover, for BT, 5MBT, DMBT and 5CBT, the reactions with the species HFeO(4)(-) predominantly controled the reaction rates. For HBT, the species H(2)FeO(4) with dissociated HBT played a major role in the reaction. The results showed that Fe(VI) has the ability to degrade benzotriazoles in water. Copyright © 2011 Elsevier Ltd. All rights reserved.

  14. Kinetics and mechanism of the deep electrochemical oxidation of sodium diclofenac on a boron-doped diamond electrode

    Science.gov (United States)

    Vedenyapina, M. D.; Borisova, D. A.; Rosenwinkel, K.-H.; Weichgrebe, D.; Stopp, P.; Vedenyapin, A. A.

    2013-08-01

    The kinetics and mechanism of the deep oxidation of sodium diclofenac on a boron-doped diamond electrode are studied to develop a technique for purifying wastewater from pharmaceutical products. The products of sodium diclofenac electrolysis are analyzed using cyclic voltammetry and nuclear magnetic resonance techniques. It is shown that the toxicity of the drug and products of its electrolysis decreases upon its deep oxidation.

  15. Syntheses of organic compounds in the presence of the fused iron catalyst and their mechanisms and kinetics

    Science.gov (United States)

    Glebov, L. S.; Kliger, G. A.

    1989-10-01

    New synthetic possibilities of the reduced promoted fused iron catalyst in intermolecular and intramolecular amination, cyanation, hydrogenation-dehydrogenation, and hydrodeoxygenation reactions and intermolecular and intramolecular dehydration, polymerisation, and isotope exchange are examined. The mechanisms and kinetics of the reactions leading to the synthesis of amines, alcohols, hydrocarbons, and other organic compunds are discussed. A laser Raman spectroscopic method is described for the investigation of heterogeneous organic catalysis in situ. The bibliography includes 148 references.

  16. A second dihydroorotate dehydrogenase (Type A) of the human pathogen Enterococcus faecalis: expression, purification, and steady-state kinetic mechanism.

    Science.gov (United States)

    Marcinkeviciene, J; Jiang, W; Locke, G; Kopcho, L M; Rogers, M J; Copeland, R A

    2000-05-01

    We report the identification, expression, and characterization of a second Dihydroorotate dehydrogenase (DHODase A) from the human pathogen Enterococcus faecalis. The enzyme consists of a polypeptide chain of 322 amino acids that shares 68% identity with the cognate type A enzyme from the bacterium Lactococcus lactis. E. faecalis DHODase A catalyzed the oxidation of l-dihydroorotate while reducing a number of substrates, including fumarate, coenzyme Q(0), and menadione. The steady-state kinetic mechanism has been determined with menadione as an oxidizing substrate at pH 7.5. Initial velocity and product inhibition data suggest that the enzyme follows a two-site nonclassical ping-pong kinetic mechanism. The absorbance of the active site FMN cofactor is quenched in a concentration-dependent manner by titration with orotate and barbituric acid, two competitive inhibitors with respect to dihydroorotate. In contrast, titration of the enzyme with menadione had no effect on FMN absorbance, consistent with nonoverlapping binding sites for dihyroorotate and menadione, as suggested from the kinetic mechanism. The reductive half-reaction has been shown to be only partially rate limiting, and an attempt to evaluate the slow step in the overall reaction has been made by simulating orotate production under steady-state conditions. Our data indicate that the oxidative half-reaction is a rate-limiting segment, while orotate, most likely, retains significant affinity for the reduced enzyme, as suggested by the product inhibition pattern. Copyright 2000 Academic Press.

  17. Kinetics of cellular transformation and competing precipitation mechanisms during sub-eutectoid annealing of U10Mo alloys

    Energy Technology Data Exchange (ETDEWEB)

    Jana, Saumyadeep; Devaraj, Arun; Kovarik, Libor; Arey, Bruce W.; Sweet, Lucas E.; Varga, Tamas; Lavender, Curt A.; Joshi, Vineet V.

    2017-11-01

    Transformation kinetics of metastable body-centered cubic γ-UMo phase in U-10 wt.percent Mo alloy during annealing at sub-eutectoid temperatures of 500C and 400C has been determined as a function of time using detailed microstructural characterization by scanning electron microscopy, X-ray diffraction analysis, scanning transmission electron microscopy, and atom probe tomography. Based on the results, we found that the phase transformation is initiated by cellular transformation at both the temperatures, which results in formation of a lamellar microstructure along prior γ-UMo grain boundaries.

  18. Kinetic bed therapy to prevent nosocomial pneumonia in mechanically ventilated patients: a systematic review and meta-analysis.

    Science.gov (United States)

    Delaney, Anthony; Gray, Hilary; Laupland, Kevin B; Zuege, Danny J

    2006-01-01

    Nosocomial pneumonia is the most important infectious complication in patients admitted to intensive care units. Kinetic bed therapy may reduce the incidence of nosocomial pneumonia in mechanically ventilated patients. The objective of this study was to investigate whether kinetic bed therapy reduces the incidence of nosocomial pneumonia and improves outcomes in critically ill mechanically ventilated patients. We searched Medline, EMBASE, CINAHL, CENTRAL, and AMED for studies, as well as reviewed abstracts of conference proceedings, bibliographies of included studies and review articles and contacted the manufacturers of medical beds. Studies included were randomized or pseudo-randomized clinical trials of kinetic bed therapy compared to standard manual turning in critically ill mechanically ventilated adult patients. Two reviewers independently applied the study selection criteria and extracted data regarding study validity, type of bed used, intensity of kinetic therapy, and population under investigation. Outcomes assessed included the incidence of nosocomial pneumonia, mortality, duration of ventilation, and intensive care unit and hospital length of stay. Fifteen prospective clinical trials were identified, which included a total of 1,169 participants. No trial met all the validity criteria. There was a significant reduction in the incidence of nosocomial pneumonia (pooled odds ratio (OR) 0.38, 95% confidence interval (CI) 0.28 to 0.53), but no reduction in mortality (pooled OR 0.96, 95%CI 0.66 to 1.14), duration of mechanical ventilation (pooled standardized mean difference (SMD) -0.14 days, 95%CI, -0.29 to 0.02), duration of intensive care unit stay (pooled SMD -0.064 days, 95% CI, -0.21 to 0.086) or duration of hospital stay (pooled SMD 0.05 days, 95% CI -0.18 to 0.27). While kinetic bed therapy has been purported to reduce the incidence of nosocomial pneumonia in mechanically ventilated patients, the overall body of evidence is insufficient to support this

  19. Real-time single-molecule tethered particle motion experiments reveal the kinetics and mechanisms of Cre-mediated site-specific recombination

    Science.gov (United States)

    Fan, Hsiu-Fang

    2012-01-01

    Tyrosine family recombinases (YRs) are widely utilized in genome engineering systems because they can easily direct DNA rearrangement. Cre recombinases, one of the most commonly used types of YRs, catalyze site-specific recombination between two loxP sites without the need for high-energy cofactors, other accessory proteins or a specific DNA target sequence between the loxP sites. Previous structural, analytical ultracentrifuge and electrophoretic analyses have provided details of the reaction kinetics and mechanisms of Cre recombinase activity; whether there are reaction intermediates or side pathways involved has been left unaddressed. Using tethered particle motion (TPM), the Cre-mediated site-specific recombination process has been delineated, from beginning to end, at the single-molecule level, including the formation of abortive complexes and wayward complexes blocking inactive nucleoprotein complexes from entering the recombination process. Reversibility in the strand-cleavage/-ligation process and the formation of a thermally stable Holliday junction intermediate were observed within the Cre-mediated site-specific recombination process. Rate constants for each elementary step, which explain the overall reaction outcomes under various conditions, were determined. Taking the findings of this study together, they demonstrate the potential of single-molecule methodology as an alternative approach for exploring reaction mechanisms in detail. PMID:22467208

  20. Presenting a new kinetic model for methanol to light olefins reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson mechanism

    Science.gov (United States)

    Javad Azarhoosh, Mohammad; Halladj, Rouein; Askari, Sima

    2017-10-01

    In this study, a new kinetic model for methanol to light olefins (MTO) reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism was presented and the kinetic parameters was obtained using a genetic algorithm (GA) and genetic programming (GP). Several kinetic models for the MTO reactions have been presented. However, due to the complexity of the reactions, most reactions are considered lumped and elementary, which cannot be deemed a completely accurate kinetic model of the process. Therefore, in this study, the LHHW mechanism is presented as kinetic models of MTO reactions. Because of the non-linearity of the kinetic models and existence of many local optimal points, evolutionary algorithms (GA and GP) are used in this study to estimate the kinetic parameters in the rate equations. Via the simultaneous connection of the code related to modelling the reactor and the GA and GP codes in the MATLAB R2013a software, optimization of the kinetic models parameters was performed such that the least difference between the results from the kinetic models and experiential results was obtained and the best kinetic parameters of MTO process reactions were achieved. A comparison of the results from the model with experiential results showed that the present model possesses good accuracy.

  1. Toward a Multi-scale Phase Transition Kinetics Methodology: From Non-Equilibrium Statistical Mechanics to Hydrodynamics

    Science.gov (United States)

    Belof, Jonathan; Orlikowski, Daniel; Wu, Christine; McLaughlin, Keith

    2013-06-01

    Shock and ramp compression experiments are allowing us to probe condensed matter under extreme conditions where phase transitions and other non-equilibrium aspects can now be directly observed, but first principles simulation of kinetics remains a challenge. A multi-scale approach is presented here, with non-equilibrium statistical mechanical quantities calculated by molecular dynamics (MD) and then leveraged to inform a classical nucleation and growth kinetics model at the hydrodynamic scale. Of central interest is the free energy barrier for the formation of a critical nucleus, with direct NEMD presenting the challenge of relatively long timescales necessary to resolve nucleation. Rather than attempt to resolve the time-dependent nucleation sequence directly, the methodology derived here is built upon the non-equilibrium work theorem in order to bias the formation of a critical nucleus and thus construct the nucleation and growth rates. Having determined these kinetic terms from MD, a hydrodynamics implementation of Kolmogorov-Johnson-Mehl-Avrami (KJMA) kinetics and metastabilty is applied to the dynamic compressive freezing of water and compared with recent ramp compression experiments [Dolan et al., Nature (2007)] Lawrence Livermore National Laboratory is operated by Lawrence Livermore National Security, LLC, for the U.S. Department of Energy, National Nuclear Security Administration under Contract DE-AC52-07NA27344.

  2. Kinetics and mechanisms of elementary chemical processes of importance in combustion

    International Nuclear Information System (INIS)

    Munk, J.; Pagsberg, P.; Ratajczak, E.; Sztuba, B.; Sillesen, A.

    1988-01-01

    The technique of pulse radiolysis combined with transient ultraviolet absorption spectrophotometry has been employed in spectrokinetic studies of shortlived free radical intermediates of importance in combustion. Various source reactions for vinyl, propargyl and carboxyl radicals have been investigated and the UV-spectra of these radicals have been recorded. The spectral features have been utilized in kinetic studies of the self-reactions of the radicals and the reactions with oxygen. Kinetic results on the reaction NO + NH 2 are also reported. 10 refs. (author)

  3. On kinetics and mechanism of preparation of phenakite in the presence of Co2O3

    International Nuclear Information System (INIS)

    Semin, E.G.; Zubenko, L.V.; Burkov, V.P.; Barabanshchikova, I.B.; Rozhnovskaya, G.I.; Aslanukova, M.M.

    1978-01-01

    The kinetics of formation of mineral phenakite (BeO-SiO 2 ) in the presence of Co 2 O 3 has been studied by the methods of thermodynamics, X-ray diffraction, infrared ESR visual spectroscopy and formal kinetic analysis. The initial stage of phenakite formation necessarily involves reactions proceeding on the mineralizer reacting components interface. Mass transfer in the system is realized by one-sided diffusion of Be 2+ ions via reaction product. The activation energy is 335-380 kJ/mole

  4. Development of a Surface Plasmon Resonance Assay for the Characterization of Small-Molecule Binding Kinetics and Mechanism of Binding to Kynurenine 3-Monooxygenase.

    Science.gov (United States)

    Poda, Suresh B; Kobayashi, Masakazu; Nachane, Ruta; Menon, Veena; Gandhi, Adarsh S; Budac, David P; Li, Guiying; Campbell, Brian M; Tagmose, Lena

    2015-10-01

    Kynurenine 3-monooxygenase (KMO), a pivotal enzyme in the kynurenine pathway, was identified as a potential therapeutic target for treating neurodegenerative and psychiatric disorders. In this article, we describe a surface plasmon resonance (SPR) assay that delivers both kinetics and the mechanism of binding (MoB) data, enabling a detailed characterization of KMO inhibitors for the enzyme in real time. SPR assay development included optimization of the protein construct and the buffer conditions. The stability and inhibitor binding activity of the immobilized KMO were significantly improved when the experiments were performed at 10°C using a buffer containing 0.05% n-dodecyl-β-d-maltoside (DDM) as the detergent. The KD values of the known KMO inhibitors (UPF648 and RO61-8048) from the SPR assay were in good accordance with the biochemical LC/MS/MS assay. Also, the SPR assay was able to differentiate the binding kinetics (k(a) and k(d)) of the selected unknown KMO inhibitors. For example, the inhibitors that showed comparable IC50 values in the LC/MS/MS assay displayed differences in their residence time (τ = 1/k(d)) in the SPR assay. To better define the MoB of the inhibitors to KMO, an SPR-based competition assay was developed, which demonstrated that both UPF648 and RO61-8048 bound to the substrate-binding site. These results demonstrate the potential of the SPR assay for characterizing the affinity, the kinetics, and the MoB profiles of the KMO inhibitors.

  5. A statistical mechanical theory of proton transport kinetics in hydrogen-bonded networks based on population correlation functions with applications to acids and bases.

    Science.gov (United States)

    Tuckerman, Mark E; Chandra, Amalendu; Marx, Dominik

    2010-09-28

    Extraction of relaxation times, lifetimes, and rates associated with the transport of topological charge defects in hydrogen-bonded networks from molecular dynamics simulations is a challenge because proton transfer reactions continually change the identity of the defect core. In this paper, we present a statistical mechanical theory that allows these quantities to be computed in an unbiased manner. The theory employs a set of suitably defined indicator or population functions for locating a defect structure and their associated correlation functions. These functions are then used to develop a chemical master equation framework from which the rates and lifetimes can be determined. Furthermore, we develop an integral equation formalism for connecting various types of population correlation functions and derive an iterative solution to the equation, which is given a graphical interpretation. The chemical master equation framework is applied to the problems of both hydronium and hydroxide transport in bulk water. For each case it is shown that the theory establishes direct links between the defect's dominant solvation structures, the kinetics of charge transfer, and the mechanism of structural diffusion. A detailed analysis is presented for aqueous hydroxide, examining both reorientational time scales and relaxation of the rotational anisotropy, which is correlated with recent experimental results for these quantities. Finally, for OH(-)(aq) it is demonstrated that the "dynamical hypercoordination mechanism" is consistent with available experimental data while other mechanistic proposals are shown to fail. As a means of going beyond the linear rate theory valid from short up to intermediate time scales, a fractional kinetic model is introduced in the Appendix in order to describe the nonexponential long-time behavior of time-correlation functions. Within the mathematical framework of fractional calculus the power law decay ∼t(-σ), where σ is a parameter of the

  6. Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Hongyan, E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil; Vaghjiani, Ghanshyam L., E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil [Propellants Branch, Rocket Propulsion Division, Aerospace Systems Directorate, Air Force Research Laboratory, AFRL/RQRP, 10 E. Saturn Blvd., Edwards AFB, California 93524 (United States)

    2015-05-28

    Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH{sub 2} group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C{sub 2v} symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of which

  7. Oxidative conversion of propane over lithium-promoted magnesia catalyst. I. Kinetics and mechanism

    NARCIS (Netherlands)

    Leveles, L.; Seshan, Kulathuiyer; Lercher, J.A.; Lefferts, Leonardus

    2003-01-01

    Oxidative conversion of lower alkanes over lithium-promoted magnesia catalysts offers a viable alternative for propene and ethene production. The catalytic performance of propane oxidative dehydrogenation and cracking shows yields up to 50% of olefin (propene and ethene). The reaction kinetics were

  8. Kinetics and mechanism of the oxidation of formic and oxalic acids ...

    Indian Academy of Sciences (India)

    The oxidation of formic and oxalic acids by benzyltrimethylammonium dichloroiodate (BTMACI), in the presence of zinc chloride, leads to the formation of carbon dioxide. The reaction is first order with respect to BTMACI, zinc chloride and organic acid. Oxidation of deuteriated formic acid indicates the presence of a kinetic ...

  9. Kinetics and mechanism of the oxidation of some vicinal and non ...

    Indian Academy of Sciences (India)

    Kinetics of oxidation of five vicinal and four non-vicinal diols, and two of their monoethers, by tetrabutylammonium tribromide (TBATB) has been studied. The vicinal diols yield products arising out of glycol-bond fission, while the non-vicinal diols produce the hydroxycarbonyl compounds. The reaction is first-order with ...

  10. Kinetics and mechanism of the oxidation of some α-hydroxy acids by ...

    Indian Academy of Sciences (India)

    Unknown

    2004-11-08

    Nov 8, 2004 ... presence of a substantial kinetic isotope effect (kH/kD = 5⋅91 at 298 K). The rates of oxidation ... have been made to correlate rate and structure in this reaction. Mechanistic ... The solvent was glacial acetic acid and temperature was ≈ 298 K. .... glacial acetic acid was evaporated to dryness under reduced ...

  11. Study of physical mechanisms and their influence on dry anaerobic digestion kinetics: experimentations and modelization

    International Nuclear Information System (INIS)

    Bollon, Julien

    2012-01-01

    Anaerobic digestion is a biological process that converts organic matter into a methane rich gas (biogas). Among industrial technologies, dry processes (above 15 % total solid content) are more and more used because of their advantages in comparison with conventional wet processes. However, dry anaerobic digestion processes are poorly known and studied because of the 'pasty' nature of digestion media (rheological behavior, equilibria, transfers, biological kinetics). This thesis focuses on two major aspects: i) the nature of the chemical equilibria (sorption, diffusion) involved in digestion media, ii) the establishment and application of a kinetic model adapted to dry media. We first demonstrated that the diffusional mass transfer is highly reduced with increasing total solid without any agitation. One of the consequences is the importance of the liquid-gas transfer for the production of biogas. Then, we have developed a dedicated kinetic model that enables to understand the variability of the kinetic with total solid content. The impacts of this work are both at the laboratory scale, especially for the operation of Specific Methanogenic Activity tests, and at industrial scale, with the need to control total solid content for optimal efficiency, and to adapt the agitation to improve degradation yields. The developed model can be useful for the design and operation of bio-methanization facilities. (author) [fr

  12. Kinetics and mechanism of the oxidation of organic sulphides by 2,2 ...

    Indian Academy of Sciences (India)

    Unknown

    In the present article, we report the kinetics of oxidation of thirty-four organic sulphides by BPCC in ..... t-Butyl alcohol. 24⋅0. Acetone. 40⋅7 .... different sensitivity to the electronic demand for the phenomenon being studied. It has the ... 144. Table 5. Temperature dependence for the reaction constants for the oxidation of.

  13. Rule-based programming and strategies for automated generation of detailed kinetic models for gas phase combustion of polycyclic hydrocarbon molecules; Programmation par regles et strategies pour la generation automatique de mecanismes de combustion d'hydrocarbures polycycliques

    Energy Technology Data Exchange (ETDEWEB)

    Ibanescu, L.

    2004-06-15

    The primary objective of this thesis is to explore the approach of using rule-based systems and strategies, for a complex problem of chemical kinetic: the automated generation of reaction mechanisms. The chemical reactions are naturally expressed as conditional rewriting rules. The control of the chemical reactions chaining is easy to describe using a strategies language, such as the one of the ELAN system, developed in the Protheo team. The thesis presents the basic concepts of the chemical kinetics, the chemical and computational problems related to the conception and validation of a reaction mechanism, and gives a general structure for the generator of reaction mechanisms called GasEI. Our research focuses on the primary mechanism generator. We give solutions for encoding the chemical species, the reactions and their chaining, and we present the prototype developed in ELAN. The representation of the chemical species uses the notion of molecular graphs, encoded by a term structure called GasEI terms. The chemical reactions are expressed by rewriting rules on molecular graphs, encoded by a set of conditional rewriting rules on GasEI terms. The strategies language of the ELAN system is used to express the reactions chaining in the primary mechanism generator. This approach is illustrated by coding ten generic reactions of the oxidizing pyrolysis. Qualitative chemical validations of the prototype show that our approach gives, for acyclic molecules, the same results as the existing mechanism generators, and for polycyclic molecules produces original results.

  14. Rule-based programming and strategies for automated generation of detailed kinetic models for gas phase combustion of polycyclic hydrocarbon molecules; Programmation par regles et strategies pour la generation automatique de mecanismes de combustion d'hydrocarbures polycycliques

    Energy Technology Data Exchange (ETDEWEB)

    Ibanescu, L

    2004-06-15

    The primary objective of this thesis is to explore the approach of using rule-based systems and strategies, for a complex problem of chemical kinetic: the automated generation of reaction mechanisms. The chemical reactions are naturally expressed as conditional rewriting rules. The control of the chemical reactions chaining is easy to describe using a strategies language, such as the one of the ELAN system, developed in the Protheo team. The thesis presents the basic concepts of the chemical kinetics, the chemical and computational problems related to the conception and validation of a reaction mechanism, and gives a general structure for the generator of reaction mechanisms called GasEI. Our research focuses on the primary mechanism generator. We give solutions for encoding the chemical species, the reactions and their chaining, and we present the prototype developed in ELAN. The representation of the chemical species uses the notion of molecular graphs, encoded by a term structure called GasEI terms. The chemical reactions are expressed by rewriting rules on molecular graphs, encoded by a set of conditional rewriting rules on GasEI terms. The strategies language of the ELAN system is used to express the reactions chaining in the primary mechanism generator. This approach is illustrated by coding ten generic reactions of the oxidizing pyrolysis. Qualitative chemical validations of the prototype show that our approach gives, for acyclic molecules, the same results as the existing mechanism generators, and for polycyclic molecules produces original results.

  15. Numerical studies of spray combustion processes of palm oil biodiesel and diesel fuels using reduced chemical kinetic mechanisms

    KAUST Repository

    Kuti, Olawole

    2014-04-01

    Spray combustion processes of palm oil biodiesel (PO) and conventional diesel fuels were simulated using the CONVERGE CFD code. Thermochemical and reaction kinetic data (115 species and 460 reactions) by Luo et al. (2012) and Lu et al. (2009) (68 species and 283 reactions) were implemented in the CONVERGE CFD to simulate the spray and combustion processes of the two fuels. Tetradecane (C14H30) and n- heptane (C7H 16) were used as surrogates for diesel. For the palm biodiesel, the mixture of methyl decanoate (C11H20O2), methyl-9-decenoate (C11H19O2) and n-heptane was used as surrogate. The palm biodiesel surrogates were combined in proportions based on the previous GC-MS results for the five major biodiesel components namely methyl palmitate, methyl stearate, methyl oleate, methyl linoleate and methyl linolenate. The Favre-Averaged Navier Stokes based simulation using the renormalization group (RNG) k-ε turbulent model was implemented in the numerical calculations of the spray formation processes while the SAGE chemical kinetic solver is used for the detailed kinetic modeling. The SAGE chemical kinetic solver is directly coupled with the gas phase calculations by renormalization group (RNG) k-ε turbulent model using a well-stirred reactor model. Validations of the spray liquid length, ignition delay and flame lift-off length data were performed against previous experimental results. The simulated liquid length, ignition delay and flame lift-off length were validated at an ambient density of 15kg/m3, and injection pressure conditions of 100, 200 and 300 MPa were utilized. The predicted liquid length, ignition delay and flame lift-off length agree with the trends obtained in the experimental data at all injection conditions. Copyright © 2014 SAE International.

  16. Composition dependence of the kinetics and mechanisms of thermal oxidation of titanium-tantalum alloys

    International Nuclear Information System (INIS)

    Park, Y.S.; Butt, D.P.

    1999-01-01

    The oxidation behavior of titanium-tantalum alloys was investigated with respective concentrations of each element ranging from 0 to 100 wt.%. Alloys were exposed to argon-20% oxygen at 800 to 1400 C. The slowest oxidation rates were observed in alloys with 5--20% Ta. The oxidation kinetics of alloys containing less than approximately 40% Ta were approximately parabolic. Pure Ta exhibited nearly linear kinetics. Alloys containing 50% or more Ta exhibited paralinear kinetics. The activation energies for oxidation ranged between 232 kJ/mole for pure Ti and 119 kJ/mole for pure Ta, with the activation energies of the alloys falling between these values and generally decreasing with increasing Ta content. The activation energies for oxidation of the end members, Ti and Ta, agree well with published values for the activation energies for diffusion of oxygen in α-Ti and Ta. Scale formation in the alloys was found to be complex exhibiting various layers of Ti-, Ta-, and TiTa-oxides. The outermost layer of the oxidized alloys was predominantly rutile (TiO 2 ). Beneath the TiO 2 grew a variety of other oxides with the Ta content generally increasing with proximity to the metal-oxide interface. It was found that the most oxidation-resistant alloys had compositions falling between Ti-5Ta and Ti-15Ta. Although Ta stabilizes the β-phase of Ti, the kinetics of oxidation appeared to be rate limited by oxygen transport through the oxygen-stabilized α-phase. However, the kinetics are complicated by the formation of a complex oxide, which cracks periodically. Tantalum appears to increase the compositional range of oxygen-stabilized α-phase and reduces both the solubility of oxygen and diffusivity of Ti in the α- and β-phases

  17. Effect of hydrophobicity of pharmaceuticals and personal care products for adsorption on activated carbon: Adsorption isotherms, kinetics and mechanism.

    Science.gov (United States)

    Kaur, Harkirat; Bansiwal, Amit; Hippargi, Girivyankatesh; Pophali, Girish R

    2017-09-11

    Adsorption of three pharmaceuticals and personal care products (PPCPs), namely caffeine, ibuprofen and triclosan on commercial powdered activated carbon was examined in aqueous medium. The contaminants were chosen based on their diverse log K ow (octanol-water partition coefficient) viz. - 0.07 for caffeine, 3.97 for ibuprofen and 4.76 for triclosan to examine the role of hydrophobicity on adsorption process. The adsorbent characterisation was achieved using BET surface area, SEM, pore size distribution studies and FTIR. Influence of mass of PAC, contact time, solution pH and initial concentration on adsorption capacity of PAC was studied. Adsorption isotherms and kinetics were applied to establish the mechanism of adsorption. The kinetics followed pseudo-second order with physisorption occurring through particle diffusion. The Freundlich model fitted best among the isotherm models. The adsorption capacity increased in the order CFN activated carbon.

  18. Adsorption of aluminum and lead from wastewater by chitosan-tannic acid modified biopolymers: Isotherms, kinetics, thermodynamics and process mechanism.

    Science.gov (United States)

    Badawi, M A; Negm, N A; Abou Kana, M T H; Hefni, H H; Abdel Moneem, M M

    2017-06-01

    Chitosan was reacted by tannic acid to obtain three modified chitosan biopolymer. Their chemical structures were characterized by FTIR and elemental analysis. The prepared biopolymers were used to adsorb Al(III) and Pb(II) metal ions from industrial wastewater. The factors affecting the adsorption process were biosorbent amount, initial concentration of metal ion and pH of the medium. The adsorption efficiency increased considerably with the increase of the biosorbent amount and pH of the medium. The adsorption process of biosorbent on different metal ions was fitted by Freundlich adsorption model. The adsorption kinetics was followed Pseudo-second-order kinetic model. The adsorption process occurred according to diffusion mechanism which was confirmed by the interparticle diffusion model. The modified biopolymers were efficient biosorbents for removal of Pb(II) and Al(III) metal ions from the medium. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. General Methods for Analysis of Sequential “n-step” Kinetic Mechanisms: Application to Single Turnover Kinetics of Helicase-Catalyzed DNA Unwinding

    Science.gov (United States)

    Lucius, Aaron L.; Maluf, Nasib K.; Fischer, Christopher J.; Lohman, Timothy M.

    2003-01-01

    Helicase-catalyzed DNA unwinding is often studied using “all or none” assays that detect only the final product of fully unwound DNA. Even using these assays, quantitative analysis of DNA unwinding time courses for DNA duplexes of different lengths, L, using “n-step” sequential mechanisms, can reveal information about the number of intermediates in the unwinding reaction and the “kinetic step size”, m, defined as the average number of basepairs unwound between two successive rate limiting steps in the unwinding cycle. Simultaneous nonlinear least-squares analysis using “n-step” sequential mechanisms has previously been limited by an inability to float the number of “unwinding steps”, n, and m, in the fitting algorithm. Here we discuss the behavior of single turnover DNA unwinding time courses and describe novel methods for nonlinear least-squares analysis that overcome these problems. Analytic expressions for the time courses, fss(t), when obtainable, can be written using gamma and incomplete gamma functions. When analytic expressions are not obtainable, the numerical solution of the inverse Laplace transform can be used to obtain fss(t). Both methods allow n and m to be continuous fitting parameters. These approaches are generally applicable to enzymes that translocate along a lattice or require repetition of a series of steps before product formation. PMID:14507688

  20. General methods for analysis of sequential "n-step" kinetic mechanisms: application to single turnover kinetics of helicase-catalyzed DNA unwinding.

    Science.gov (United States)

    Lucius, Aaron L; Maluf, Nasib K; Fischer, Christopher J; Lohman, Timothy M

    2003-10-01

    Helicase-catalyzed DNA unwinding is often studied using "all or none" assays that detect only the final product of fully unwound DNA. Even using these assays, quantitative analysis of DNA unwinding time courses for DNA duplexes of different lengths, L, using "n-step" sequential mechanisms, can reveal information about the number of intermediates in the unwinding reaction and the "kinetic step size", m, defined as the average number of basepairs unwound between two successive rate limiting steps in the unwinding cycle. Simultaneous nonlinear least-squares analysis using "n-step" sequential mechanisms has previously been limited by an inability to float the number of "unwinding steps", n, and m, in the fitting algorithm. Here we discuss the behavior of single turnover DNA unwinding time courses and describe novel methods for nonlinear least-squares analysis that overcome these problems. Analytic expressions for the time courses, f(ss)(t), when obtainable, can be written using gamma and incomplete gamma functions. When analytic expressions are not obtainable, the numerical solution of the inverse Laplace transform can be used to obtain f(ss)(t). Both methods allow n and m to be continuous fitting parameters. These approaches are generally applicable to enzymes that translocate along a lattice or require repetition of a series of steps before product formation.

  1. Photocatalytic degradation kinetics and mechanism of antivirus drug-lamivudine in TiO{sub 2} dispersion

    Energy Technology Data Exchange (ETDEWEB)

    An, Taicheng, E-mail: antc99@gig.ac.cn [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); An, Jibin [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou 730050 (China); Graduate School of Chinese Academy of Sciences, Beijing 100049 (China); Yang, Hai [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate School of Chinese Academy of Sciences, Beijing 100049 (China); Li, Guiying [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Feng, Huixia [College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou 730050 (China); Nie, Xiangping [Institute of Hydrobiology, Jinan University, Guangzhou 510632 (China)

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer Photocatalytic degradation kinetics of antivirus drug lamivudine. Black-Right-Pointing-Pointer The degradation kinetics was optimized by the single-variable-at-a-time. Black-Right-Pointing-Pointer The degradation kinetics was optimized by central composite design. Black-Right-Pointing-Pointer The contribution of reactive species was investigated with addition of scavengers. Black-Right-Pointing-Pointer Six intermediates were identified and a degradation mechanism was proposed. - Abstract: Photocatalytic degradation kinetics of antivirus drug-lamivudine in aqueous TiO{sub 2} dispersions was systematically optimized by both single-variable-at-a-time and central composite design based on the response surface methodology. Three variables, TiO{sub 2} content, initial pH and lamivudine concentration, were selected to determine the dependence of degradation efficiencies of lamivudine on independent variables. Response surface methodology modeling results indicated that degradation efficiencies of lamivudine were highly affected by TiO{sub 2} content and initial lamivudine concentration. The highest degradation efficiency was achieved at suitable amount of TiO{sub 2} and with maintaining initial lamivudine concentration to a minimum. In addition, the contribution experiments of various primary reactive species produced during the photocatalysis were investigated with the addition of different scavengers and found that hydroxyl radicals was the major reactive species involved in lamivudine degradation in aqueous TiO{sub 2}. Six degradation intermediates were identified using HPLC/MS/MS, and photocatalytic degradation mechanism of lamivudine was proposed by utilizing collective information from both experimental results of HPLC/MS/MS, ion chromatography as well as total organic carbon and theoretical data of frontier electron densities and point charges.

  2. Ozone-surface interactions: Investigations of mechanisms, kinetics, mass transport, and implications for indoor air quality

    Energy Technology Data Exchange (ETDEWEB)

    Morrison, Glenn Charles [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    In this dissertation, results are presented of laboratory investigations and mathematical modeling efforts designed to better understand the interactions of ozone with surfaces. In the laboratory, carpet and duct materials were exposed to ozone and measured ozone uptake kinetics and the ozone induced emissions of volatile organic compounds. To understand the results of the experiments, mathematical methods were developed to describe dynamic indoor aldehyde concentrations, mass transport of reactive species to smooth surfaces, the equivalent reaction probability of whole carpet due to the surface reactivity of fibers and carpet backing, and ozone aging of surfaces. Carpets, separated carpet fibers, and separated carpet backing all tended to release aldehydes when exposed to ozone. Secondary emissions were mostly n-nonanal and several other smaller aldehydes. The pattern of emissions suggested that vegetable oils may be precursors for these oxidized emissions. Several possible precursors and experiments in which linseed and tung oils were tested for their secondary emission potential were discussed. Dynamic emission rates of 2-nonenal from a residential carpet may indicate that intermediate species in the oxidation of conjugated olefins can significantly delay aldehyde emissions and act as reservoir for these compounds. The ozone induced emission rate of 2-nonenal, a very odorous compound, can result in odorous indoor concentrations for several years. Surface ozone reactivity is a key parameter in determining the flux of ozone to a surface, is parameterized by the reaction probability, which is simply the probability that an ozone molecule will be irreversibly consumed when it strikes a surface. In laboratory studies of two residential and two commercial carpets, the ozone reaction probability for carpet fibers, carpet backing and the equivalent reaction probability for whole carpet were determined. Typically reaction probability values for these materials were 10

  3. Chemical Kinetics for Bridging Molecular Mechanisms and Macroscopic Measurements of Amyloid Fibril Formation.

    Science.gov (United States)

    Michaels, Thomas C T; Šarić, Anđela; Habchi, Johnny; Chia, Sean; Meisl, Georg; Vendruscolo, Michele; Dobson, Christopher M; Knowles, Tuomas P J

    2018-04-20

    Understanding how normally soluble peptides and proteins aggregate to form amyloid fibrils is central to many areas of modern biomolecular science, ranging from the development of functional biomaterials to the design of rational therapeutic strategies against increasingly prevalent medical conditions such as Alzheimer's and Parkinson's diseases. As such, there is a great need to develop models to mechanistically describe how amyloid fibrils are formed from precursor peptides and proteins. Here we review and discuss how ideas and concepts from chemical reaction kinetics can help to achieve this objective. In particular, we show how a combination of theory, experiments, and computer simulations, based on chemical kinetics, provides a general formalism for uncovering, at the molecular level, the mechanistic steps that underlie the phenomenon of amyloid fibril formation.

  4. Thermal degradation behaviors of polyethylene and polypropylene. Part I: Pyrolysis kinetics and mechanisms

    International Nuclear Information System (INIS)

    Aboulkas, A.; El harfi, K.; El Bouadili, A.

    2010-01-01

    Study of the decomposition kinetics is an important tool for the development of polymer recycling in industrial scale. In this work, the activation energy and the reaction model of the pyrolysis of high density polyethylene (HDPE), low density polyethylene (LDPE) and polypropylene (PP) have been estimated from non-isothermal kinetic results. Firstly, the activation energy values obtained by Friedman, Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa isoconversional methods, are 238-247 kJ/mol for HDPE, 215-221 kJ/mol for LDPE and 179-188 kJ/mol for PP. Secondly, the appropriate conversion model of the process was determined by Coats-Redfern and Criado methods. The pyrolysis reaction models of HDPE and LDPE are accounted for by 'Contracting Sphere' model, whereas that of PP by 'Contracting Cylinder' model.

  5. Kinetic and Mechanism Study of Vanadium Acid Leaching from Black Shale Using Microwave Heating Method

    Science.gov (United States)

    Wang, Jing-peng; Zhang, Yi-min; Huang, Jing; Liu, Tao

    2018-06-01

    The leaching kinetics of the vanadium leaching process were investigated by the comparison of microwave heating and conventional heating methods. Microwave heating with CaF2 had a synergistic effect and improved the vanadium leaching efficiency. In contrast to conventional heating leaching, microwave heating accelerated the vanadium leaching rate by approximately 1-3% and by approximately 15% when CaF2 was also used. The kinetics analysis showed that the calculated activation energy decreased in the microwave heating method in the presence and absence of CaF2. The control procedure of leaching also changed from a chemical reaction control step to a mixed chemical diffusion control step upon the addition of CaF2. Microwave heating was shown to be suitable for leaching systems with diffusion or mixed chemical diffusion control steps when the target mineral does not have a microwave absorbing ability.

  6. Kinetic and Mechanism Study of Vanadium Acid Leaching from Black Shale Using Microwave Heating Method

    Science.gov (United States)

    Wang, Jing-peng; Zhang, Yi-min; Huang, Jing; Liu, Tao

    2018-04-01

    The leaching kinetics of the vanadium leaching process were investigated by the comparison of microwave heating and conventional heating methods. Microwave heating with CaF2 had a synergistic effect and improved the vanadium leaching efficiency. In contrast to conventional heating leaching, microwave heating accelerated the vanadium leaching rate by approximately 1-3% and by approximately 15% when CaF2 was also used. The kinetics analysis showed that the calculated activation energy decreased in the microwave heating method in the presence and absence of CaF2. The control procedure of leaching also changed from a chemical reaction control step to a mixed chemical diffusion control step upon the addition of CaF2. Microwave heating was shown to be suitable for leaching systems with diffusion or mixed chemical diffusion control steps when the target mineral does not have a microwave absorbing ability.

  7. Kinetics and mechanism of the dissociation of chlorophyll and its metalloanalogues in proton-donating media

    International Nuclear Information System (INIS)

    Berezin, B.D.; Drobysheva, A.N.; Karmanova, L.P.

    1976-01-01

    The kinetics of the dissociation of chlorophyll a and its metalloanalogues (Zn 2+ and Cd 2+ complexes of chlorophyllic acid) have been investigated in t-butyl alcohol-trichloracetic acid mixtures. The dissociation reaction is kinetically firts-order with respect to the complex. The rate constants and the activation energies and entropies for the dissociation reaction have been calculated. In order to determine the order of the reaction with respect to the protogenic species, a study was made of the ionisation of m-nitroaniline in t-butyl alcohol at 25 0 C in the trichloroacetic acid concentration range from 0.15 to 4.75 M. The dissociation reaction of chlorophyll and its zinc-containing metalloanalogue has been shown to be of second order with respect to the solvated proton. The cadmium complex dissociates by a second-order reaction with respect to trichloroacetic acid

  8. Chemical Kinetics for Bridging Molecular Mechanisms and Macroscopic Measurements of Amyloid Fibril Formation

    Science.gov (United States)

    Michaels, Thomas C. T.; Šarić, Anđela; Habchi, Johnny; Chia, Sean; Meisl, Georg; Vendruscolo, Michele; Dobson, Christopher M.; Knowles, Tuomas P. J.

    2018-04-01

    Understanding how normally soluble peptides and proteins aggregate to form amyloid fibrils is central to many areas of modern biomolecular science, ranging from the development of functional biomaterials to the design of rational therapeutic strategies against increasingly prevalent medical conditions such as Alzheimer's and Parkinson's diseases. As such, there is a great need to develop models to mechanistically describe how amyloid fibrils are formed from precursor peptides and proteins. Here we review and discuss how ideas and concepts from chemical reaction kinetics can help to achieve this objective. In particular, we show how a combination of theory, experiments, and computer simulations, based on chemical kinetics, provides a general formalism for uncovering, at the molecular level, the mechanistic steps that underlie the phenomenon of amyloid fibril formation.

  9. An atmospheric pressure flow reactor: Gas phase kinetics and mechanism in tropospheric conditions without wall effects

    Science.gov (United States)

    Koontz, Steven L.; Davis, Dennis D.; Hansen, Merrill

    1988-01-01

    A new type of gas phase flow reactor, designed to permit the study of gas phase reactions near 1 atm of pressure, is described. A general solution to the flow/diffusion/reaction equations describing reactor performance under pseudo-first-order kinetic conditions is presented along with a discussion of critical reactor parameters and reactor limitations. The results of numerical simulations of the reactions of ozone with monomethylhydrazine and hydrazine are discussed, and performance data from a prototype flow reactor are presented.

  10. On kinetics and mechanism of' furfural oxidation by ions of heterovalent metals

    International Nuclear Information System (INIS)

    Krupenskij, V.I.

    1983-01-01

    Real constants of rate of furfural oxidation by Cu 2+ , Fe 3+ , Ce 4+ , Ag + , Hg 2+ 2 ions are determined, other kinetic and activation parameters of reactions are calculated, constants of stability and other thermodynamic characteristics of furfural complex with cations-oxidizers are found. Schemes of furfural transformations at one- and two-electron oxidation by ions of variable-valency metals are suggested

  11. Kinetics and mechanism of furfural oxidation by ions of heterovalent metals

    Energy Technology Data Exchange (ETDEWEB)

    Krupenskij, V.I. (Ukhtinskij Industrial' nyj Inst. (USSR))

    1983-01-01

    Real constants of rate of furfural oxidation by Cu/sup 2 +/, Fe/sup 3 +/, Ce/sup 4 +/, Ag/sup +/, Hg/sup 2 +//sub 2/ ions are determined, other kinetic and activation parameters of reactions are calculated, constants of stability and other thermodynamic characteristics of furfural complex with cations-oxidizers are found. Schemes of furfural transformations at one- and two-electron oxidation by ions of variable-valency metals are suggested.

  12. Frustrated Kinetic Energy, the Optical Sum Rule, and the Mechanism of Superconductivity

    International Nuclear Information System (INIS)

    Chakravarty, S.; Kee, H.; Abrahams, E.

    1999-01-01

    The basis of the interlayer tunneling theory of high-temperature superconductivity is that the electronic kinetic energy in a direction perpendicular to the copper-oxygen planes is a substantial fraction of the condensation energy. This issue is critically examined, and it is argued from a rigorous conductivity sum rule that the consequences of this theory are consistent with recent optical and penetration depth measurements. copyright 1999 The American Physical Society

  13. The heterogeneous interaction of trace gases on mineral dust and soot: kinetics and mechanism

    OpenAIRE

    Karagulian, Federico; Rossi, Michel

    2007-01-01

    The present thesis work deals with the investigation of the heterogeneous reactions involving nitrate radical (NO3), dinitrogen pentoxide (N2O5) and ozone (O3) on surrogates of atmospheric mineral dust particles characteristic of the troposphere. An additional investigation of heterogeneous reaction of NO3 on flame soot was carried out. The goal is to characterize the kinetics (the uptake coefficient γ) as well as the reaction products. The obtained results are intended to provide reliable da...

  14. Evidence for a Shared Mechanism in the Formation of Urea-Induced Kinetic and Equilibrium Intermediates of Horse Apomyoglobin from Ultrarapid Mixing Experiments

    Science.gov (United States)

    Mizukami, Takuya; Abe, Yukiko; Maki, Kosuke

    2015-01-01

    In this study, the equivalence of the kinetic mechanisms of the formation of urea-induced kinetic folding intermediates and non-native equilibrium states was investigated in apomyoglobin. Despite having similar structural properties, equilibrium and kinetic intermediates accumulate under different conditions and via different mechanisms, and it remains unknown whether their formation involves shared or distinct kinetic mechanisms. To investigate the potential mechanisms of formation, the refolding and unfolding kinetics of horse apomyoglobin were measured by continuous- and stopped-flow fluorescence over a time range from approximately 100 μs to 10 s, along with equilibrium unfolding transitions, as a function of urea concentration at pH 6.0 and 8°C. The formation of a kinetic intermediate was observed over a wider range of urea concentrations (0–2.2 M) than the formation of the native state (0–1.6 M). Additionally, the kinetic intermediate remained populated as the predominant equilibrium state under conditions where the native and unfolded states were unstable (at ~0.7–2 M urea). A continuous shift from the kinetic to the equilibrium intermediate was observed as urea concentrations increased from 0 M to ~2 M, which indicates that these states share a common kinetic folding mechanism. This finding supports the conclusion that these intermediates are equivalent. Our results in turn suggest that the regions of the protein that resist denaturant perturbations form during the earlier stages of folding, which further supports the structural equivalence of transient and equilibrium intermediates. An additional folding intermediate accumulated within ~140 μs of refolding and an unfolding intermediate accumulated in <1 ms of unfolding. Finally, by using quantitative modeling, we showed that a five-state sequential scheme appropriately describes the folding mechanism of horse apomyoglobin. PMID:26244984

  15. Electro-oxidation of the dye azure B: kinetics, mechanism, and by-products.

    Science.gov (United States)

    Olvera-Vargas, Hugo; Oturan, Nihal; Aravindakumar, C T; Paul, M M Sunil; Sharma, Virender K; Oturan, Mehmet A

    2014-01-01

    In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals ((•)OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by (•)OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19 × 10(9) M(-1) s(-1). It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.

  16. Early Events, Kinetic Intermediates and the Mechanism of Protein Folding in Cytochrome c

    Directory of Open Access Journals (Sweden)

    David S. Kliger

    2009-04-01

    Full Text Available Kinetic studies of the early events in cytochrome c folding are reviewed with a focus on the evidence for folding intermediates on the submillisecond timescale. Evidence from time-resolved absorption, circular dichroism, magnetic circular dichroism, fluorescence energy and electron transfer, small-angle X-ray scattering and amide hydrogen exchange studies on the t £ 1 ms timescale reveals a picture of cytochrome c folding that starts with the ~ 1-ms conformational diffusion dynamics of the unfolded chains. A fractional population of the unfolded chains collapses on the 1 – 100 ms timescale to a compact intermediate IC containing some native-like secondary structure. Although the existence and nature of IC as a discrete folding intermediate remains controversial, there is extensive high time-resolution kinetic evidence for the rapid formation of IC as a true intermediate, i.e., a metastable state separated from the unfolded state by a discrete free energy barrier. Final folding to the native state takes place on millisecond and longer timescales, depending on the presence of kinetic traps such as heme misligation and proline mis-isomerization. The high folding rates observed in equilibrium molten globule models suggest that IC may be a productive folding intermediate. Whether it is an obligatory step on the pathway to the high free energy barrier associated with millisecond timescale folding to the native state, however, remains to be determined.

  17. Detailed sedimentology and geomorphology elucidate mechanisms of formation of modern and historical sequences of minor moraines in the European Alps

    Science.gov (United States)

    Wyshnytzky, Cianna; Lukas, Sven

    2016-04-01

    Suites of closely-spaced minor moraines may help further understanding of glacier retreat and predict its geomorphological effects through the observations of moraine formation on short timescales. This research is common in lowland, maritime settings (Sharp, 1984; Boulton, 1986; Krüger, 1995; Reinardy et al., 2013), but remains sparse in high-mountain settings (Hewitt, 1967; Ono, 1985; Beedle et al., 2009; Lukas, 2012). This research presents detailed sedimentological and geomorphological research on minor moraines at two high-mountain settings in the Alps: Silvrettagletscher, Switzerland, as a modern setting and Schwarzensteinkees, Austria, as a historical setting. Geomorphological investigations included mapping and measurements through field observations and assessing aerial imagery. Additionally, terrestrial laser scanning and ground-penetrating radar data were collected in the Schwarzensteinkees foreland. Detailed sedimentological investigations followed excavation of seven moraines at Silvrettagletscher and five moraines at Schwarzensteinkees and include multiple scales of observation and measurements to support interpretations of sediment transport and deposition (e.g. Evans and Benn, 2004). The modern moraines at Silvrettagletscher, in the immediately proglacial foreland, have been forming since before 2003. Four mechanisms of formation show distinct sedimentological signatures: formerly ice-cored moraines (e.g. Kjær & Krüger, 2001; Lukas, 2012; Reinardy et al., 2013) , push moraine formation on a reverse bedrock slope (e.g. Lukas, 2012), push moraine formation incorporating sediments deposited in a former proglacial basin, and basal freeze-on (e.g. Andersen & Sollid, 1971; Krüger, 1995; Reinardy et al., 2013). Schwarzensteinkees still exists but is currently restricted to steeply-dipping bedrock slabs above the main valley. This study therefore investigates the moraines in the foreland that formed between approximately 1850 and 1930. The minor

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

    International Nuclear Information System (INIS)

    Raković, Milun J

    2011-01-01

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

  19. Influence of various irradiation processes on the mechanical properties and polymerisation kinetics of bulk-fill resin based composites.

    Science.gov (United States)

    Ilie, Nicoleta; Keßler, Andreas; Durner, Jürgen

    2013-08-01

    To assess the effect of irradiation time and distance of the light tip on the micro-mechanical properties and polymerisation kinetics of two bulk-fill resin-based composites at simulated clinically relevant filling depth. Micro-mechanical properties (Vickers hardness (HV), depth of cure (DOC) and indentation modulus (E)) and polymerisation kinetics (real-time increase of degree of cure (DC)) of two bulk-fill resin-based composites (Tetric EvoCeram(®) Bulk Fill, Ivoclar Vivadent and x-tra base, Voco) were assessed at varying depth (0.1-6mm in 100μm steps for E and HV and 0.1, 2, 4 and 6mm for DC), irradiation time (10, 20 or 40s, Elipar Freelight2) and distances from the light tip (0 and 7mm). Curing unit's irradiance was monitored in 1mm steps at distances up to 10mm away from the light tip on a laboratory-grade spectrometer. Multivariate analysis (α=0.05), Student's t-test and Pearson correlation analysis were considered. The influence of material on the measured mechanical properties was significant (η(2)=0.080 for E and 0.256 for HV), while the parameters irradiation time, distance from the light tip and depth emphasise a stronger influence on Tetric EvoCeram(®) Bulk Fill. The polymerisation kinetics could be described by an exponential sum function, distinguishing between the gel and the glass phase. The above mentioned parameters strongly influenced the start of polymerisation (gel phase), and were of less importance for the glass phase. Both materials enable at least 4mm thick increments to be cured in one step under clinically relevant curing conditions. The susceptibility to variation in irradiance was material dependent, thus properties measured under clinically simulated curing conditions might vary to a different extent from those measured under ideal curing conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. The Effect of Prestrain Temperature on Kinetics of Static Recrystallization, Microstructure Evolution, and Mechanical Properties of Low Carbon Steel

    Science.gov (United States)

    Akbari, Edris; Karimi Taheri, Kourosh; Karimi Taheri, Ali

    2018-05-01

    In this research, the samples of a low carbon steel sheet were rolled up to a thickness prestrain of 67% at three different temperatures consisted of room, blue brittleness, and subzero temperature. Microhardness, SEM, and tensile tests were carried out to evaluate the static recrystallization kinetics defined by the Avrami equation, microstructural evolution, and mechanical properties. It was found that the Avrami exponent is altered with change in prestrain temperature and it achieves the value of 1 to 1. 5. Moreover, it was indicated that prestraining at subzero temperature followed by annealing at 600 °C leads to considerable enhancement in tensile properties and kinetics of static recrystallization compared to room and blue brittleness temperatures. The prestraining at blue brittleness temperature followed by annealing treatment caused, however, a higher strength and faster kinetics compared with that at room temperature. It was concluded that although from the steel ductility point of view, the blue brittleness temperature is called an unsuitable temperature, but it can be used as prestraining temperature to develop noticeable combination of strength and ductility in low carbon steel.

  1. Genetic characterization, nickel tolerance, biosorption, kinetics, and uptake mechanism of a bacterium isolated from electroplating industrial effluent.

    Science.gov (United States)

    Nagarajan, N; Gunasekaran, P; Rajendran, P

    2015-04-01

    Electroplating industries in Madurai city produce approximately 49,000 L of wastewater and 1200 L of sludge every day revealing 687-5569 ppm of nickel (Ni) with other contaminants. Seventeen Ni-tolerant bacterial strains were isolated from nutrient-enriched effluents. Among them one hyper Ni accumulating strain was scored and identified as Bacillus cereus VP17 on the basis of morphology, biochemical tests, 16S rDNA gene sequencing, and phylogenetic analysis. Equilibrium data of Ni(II) ions using the bacterium as sorbent at isothermal conditions (37 °C) and pH 6 were best adjusted by Langmuir (R(2) = 0.6268) and Freundlich models (R(2) = 0.9505). Experimental validation reveals Ni sorption takes place on a heterogeneous surface of the biosorbent, and predicted metal sorption capacity is 434 ppm. The pseudo-second-order kinetic model fitted the biosorption kinetic data better than the pseudo-first-order kinetic model (R(2) = 0.9963 and 0.3625). Scanning electron microscopy, energy dispersive X-ray, and Fourier transform infrared spectroscopy studies of the bacterial strain with and without Ni(II) ion reveals the biosorption mechanism. The results conclude possibilities of using B. cereus VP17 for Ni bioremediation.

  2. Catecholase activity of dicopper(II)-bispidine complexes: stabilities and structures of intermediates, kinetics and reaction mechanism.

    Science.gov (United States)

    Born, Karin; Comba, Peter; Daubinet, André; Fuchs, Alexander; Wadepohl, Hubert

    2007-01-01

    A mechanism for the oxidation of 3,5-di-tert-butylcatechol (dtbc) with dioxygen to the corresponding quinone (dtbq), catalyzed by bispidine-dicopper complexes (bispidines are various mono- and dinucleating derivatives of 3,7-diazabicyclo[3.3.1]nonane with bis-tertiary-amine-bispyridyl or bis-tertiary-amine-trispyridyl donor sets), is proposed on the basis of (1) the stoichiometry of the reaction as well as the stabilities and structures [X-ray, density functional theory (B3LYP, TZV)] of the bispidine-dicopper(II)-3,4,5,6-tetrachlorcatechol intermediates, (2) formation kinetics and structures (molecular mechanics, MOMEC) of the end-on peroxo-dicopper(II) complexes and (3) kinetics of the stoichiometric (anaerobic) and catalytic (aerobic) copper-complex-assisted oxidation of dtbc. This involves (1) the oxidation of the dicopper(I) complexes with dioxygen to the corresponding end-on peroxo-dicopper(II) complexes, (2) coordination of dtbc as a bridging ligand upon liberation of H(2)O(2) and (3) intramolecular electron transfer to produce dtbq, which is liberated, and the dicopper(I) catalyst. Although the bispidine complexes have reactivities comparable to those of recently published catalysts with macrocyclic ligands, which seem to reproduce the enzyme-catalyzed process in various reaction sequences, a strikingly different oxidation mechanism is derived from the bispidine-dicopper-catalyzed reaction.

  3. Evaluation of reaction mechanisms and the kinetic parameters for the transesterification of castor oil by liquid enzymes

    DEFF Research Database (Denmark)

    Andrade, Thalles Allan; Errico, Massimiliano; Christensen, Knud Villy

    2017-01-01

    of the transesterification of castor oil with methanol using the enzyme Eversa® Transform as catalyst were investigated. Reactions were carried out for 8 hours at 35 °C with: an alcohol-to-oil molar ratio equal to 6:1, a 5 wt% of liquid enzyme solution and addition of 5 wt% of water by weight of castor oil. From...... methanolysis rates of glycerides obtained, indicated that transesterification dominates over hydrolysis. The mechanism among the four models proposed that gave the best fit could be simplified, eliminating the kinetic parameters with negligible effects on the reaction rates. This model was able to fit...

  4. The effect of antimony presence in anodic copper on kinetics and mechanism of anodic dissolution and cathodic deposition of copper

    Directory of Open Access Journals (Sweden)

    Stanković Z.D.

    2008-01-01

    Full Text Available The influence of the presence of Sb atoms, as foreign metal atoms in anode copper, on kinetics, and, on the mechanism of anodic dissolution and cathodic deposition of copper in acidic sulfate solution has been investigated. The galvanostatic single-pulse method has been used. Results indicate that presence of Sb atoms in anode copper increase the exchange current density as determined from the Tafel analysis of the electrode reaction. It is attributed to the increase of the crystal lattice parameter determined from XRD analysis of the electrode material.

  5. Decomposition mechanisms and non-isothermal kinetics of LiHC_2O_4·H_2O

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    The thermal decomposition process of LiHC2O4·H2O from 30 to 600 ℃ was investigated by the thermogravimetric and differential scanning calorimetry (TG-DSC). The phases decomposited at different temperature were characterized by X-ray diffraction (XRD), which indicated the decompositions at 150, 170, and 420℃, relating to LiHC2O4, Li2C2O4, Li2C2O4, and Li2CO3, respectively. Reaction mechanisms in the whole sintering process were determined, and the model fitting kinetic approaches were applied to data for non...

  6. Kinetics of cyclopropane formation by 1,3-deoxystannylation. A kinetic isotope effect as a probe for the mechanism of neighboring group participation

    International Nuclear Information System (INIS)

    McWilliam, D.C.; Balasubramanian, T.R.; Kuivila, H.G.

    1978-01-01

    1-Aryl-3-trimethylstannyl 3,5-dinitrobenzoates, Me 3 SnCH 2 CH 2 CHAr(ODNB), 4H, undergo solvolysis in 2,2,2-trifluoroethanol to form arylcyclopropanes and trimethylstannyl dinitrobenzoate. The rates for nine substituents on Ar are correlated by sigma + with a rho value of -3.63 at 100 0 C. The rates for a series of model compounds, Me 3 CCH 2 CH 2 CHAr(ODNB), 5H (six substituents), are also correlated by sigma + with a rho value of -4.90. In each case the rate for a given 4H is greater than that for the corresponding 5H. The Winstein-Grunwald m values for 4H and 5H in aqueous acetic acid at 100 0 C are 0.41 and 0.46, respectively. Measurements of the rates of solvolyses in trifluoroethanol of the 2.2-d 2 analogues of 4H and 5H revealed kinetic isotope effects of 0.94 and 1.08, respectively. These results are taken as evidence that the mechanism for the rate acceleration observed in the 4H series is due to direct participation of the C--Sn sigma electrons in the transition state of the rate-determining step of the 1,3-elimination reaction

  7. Final Report: Mechanisms of sputter ripple formation: coupling among energetic ions, surface kinetics, stress and composition

    Energy Technology Data Exchange (ETDEWEB)

    Chason, Eric; Shenoy, Vivek

    2013-01-22

    Self-organized pattern formation enables the creation of nanoscale surface structures over large areas based on fundamental physical processes rather than an applied template. Low energy ion bombardment is one such method that induces the spontaneous formation of a wide variety of interesting morphological features (e.g., sputter ripples and/or quantum dots). This program focused on the processes controlling sputter ripple formation and the kinetics controlling the evolution of surfaces and nanostructures in high flux environments. This was done by using systematic, quantitative experiments to measure ripple formation under a variety of processing conditions coupled with modeling to interpret the results.

  8. Spatial distribution of mechanical forces and ionic flux in electro-kinetic instability near a permselective membrane

    Science.gov (United States)

    Magnico, Pierre

    2018-01-01

    This paper is devoted to the numerical investigation of electro-kinetic instability in a polarization layer next to a cation-exchange membrane. An analysis of some properties of the electro-kinetic instability is followed by a detailed description of the fluid flow structure and of the spatial distribution of the ionic flux. In this aim, the Stokes-Poisson-Nernst-Planck equation set is solved until the Debye length scale. The results show that the potential threshold of the marginal instability and the current density depend on the logarithm of the concentration at the membrane surface. The size of the stable vortices seems to be an increasing function of the potential drop. The fluid motion is induced by the electric force along the maximum concentration in the extended space charge (ESC) region and by the pressure force in the region around the inner edge of the ESC layer. Two spots of kinetic energy are located in the ESC region and between the vortices. The cationic motion, controlled by the electric field and the convection, presents counter-rotating vortices in the stagnation zone located in the fluid ejection region. The anion transport is also characterized by two independent layers which contain counter-rotating vortices. The first one is in contact with the stationary reservoir. In the second layer against the membrane, the convection, and the electric field control, the transversal motion, the Fickian diffusion, and the convection are dominant in the longitudinal direction. Finally, the longitudinal disequilibrium of potential and pressure along the membrane is analyzed.

  9. Kinetics of heat damage autologous red blood cells. Mechanism of clearance from blood

    Energy Technology Data Exchange (ETDEWEB)

    Peters, A.M.; Ryan, P.F.J.; Klonizakis, I.; Elkon, K.B.; Lewis, S.M.; Hughes, G.R.V.; Lavender, J.P. (Hammersmith Hospital, London (UK))

    1982-01-01

    The kinetics of radiolabelled heat damage red cell (HDRBC) distribution have been studied in humans using a gamma camera, and compared with the kinetics of other blood cells. Liver uptake of /sup 111/In labelled HDRBC was completed within about 10 min of injection; splenic uptake was biphasic with a half time of about 5 min over the first 20 min in following injection, and a later half time much longer than this. Activity initially present in the lung fields cleared within 24 h. The rate constant of liver uptake of sup(99m)Tc labelled HDRBC and of /sup 111/In labelled platelets were very similar; the rate constants of splenic uptake of these 2 particles were also very similar up to about 20 min following injection when the splenic platelet levels became constant and the HDRBC level continued to slowly rise. Splenic uptake and blood clearance of red cells coated with IgG (IgG-RBC), in contrast to HDRBC, were monoexponential. It was concluded that: (1) the blood clearance of HDRBC was due to pooling within, and to irreversible extraction by, the spleen; (2) liver uptake of HDRBC, which was irreversible, was completed within 10 min of injection; (3) IgG-RBC clearance was due to irreversible extraction by the spleen; (4) HDRBC uptake in the lung was unrelated to reticuloendothelial function, and represented prolonged transit through the lung microvasculature.

  10. Fixation and reduction of uranium by natural organic matter: reaction mechanisms and kinetics

    International Nuclear Information System (INIS)

    Nakashima, S.; Perruchot, A.; Trichet, J.; Disnar, J.R.

    1987-01-01

    The reactivity of lignite towards soluble uranyl species in an aqueous medium is experimentally investigated as a function of temperature (between 20 0 C and 400 0 C). The fixation process starts near 45 0 C, with reduction beginning around 120 0 C. The fixation process leads to the formation of chemically and thermally stable organo-uranyl species. The reduction of free uranyl species is accompanied by a stoichiometric (2:1) liberation of protons into the medium. These protons originate from the organic matter which thus undergoes dehydrogenation. The general evolution of the carbonaceous residue in the course of this reaction shows that alcoholic and aliphatic hydrocarbon groups are responsible for the reduction. This chemical dehydrogenation could explain the low hydrogen content of natural organic materials associated with uraniferous deposits. The kinetics of the reduction step have been studied at 180 0 C, 190 0 C and 200 0 C. The kinetic parameters determined over this temperature range, and the extrapolation made to 20 0 C, show that reduction can be a crucial process in the geochemical behaviour of uranium especially in the thermal conditions in which sedimentary basins evolve [fr

  11. Kinetics and mechanism of the cutinase-catalyzed transesterification of oils in AOT reversed micellar system.

    Science.gov (United States)

    Badenes, Sara M; Lemos, Francisco; Cabral, Joaquim M S

    2011-11-01

    The kinetics of the enzymatic transesterification between a mixture of triglycerides (oils) and methanol for biodiesel production in a bis(2-ethylhexyl) sodium sulfosuccinate (AOT)/isooctane reversed micellar system, using recombinant cutinase from Fusarium solani pisi as a catalyst, was investigated. In order to describe the results that were obtained, a mechanistic scheme was proposed, based on the literature and on the experimental data. This scheme includes the following reaction steps: the formation of the active enzyme-substrate complex, the addition of an alcohol molecule to the complex followed by the separation of a molecule of the fatty acid alkyl ester and a glycerol moiety, and release of the active enzyme. Enzyme inhibition and deactivation effects due to methanol and glycerol were incorporated in the model. This kinetic model was fitted to the concentration profiles of the fatty acid methyl esters (the components of biodiesel), tri-, di- and monoglycerides, obtained for a 24 h transesterification reaction performed in a stirred batch reactor under different reaction conditions of enzyme and initial substrates concentration.

  12. PCB congener sorption to carbonaceous sediment components: Macroscopic comparison and characterization of sorption kinetics and mechanism

    International Nuclear Information System (INIS)

    Choi, Hyeok; Al-Abed, Souhail R.

    2009-01-01

    Sorption of polychlorinated biphenyls (PCBs) to sediment is a key process in determining their mobility, bioavailability, and chemical decomposition in aquatic environments. In order to examine the validity of currently used interpretation approaches for PCBs sorption, comparative results on 2-chlorobiphenyl sorption to carbonaceous components in sediments (activated carbon, carbon black, coal, soot, graphite, flyash, wood) were macroscopically correlated with the structural, morphological, crystallographic, and compositional properties of the carbonaceous components. Since the Freundlich sorption constant, K F (L kg -1 ) spanned several orders of magnitude, ranging from log K F of 6.13-5.27 for activated carbon, 5.04 for carbon black, 3.83 for coal to 3.08 for wood, organic carbon partitioning approach should be more specifically categorized, considering the various forms, nature and origins of organic carbon in sediment. Sorption rate constants and fraction parameters, which were numerically defined from empirical kinetic model with fast and slow sorption fractions, were closely related to the physicochemical properties of the carbonaceous components. Sorption interpretation approaches with a specific property and viewpoint, such as organic carbon partitioning, soot carbon distribution, or surface area correlation, did not properly explain the overall results on sorption capacity, fast and slow sorption kinetics, and partitioning coefficient. It is also important to emphasize the heterogeneous nature of sediment and the difficulties of encompassing the partitioning among its carbonaceous components.

  13. PCB congener sorption to carbonaceous sediment components: Macroscopic comparison and characterization of sorption kinetics and mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Hyeok [National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 West Martin Luther King Drive, Cincinnati, OH 45268 (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)

    2009-06-15

    Sorption of polychlorinated biphenyls (PCBs) to sediment is a key process in determining their mobility, bioavailability, and chemical decomposition in aquatic environments. In order to examine the validity of currently used interpretation approaches for PCBs sorption, comparative results on 2-chlorobiphenyl sorption to carbonaceous components in sediments (activated carbon, carbon black, coal, soot, graphite, flyash, wood) were macroscopically correlated with the structural, morphological, crystallographic, and compositional properties of the carbonaceous components. Since the Freundlich sorption constant, K{sub F} (L kg{sup -1}) spanned several orders of magnitude, ranging from log K{sub F} of 6.13-5.27 for activated carbon, 5.04 for carbon black, 3.83 for coal to 3.08 for wood, organic carbon partitioning approach should be more specifically categorized, considering the various forms, nature and origins of organic carbon in sediment. Sorption rate constants and fraction parameters, which were numerically defined from empirical kinetic model with fast and slow sorption fractions, were closely related to the physicochemical properties of the carbonaceous components. Sorption interpretation approaches with a specific property and viewpoint, such as organic carbon partitioning, soot carbon distribution, or surface area correlation, did not properly explain the overall results on sorption capacity, fast and slow sorption kinetics, and partitioning coefficient. It is also important to emphasize the heterogeneous nature of sediment and the difficulties of encompassing the partitioning among its carbonaceous components.

  14. A new kinetic model based on the remote control mechanism to fit experimental data in the selective oxidation of propene into acrolein on biphasic catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Abdeldayem, H.M.; Ruiz, P.; Delmon, B. [Unite de Catalyse et Chimie des Materiaux Divises, Universite Catholique de Louvain, Louvain-La-Neuve (Belgium); Thyrion, F.C. [Unite des Procedes Faculte des Sciences Appliquees, Universite Catholique de Louvain, Louvain-La-Neuve (Belgium)

    1998-12-31

    A new kinetic model for a more accurate and detailed fitting of the experimental data is proposed. The model is based on the remote control mechanism (RCM). The RCM assumes that some oxides (called `donors`) are able to activate molecular oxygen transforming it to very active mobile species (spillover oxygen (O{sub OS})). O{sub OS} migrates onto the surface of the other oxide (called `acceptor`) where it creates and/or regenerates the active sites during the reaction. The model contains tow terms, one considering the creation of selective sites and the other the catalytic reaction at each site. The model has been tested in the selective oxidation of propene into acrolein (T=380, 400, 420 C; oxygen and propene partial pressures between 38 and 152 Torr). Catalysts were prepared as pure MoO{sub 3} (acceptor) and their mechanical mixtures with {alpha}-Sb{sub 2}O{sub 4} (donor) in different proportions. The presence of {alpha}-Sb{sub 2}O{sub 4} changes the reaction order, the activation energy of the reaction and the number of active sites of MoO{sub 3} produced by oxygen spillover. These changes are consistent with a modification in the degree of irrigation of the surface by oxygen spillover. The fitting of the model to experimental results shows that the number of sites created by O{sub SO} increases with the amount of {alpha}-Sb{sub 2}O{sub 4}. (orig.)

  15. Author Details

    African Journals Online (AJOL)

    PROMOTING ACCESS TO AFRICAN RESEARCH. AFRICAN JOURNALS ONLINE (AJOL) · Journals · Advanced Search · USING AJOL · RESOURCES. Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads.

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    African Journals Online (AJOL)

    Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads. ... An algorithm to retrieve Land Surface Temperature using Landsat-8 Dataset Abstract PDF. ISSN: 2225-8531.

  17. Kinetics and Mechanism of Oxidation of Triethylene Glycol and Tetraethylene Glycol by Ditelluratoargentate (III in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Jinhuan Shan

    2013-01-01

    Full Text Available The kinetics of oxidation of triethylene glycol and tetraethylene glycol by ditelluratoargentate (III (DTA in alkaline liquids has been studied spectrophotometrically in the temperature range of 293.2 K–313.2 K. The reaction rate showed first-order dependence in DTA and fractional order with respect to triethylene glycol or tetraethylene glycol. It was found that the pseudo-first-order rate constant (kobs increased with an increase in concentration of OH− and a decrease in concentration of H4TeO6 2−. There was a negative salt effect and no free radicals were detected. A plausible mechanism involving a two-electron transfer was proposed, and the rate equations derived from the mechanism explained all the experimental results and observations. The activation parameters along with the rate constants of the rate-determining step were calculated.

  18. Mechanism and kinetic considerations of TOC removal from the powdered activated carbon ozonation of diclofenac aqueous solutions.

    Science.gov (United States)

    Beltrán, Fernando J; Pocostales, J Pablo; Alvarez, Pedro M; Jaramillo, Josefa

    2009-09-30

    Ozonation of DCF in aqueous solution in the presence of powdered activated carbon (PAC) has been studied for mechanistic and kinetic purposes. The effects of gas flow rate, ozone gas concentration and initial TOC on the TOC elimination rate were then investigated. The use of PAC allows liquid-solid and internal diffusion mass transfer resistances being eliminated. Gas-liquid mass transfer resistance is also eliminated when ozonation is applied to DCF preozonated solutions. In the absence of mass transfer resistances a mechanism of reactions involving homogeneous and heterogeneous steps for TOC removal was proposed. From this mechanism a mathematical model constituted by mass balances of main species in water was established. Considerations about the changing nature of ozonation intermediates, as being promoters or inhibitors of ozone decomposition, is a key point to better predict the experimental concentrations of species present in this system.

  19. Crystallization Mechanism and Kinetics of BaO-Li2O-ZrO2-SiO2 Glasses

    Directory of Open Access Journals (Sweden)

    Cristian Berto da Silveira

    2002-03-01

    Full Text Available Differential thermal analysis and scanning electron microscopy were used to determine the influence of the addition of BaO on the crystallization mechanism of Li2O-ZrO2-SiO2 systems. As the concentration of BaO in the samples increased, a transition occurred in the predominant crystallization mechanism, which passed from superficial to volumetric. To determine the maximum nucleation rate, the crystallization kinetics of the sample containing 20 mole % BaO, which showed the most uniform crystallization, was studied by counting the nuclei with an image analyzer. The first nuclei appeared at the first endothermic inflection point (at the start of Tg, at 440 °C, while the maximum number of nuclei was counted at the midpoint of the glass transition region (446 °C. These results are similar to those observed for other materials that crystallize in volume, and confirm scanning electron microscopy data.

  20. Kinetics and mechanism of the gas-phase reaction of Cl atoms and OH radicals with fluorobenzene at 296 K

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Nielsen, Ole John; Hurley, MD

    2002-01-01

    Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms and OH radicals with fluorobenzene, C6H5F, in 700 Torr of N-2 or air diluent at 296 K. Reaction of Cl atoms with C6H5F proceeds via two pathways: H-atom abstraction to give HCl and the C6H4F...... with Cl atoms via a mechanism which, at least in part, leads neither to production of C6H5Cl nor to reformation of C6H5F. As the steady-state Cl atom concentration is increased, the fraction of the C6H5F-Cl adduct undergoing reaction with Cl atoms increases causing an increase in the effective rate...

  1. Author Details

    African Journals Online (AJOL)

    Details PDF · Vol 22, No 2 (1999) - Articles Vegetation under different tree species in Acacia woodland in the Rift Valley of Ethiopia Details PDF · Vol 22, No 2 (1999) - Articles Preliminary evaluation of Phytomyza orobanchia (Diptera: Agromyzidae) as a controller of Orobanche spp in Ethiopia Details PDF. ISSN: 2520–7997.

  2. Evaluation of reduced chemical kinetic mechanisms used for modeling mild combustion for natural gas

    Directory of Open Access Journals (Sweden)

    Hamdi Mohamed

    2009-01-01

    Full Text Available A numerical and parametric study was performed to evaluate the potential of reduced chemistry mechanisms to model natural gas chemistry including NOx chemistry under mild combustion mode. Two reduced mechanisms, 5-step and 9-step, were tested against the GRI-Mech3.0 by comparing key species, such as NOx, CO2 and CO, and gas temperature predictions in idealized reactors codes under mild combustion conditions. It is thus concluded that the 9-step mechanism appears to be a promising reduced mechanism that can be used in multi-dimensional codes for modeling mild combustion of natural gas.

  3. Kinetic and mechanisms of methanimine reactions with singlet and triplet molecular oxygen: Substituent and catalyst effects

    Science.gov (United States)

    Asgharzadeh, Somaie; Vahedpour, Morteza

    2018-06-01

    Methanimine reaction with O2 on singlet and triplet potential energy surfaces are investigated using B3PW91, M06-2X, MP2 and CCSD(T) methods. Thermodynamic and kinetic parameters are calculated at M06-2X method. The most favorable channel involves H-abstraction of CH2NH+O2 to the formation of HCN + H2O2 products via low level energy barrier. The catalytic effect of water molecule on HCN + H2O2 products pathway are investigated. Result shows that contribution of water molecule using complex formation with methanimine can decreases barrier energy of transition state and the reaction rate increases. Also, substituent effect of fluorine atom as deactivating group are investigated on the main reaction pathway.

  4. Kinetics and mechanisms of the oxidation of cobalt at 600-8000C

    International Nuclear Information System (INIS)

    Hsu, H.S.; Yurek, G.J.

    1982-01-01

    Two-phase layered scales comprising CoO and Co 3 O 4 formed on cobalt during oxidation at 600 0 , 700 0 , and 800 0 C and at oxygen partial pressures in the range 0.001-1 atm. The kinetics, which were obtained by thermogravimetric analysis, obeyed a parabolic rate law after an initial, nonparabolic stage of oxidation. The monoxide consisted of relatively large grains (10μ) and the spinel comprised small grains (3μ) for all conditions of oxidation. Grain boundary diffusion of cations played a significant role in the growth of the spinal layer. Thermogravimetric data and the steady-state ratio of the oxide layer thicknesses were employed to calculate the rates of thickening of the individual oxide layers and the rate of oxidation of CoO to Co 3 O 4

  5. The mechanism distinguishability problem in biochemical kinetics: the single-enzyme, single-substrate reaction as a case study.

    Science.gov (United States)

    Schnell, Santiago; Chappell, Michael J; Evans, Neil D; Roussel, Marc R

    2006-01-01

    A theoretical analysis of the distinguishability problem of two rival models of the single enzyme-single substrate reaction, the Michaelis-Menten and Henri mechanisms, is presented. We also outline a general approach for analysing the structural indistinguishability between two mechanisms. The approach involves constructing, if possible, a smooth mapping between the two candidate models. Evans et al. [N.D. Evans, M.J. Chappell, M.J. Chapman, K.R. Godfrey, Structural indistinguishability between uncontrolled (autonomous) nonlinear analytic systems, Automatica 40 (2004) 1947-1953] have shown that if, in addition, either of the mechanisms satisfies a particular criterion then such a transformation always exists when the models are indistinguishable from their experimentally observable outputs. The approach is applied to the single enzyme-single substrate reaction mechanism. In principle, mechanisms can be distinguished using this analysis, but we show that our ability to distinguish mechanistic models depends both on the precise measurements made, and on our knowledge of the system prior to performing the kinetics experiments.

  6. Research Article. Kinetics and Mechanism of Drug Release from Loratadine Orodispersible Tablets Developed without Lactose

    Directory of Open Access Journals (Sweden)

    Ciurba Adriana

    2017-03-01

    Full Text Available Objective: The aim of this study is to develop lactose-free orodispersible tablets with loratadine for patients with lactose intolerance. Materials and methods: Seven compositions (F1-F7 of 10 mg loratadine were prepared in form of orally disintegrating tablets, by direct compression, using croscarmellose sodium and pre-gelatinized starch in various concentrations as superdisintegrants, diluted with microcrystalline cellulose and combined with mannitol and maltodextrin as binder agents. The tablets had been studied in terms of their pharmacotechnical characteristics, by determining: the weight uniformity of the tablets, their friability, breaking strength and disintegration time, drug content and the dissolution profile of loratadine. The statistical analyses were performed with GraphPad Prism Software Inc. As dependent variables, both the hardness of the tablets and their disintegration ability differ between batches due to their compositional differences (as independent variables. DDSolver were used for modeling the kinetic of the dissolution processes by fitting the dissolution profiles with time-dependent equations (Zero-order, First-order, Higuchi, Korsmeyer-Peppas, Peppas-Sahlin. Results: All proposed formulas shows rapid disintegration, in less than 15 seconds, and the dissolution loratadine spans a period of about 10 minutes. Akaike index as well as R2 adjusted parameter have demonstrated that the studied dissolution profiles are the best fitted by Zero-order kinetic. Conclusion: In conclusion, association of croscarmellose sodium (7.5% with pre-gelatinized starch (6% as superdisintegrants and mannitol as the binder agent (35%, positively influences the dissolution properties of loratadine from orally fast dispersible tablets.

  7. Synthesis, kinetic mechanism and docking studies of vanillin derivatives as inhibitors of mushroom tyrosinase.

    Science.gov (United States)

    Ashraf, Zaman; Rafiq, Muhammad; Seo, Sung-Yum; Babar, Mustafeez Mujtaba; Zaidi, Najam-us-Sahar Sadaf

    2015-09-01

    The purpose of the present study was to discover the extent of contribution to antityrosinase activity by adding hydroxy substituted benzoic acid, cinnamic acid and piperazine residues to vanillin. The study showed the transformation of vanillin into esters as shown in (4a-4d), (6a-6b), and (8a-8b). In addition, the relationship between structures of these esters and their mushroom tyrosinase inhibitory activity was explored. The kinetics of inhibition on mushroom tyrosinase by these esters was also investigated. It was found that hydroxyl substituted benzoic acid derivatives were weak inhibitors; however hydroxy or chloro substituted cinnamic acid and piperazine substituted derivatives were able to induce significant tyrosinase inhibition. The mushroom tyrosinase (PDBID 2ZWE) was docked with synthesized vanillin derivatives and their calculated binding energies were compared with experimental IC50 values which provided positive correlation. The most potent derivative 2-(4-formyl-2-methoxyphenoxy)-2-oxoethyl (2E)-3-(4-hydroxyphenyl)prop-2-enoate (6a) possesses hydroxy substituted cinnamic acid scaffold having IC50 value 16.13 μM with binding energy of -7.2 kcal/mol. The tyrosinase inhibitory activity of (6a) is comparable with standard kojic acid. Kinetic analysis indicated that compound 6a was mixed-type tyrosinase inhibitor with inhibition constant values Ki (13 μM) and Ki' (53 μM) and formed reversible enzyme inhibitor complex. The active vanillin analog (6a) was devoid of toxic effects as shown in cytotoxic studies. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Study of radionuclides migration in hydraulic binders. Influence of binder alteration on transfer mechanisms and kinetic

    International Nuclear Information System (INIS)

    Richet, C.

    1992-01-01

    In the framework of low and medium activity wastes surface storage, hydraulic binders materials are usually used as containment barrier. The safety analysis of this storage mode involves the knowledge of their behaviour and of their retention capacity towards radionuclides, at short and long-term. The knowledge of diffusional processes inside their liquid phase and those of the interactions existing between the diffusing element and the cement matrix, as well as their kinetics, are essential elements for the study of their durability on 300 years. An experimental methodology has been defined, allowing the characterization of the transfer of an element j in a porous material by the determination of the diffusion coefficient of j in the pores of the material x and the determination of the local equilibrium constant characterizing the interaction of j with the material x. This can be made from the analytical expressions coming from the Fick laws. These parameters have been studied from diffusion and leaching experiments of radionuclides in pure cement pastes. A modelling of the leaching processes is proposed here. The decomposition of the hydraulic binders, by their leaching in a demineralized solution at 'aggressive' pH, leads essentially to their decalcification - whose kinetics answers to a pure diffusion law in √t - and an increase of their porosity. In these attack conditions, it seems that it exists a decalcification limit condition, from which a lattice of interconnected microcracks is developed in all the material. In consequence, the retention capacity of these degraded materials towards radionuclides decreases. The cesium transfer appears more sensitive to the degradation of the material than of those of the tritium. (O.M.)

  9. Ejecta cloud from the AIDA space project kinetic impact on the secondary of a binary asteroid: I. mechanical environment and dynamical model

    Science.gov (United States)

    Yu, Yang; Michel, Patrick; Schwartz, Stephen R.; Naidu, Shantanu P.; Benner, Lance A. M.

    2017-01-01

    An understanding of the post-impact dynamics of ejecta clouds are crucial to the planning of a kinetic impact mission to an asteroid, and also has great implications for the history of planetary formation. The purpose of this article is to track the evolution of ejecta produced by AIDA mission, which targets for kinetic impact the secondary of near-Earth binary asteroid (65803) Didymos on 2022, and to feedback essential informations to AIDA's ongoing phase-A study. We present a detailed dynamic model for the simulation of an ejecta cloud from a binary asteroid that synthesizes all relevant forces based on a previous analysis of the mechanical environment. We apply our method to gain insight into the expected response of Didymos to the AIDA impact, including the subsequent evolution of debris and dust. The crater scaling relations from laboratory experiments are employed to approximate the distributions of ejecta mass and launching speed. The size distribution of fragments is modeled with a power law fitted from observations of real asteroid surface. A full-scale demonstration is simulated using parameters specified by the mission. We report the results of the simulation, which include the computed spread of the ejecta cloud and the recorded history of ejecta accretion and escape. The violent period of the ejecta evolution is found to be short, and is followed by a stage where the remaining ejecta is gradually cleared. Solar radiation pressure proves to be efficient in cleaning dust-size ejecta, and the simulation results after two weeks shows that large debris on polar orbits (perpendicular to the binary orbital plane) has a survival advantage over smaller ejecta and ejecta that keeps to low latitudes.

  10. Statistical mechanics and the description of the early universe II. Principle of detailed balance and primordial 4He formation

    DEFF Research Database (Denmark)

    Pessah, Martin Elias; F. Torres, Diego

    2001-01-01

    If the universe is slightly non-extensive, and the distribution functions are not exactly given by those of Boltzmann-Gibbs, the primordial production of light elements will be non-trivially modified. In particular, the principle of detailed balance (PDB), of fundamental importance in the standard...... the formation of Helium and Deuterium, and study the kind of deviation one could expect from the standard regime. The correction to the capture time, the moment in which Deuterium can no longer be substantially photo-disintegrated, is also presented. This allows us to take into account the process of the free...

  11. Author Details

    African Journals Online (AJOL)

    Igwe, JC. Vol 4, No 6 (2010) - Articles Studies on the kinetics and intraparticle diffusivities of BOD, colour and TSS reduction from palm oil mill effluent (POME) using boiler fly ash. Abstract PDF. ISSN: 1996-0786. AJOL African Journals Online. HOW TO USE AJOL... for Researchers · for Librarians · for Authors · FAQ's · More ...

  12. Author Details

    African Journals Online (AJOL)

    Onyegbado, CO. Vol 4, No 6 (2010) - Articles Studies on the kinetics and intraparticle diffusivities of BOD, colour and TSS reduction from palm oil mill effluent (POME) using boiler fly ash. Abstract PDF. ISSN: 1996-0786. AJOL African Journals Online. HOW TO USE AJOL... for Researchers · for Librarians · for Authors · FAQ's ...

  13. Author Details

    African Journals Online (AJOL)

    Cherfia, Radia. Vol 16, No 3 (2017) - Articles Kinetic models and parameters estimation study of biomass and ethanol production from inulin by Pichia caribbica (KC977491) Abstract PDF. ISSN: 1684-5315. AJOL African Journals Online. HOW TO USE AJOL... for Researchers · for Librarians · for Authors · FAQ's · More about ...

  14. Author Details

    African Journals Online (AJOL)

    Immobilization of lead in shooting range soil using biochar from spent mushroomsubstrateImmobilization of lead in shooting range soil using biochar from spent mushroomsubstrate. Abstract PDF · Vol 9, No 6S (2017) - Articles Sorption of malachite green (MG) by cassava stem biochar (CSB) kinetic and isotherm studies

  15. Author Details

    African Journals Online (AJOL)

    Tan, K. Vol 9, No 6S (2017) - Articles Lower limb kinematics analysis during roundhouse kick among novices in muay thai. Abstract PDF · Vol 9, No 6S (2017) - Articles Kinetics analysis of step and jump forward lunge among badminton players. Abstract PDF. ISSN: 1112-9867. AJOL African Journals Online. HOW TO USE ...

  16. Author Details

    African Journals Online (AJOL)

    Kinetic studies of alkaline phosphatase extracted from rabbit (Lepus townsendii) liver. Abstract PDF · Vol 10, No 32 (2011) - Articles Sodium metabisulphite induced polymerization of sickle cell haemoglobin incubated in extracts of three medicinal plants (Anacardium occidentale, Psidium guajava and Terminalia catappa)

  17. Author Details

    African Journals Online (AJOL)

    Iwalokun, B A. Vol 1, No 2 (2002) - Articles Comparative kinetics of digoxin sensitive (NAK) ATPase and Ca 2+ ATPase in symptomatic and asymptomatic patients with faciparum malaria. Abstract. ISSN: 1596-3381. AJOL African Journals Online. HOW TO USE AJOL... for Researchers · for Librarians · for Authors · FAQ's ...

  18. Author Details

    African Journals Online (AJOL)

    Afolabi, B M. Vol 1, No 2 (2002) - Articles Intercurrent infections during episode of sever falciparum malaria attack in Nigerian children. Abstract · Vol 1, No 2 (2002) - Articles Comparative kinetics of digoxin sensitive (NAK) ATPase and Ca 2+ ATPase in symptomatic and asymptomatic patients with faciparum malaria

  19. Author Details

    African Journals Online (AJOL)

    Simoyi, Reuben H. Vol 55 (2002) - Articles Complex Kinetics in the Reaction of Taurine with Aqueous Bromine and Acidic Bromate : A Possible Cytoprotective Role against Hypobromous Acid Abstract PDF. ISSN: 0379-4350. AJOL African Journals Online. HOW TO USE AJOL... for Researchers · for Librarians · for Authors ...

  20. Author Details

    African Journals Online (AJOL)

    Ayodele, E.T., Ethiopia. Vol 15, No 1 (2001) - Articles Synthesis and fungicidal activity of substituted dibenzyl trisulfides. Abstract PDF · Vol 14, No 2 (2000) - Articles Kinetics of periodate oxidation of tris-(4,4'-dimethyl-2,2'-bipyridine) iron(II) in acid medium. Abstract PDF. ISSN: 1726-801X. AJOL African Journals Online.

  1. Author Details

    African Journals Online (AJOL)

    Effets De Thonningia sanguinea (Thos) Sur La Qualite Des Oeufs Et Le Taux De Ponte Des Poules Au Cours D\\'une Salmonellose Experimentale A Salmonella enterica Serotype Enteritidis Lysotype 6. Abstract PDF · Vol 7, No 2 (2008) - Articles Uptake and kinetic properties of choline and ethanolamine in Plasmodium ...

  2. Kinetics and mechanisms of metal retention/release in geochemical processes in soil. 1997 annual progress report

    International Nuclear Information System (INIS)

    Taylor, R.W.

    1997-01-01

    'Remediation of soils polluted with heavy metals is a major challenge facing the nation. This is especially so at many DOE facilities and other superfund sites. In many cases, speciation of the metals is inaccurate and difficult and the mechanisms by which the metals are retained/released in soils over long times are poorly understood. Consequently, the long-term fate of metals in soils cannot be precisely predicted and often, the remediation recommendations and techniques that are employed to clean up soils may be ineffective or unnecessary. Accordingly, the authors are proposing work to generate basic knowledge on the kinetics and mechanism(s) of heavy metal retention/release by soil mineral colloids as affected by inorganic anion. The nature of the interaction of Cd(II), Co(II), Cr(VI), Cu(II), Ni(II) and Pb(II) with pure soil minerals and extracted soil clays will be investigated. The colloids will be characterized in terms of surface area, surface charge and surface site density. They will be used to study the effect(s) of pH, phosphate rate, and temperature on metals retention/release. The experiments will involve using various kinetic and isothermic sorption equations as models to describe the data thus acquired. The spectroscopic methods will involve using extended x-ray absorption fine structure spectroscopy (EXAFS) and Fourier Transform Infrared Spectroscopy (FTIR). The data generated from the proposed study will assist in designing better remediation strategies to effectively clean up toxic heavy metal contaminated soils at DOE facilities and other superfund sites.'

  3. Kinetics and mechanism of the oxidation of some vicinal and non ...

    Indian Academy of Sciences (India)

    Unknown

    2.1 Materials. The diols and monoethers used were commercial products (BDH or Fluka) and were ..... charge separation takes place in the transition state of the reaction. ... The following mechanism (scheme 1) accounts for the observed data.

  4. PAH growth initiated by propargyl addition: Mechanism development and computational kinetics

    KAUST Repository

    Raj, Abhijeet Dhayal; Rachidi, Mariam El; Chung, Suk-Ho; Sarathy, Mani

    2014-01-01

    Polycyclic aromatic hydrocarbon (PAH) growth is known to be the principal pathway to soot formation during fuel combustion, as such, a physical understanding of the PAH growth mechanism is needed to effectively assess, predict, and control soot

  5. Conformational inversion-topomerization mechanism of ethylcyclohexyl isomers and its role in combustion kinetics

    KAUST Repository

    Bian, Huiting; Wang, Zhandong; Sun, Jinhua; Zhang, Feng

    2016-01-01

    the formation of subsequent decomposition products. In this work, the conformational inversion-topomerization mechanism and H-migration reactions for six ethylcyclohexyl radical isomers were systematically studied by ab initio calculations and the transition

  6. Kinetics and mechanism of carbon-8 methylation of purine bases and nucleosides by methyl radical

    International Nuclear Information System (INIS)

    Zady, M.F.; Wong, J.L.

    1977-01-01

    The kinetics of homolytic methylation of the model purine compound caffeine at carbon-8 were determined as a function of several reaction variables. The methyl radical was generated from tert-butyl peracetate (BPA) either thermally (65 to 95 0 C) or photochemically (greater than 300 nm, 25 0 C). The thermal reaction k (25 0 C) was found to be 3.09 x 10 -8 s -1 from the linear log k (pseudo-first-order) vs. l/T plot. The light reactions using the 450- and 1200-W mercury lamps proceeded with k (25 0 C) 450- and 2160-fold greater, respectively. The derived activation energies are consistent with an S/sub E/Ar reaction. Increasing the concentration of caffeine from 0.25 M to 1.67 M in the presence of 3 molar equiv of BPA did not cause any side reaction. The pH-rate profile can be predicted by rate equations, which are derived on the basis of an electrophilic substitution occurring on the free base and conjugate acid of a heteroaromatic system. A competition study using tetrahydrofuran reveals the presence of a radical sigma complex IIIa and a charge transfer complex IIIb as intermediates for methylation under neutral and acidic conditions, respectively. Their rate-determining nature was indicated by the small positive kinetic isotope effect and the inverse solvent isotope effects: k/sub H 3 O + //k/sub D 3 O + / = 0.87 and k/sub H 2 O//k/sub D 2 O/ = 0.32. Thus, in acidic medium, a preequilibrium proton transfer to form the caffeine conjugate acid precedes the rate-controlling formation of IIIb. In neutral solution, the rate-determining step appears to be the protonation of the radical nitrogen in IIIa converting it to III. The acid-catalyzed caffeine-BPA reaction was shown to be general for other purines such as adenine, adenosine, guanine, guanosine, hypoxanthine, and inosine

  7. Removal of methylene blue from aqueous solution with magnetite loaded multi-wall carbon nanotube: Kinetic, isotherm and mechanism analysis

    International Nuclear Information System (INIS)

    Ai, Lunhong; Zhang, Chunying; Liao, Fang; Wang, Yao; Li, Ming; Meng, Lanying; Jiang, Jing

    2011-01-01

    Highlights: ► M-MWCNTs were synthesized by a facile one-pot solvothermal method and used as an efficient adsorbent for removing toxic dye from aqueous solution. ► The adsorption process was characterized by kinetics and isotherm analysis. ► FTIR analysis was employed to investigate the interactions between M-MWCNTs and dye. - Abstract: In this study, we have demonstrated the efficient removal of cationic dye, methylene blue (MB), from aqueous solution with the one-pot solvothermal synthesized magnetite-loaded multi-walled carbon nanotubes (M-MWCNTs). The as-prepared M-MWCNTs were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) spectroscopy. The effects of contact time, initial dye concentration, and solution pH on the adsorption of MB onto M-MWCNTs were systematically studied. It was shown that the MB adsorption was pH-dependent. Adsorption kinetics was best described by the pseudo-second-order model. Equilibrium data were well fitted to the Langmuir isotherm model, yielding maximum monolayer adsorption capacity of 48.06 mg g −1 . FTIR analysis suggested that the adsorption mechanism was possibly attributed to the electrostatic attraction and π–π stacking interactions between MWCNTs and MB.

  8. Kinetics and mechanism of reduction of iron(iii) kojic acid complex by hydroquinone and l-cysteine

    International Nuclear Information System (INIS)

    Hussain, Z.; Perviaz, M.; Kazmi, S.A.; Johnson, A.S.; Offiong, O.E.

    2014-01-01

    The effect of pH on the kinetics of reduction of iron(III) kojic acid complex by hydroquinone (H/sub 2/Q) and L-cysteine (L-Cys) was studied in the pH range of 2.34 - 4.03 for H/sub 2/Q and 3.04 - 5.5 for L-cysteine at ionic strength of 0.5 M and at 35 degree C. The pseudo-first order rate constants for the reduction of Fe(KA)3 by L-cysteine and hydroquinone increase linearly with increasing reductant concentration, indicating first-order kinetics in reductant concentration. However, whereas the rate of reduction by H2Q increases with increasing pH, an opposite trend was observed in the case of reduction by L-cysteine. Plausible rate laws and mechanisms have been proposed in line with these observations. Activation parameters (delta H no and delta S no) were evaluated for the reduction of iron (III) kojic acid complex by cysteine and the values obtained are 35.25 kJmol-1, -141.4 JK-1mol-1 and 28.14 kJmol-1 , 161.2 JK-1mol-1 for pH 4.5 and 3.52 respectively. (author)

  9. Growth kinetics and mass transport mechanisms of GaN columns by selective area metal organic vapor phase epitaxy

    Science.gov (United States)

    Wang, Xue; Hartmann, Jana; Mandl, Martin; Sadat Mohajerani, Matin; Wehmann, Hergo-H.; Strassburg, Martin; Waag, Andreas

    2014-04-01

    Three-dimensional GaN columns recently have attracted a lot of attention as the potential basis for core-shell light emitting diodes for future solid state lighting. In this study, the fundamental insights into growth kinetics and mass transport mechanisms of N-polar GaN columns during selective area metal organic vapor phase epitaxy on patterned SiOx/sapphire templates are systematically investigated using various pitch of apertures, growth time, and silane flow. Species impingement fluxes on the top surface of columns Jtop and on their sidewall Jsw, as well as, the diffusion flux from the substrate Jsub contribute to the growth of the GaN columns. The vertical and lateral growth rates devoted by Jtop, Jsw and Jsub are estimated quantitatively. The diffusion length of species on the SiOx mask surface λsub as well as on the sidewall surfaces of the 3D columns λsw are determined. The influences of silane on the growth kinetics are discussed. A growth model is developed for this selective area metal organic vapor phase epitaxy processing.

  10. Kinetics and mechanism of photoaccelerated isotope exchange between U(VI) and U(IV) in oxalate solutions

    International Nuclear Information System (INIS)

    Shaban, I.S.; Owreit, M.F.; Nikitenko, S.I.

    1992-01-01

    A kinetic study of thermal and photoaccelerated U(IV)-U(VI) isotope exchange has been carried out in oxalate solutions at 11-40 deg C. The rate and quantum yield were determined as a function of U(IV), U(VI) and oxalate concentration, wavelength of incident light, temperature and absorbed dose of γ-radiation. The kinetic equations for thermal and photoaccelerated exchange have been obtained. It was assumed that the mechanism of exchange involves formation of U(V) as an intermediate, followed by slow exchange between U(V) and U(IV). The isokinetic dependence confirms the identity of limiting stages for thermal and photostimulated exchange. The upper component of photoexcited T 1 level of uranyl is supposed to be the most reactive in the process of U(V) generation. It was observed that the small doses of γ-radiation evoke the acceleration of isotope exchange, however, at D>100 krad the rate of exchange is reduced to the level of thermal exchange. (author) 8 refs.; 4 figs.; 2 tabs

  11. Laser flash-photolysis and gas discharge in N2O-containing mixture: kinetic mechanism

    Science.gov (United States)

    Kosarev, Ilya; Popov, Nikolay; Starikovskaia, Svetlana; Starikovskiy, Andrey; mipt Team

    2011-10-01

    The paper is devoted to further experimental and theoretical analysis of ignition by ArF laser flash-photolysis and nanosecond discharge in N2O-containing mixture has been done. Additional experiments have been made to assure that laser emission is distributed uniformly throughout the cross-section. The series of experiments was proposed and carried out to check validity of O(1D) determination in experiments on plasma assisted ignition initiated by flash-photolysis. In these experiments, ozone density in the given mixture (mixture composition and kinetics has been preliminary analyzed) was measured using UV light absorption in Hartley band. Good coincidence between experimental data and results of calculations have been obtained Temporal behavior of energy input, electric field and electric current has been measured and analyzed. These data are considered as initial conditions for numerical modeling of the discharge in O2:N2O:H2:Ar = 0.3:1:3:5 mixture. Ion-molecular reactions and reactions of active species production in Ar:H2:O2:N2O mixture were analyzed. The set of reactions to describe chemical transformation in the system due to the discharge action has been selected.

  12. Mechanism and Kinetics for the Dissolution of Apatitic Materials in Acid Solutions

    Directory of Open Access Journals (Sweden)

    Calmanovici C.E.

    1997-01-01

    Full Text Available Abstract - This work concerns the study of the digestion step in the production process of phosphoric acid. Some qualitative experiments indicate that the difference between the pH at the surface of the phosphate and that in the bulk of the solution is negligible and that the dissolution is controlled by diffusion of products away from the phosphate particle. In further experiments, to isolate the dissolution phenomenon from the formation of calcium sulfate, the sulfuric acid normally used industrially is replaced by hydrochloric acid. The phosphate material used in our experiments is a model apatitic material: synthetic hydroxyapatite (HAP. The dissolution of calcium hydroxyapatite was studied with increasing amounts of calcium and phosphate at different temperatures. A simple method was developed for this observation based on the time required for complete dissolution of the HAP powder. The results confirm that the dissolution is controlled by a diffusional process through an interface of calcium and phosphate ions released from the solid surface. A kinetic model for the dissolution of apatitic materials is proposed which assumes a shrinking particle behaviour controlled by diffusion of calcium ions. The experimental results are fitted to this model to determine the mass transfer constant for HAP dissolution in acid solutions. The activation energy of the reaction is about 14kJ/mol. This study was carried on in conditions similar to the industrial ones for the production of phosphoric acid by the dihydrate-process

  13. Development of a precise size-controllable pellet injector for the detailed studies of ablation phenomena and mechanism

    International Nuclear Information System (INIS)

    Ichizono, K.; Kugimiya, S.; Nourgostar, S.; Sato, K.N.

    2004-01-01

    A pellet injector of new type with accurately and continuously controllable system of pellet size has started to be developed. This has a unique mechanics and structure of producing a frozen pellet in extremely low temperature region. In the device presently developed in this research, we will precisely adjust the length of the cylindrical pellet (diameter 1.0 mm) from 0.5 to 3 mm by using the special 'length limiting rod' system

  14. Difference between electrostriction kinetics, and mechanical response of segmented polyurethane-based EAP

    Science.gov (United States)

    Jomaa, M. H.; Seveyrat, L.; Perrin, V.; Lebrun, L.; Masenelli-Varlot, K.; Diguet, Gildas; Cavaille, J. Y.

    2017-03-01

    Among the key parameters, which must be taken into account for the choice of actuators used as electrical to mechanical energy converters, the response to a step function and/or the frequency dependence of this response is extremely important. For polymeric actuators and more generally for electroactive polymers, three mechanisms can be at the origin of energy losses, namely dielectric relaxations, viscoelastic relaxations and possible electrical conductivity. In a previous paper, we studied the electrical behavior of segmented polyurethanes with different weight fractions of hard (MDI-BDO) and soft (PTMO) segments. They were shown to exhibit three main mechanisms, namely, from the fastest to the slowest, a secondary or β-relaxation, the main or α-relaxation associated with the glass-rubber transition of the soft phase, and finally, their electrical conductivity. In the present work, we present the general viscoelastic response (as measured through mechanical spectrometry) of the same polyurethanes and their respective time dependent electrostriction responses, and compare it with the relaxation characteristic times of electrical and mechanical spectroscopy data.

  15. Conformational inversion-topomerization mechanism of ethylcyclohexyl isomers and its role in combustion kinetics

    KAUST Repository

    Bian, Huiting

    2016-07-26

    With the "strain-free" cyclic structure, cyclohexane and alkyl cyclohexanes (and their radicals) have various conformers (e.g. chair, boat, and twist etc.) by pseudorotation of the alkyl ring. Noting that different conformers will undergo different types of H-migration reactions, the mechanism of conformational change may impact the distribution of cyclohexyl and the branched cyclohexyl radical isomers during cyclohexane and alkyl cyclohexanes combustion. Consequently, it will influence the formation of subsequent decomposition products. In this work, the conformational inversion-topomerization mechanism and H-migration reactions for six ethylcyclohexyl radical isomers were systematically studied by ab initio calculations and the transition state theory. The updated sub-mechanism of these conformational changes is incorporated into an ethylcyclohexane pyrolysis model. By comparing the simulated results of the "complete" model including the sub-mechanism of conformational changes and the simplified model ignoring these processes, the effect of inversion-topomerization mechanism on the relative concentrations of various ethylcyclohexyl radicals and the formation of subsequent decomposition products were revealed. © 2016.

  16. Author Details

    African Journals Online (AJOL)

    Petrology of the Cenomanian Upper Member of the Mamfe Embayment, southwestern Cameroon Details · Vol 38, No 1 (2002) - Articles Sequence stratigraphy of Iso field, western onshore Niger Delta, Nigeria Details · Vol 39, No 2 (2003) - Articles Preliminary studies on the lithostratigraphy and depositional environment of ...

  17. Author Details

    African Journals Online (AJOL)

    An Overview of Africa's Marine Resources: Their Utilization and Sustainable Management Details · Vol 12, No 3 (2000) - Articles EDITORIAL Ganoderma Lucidum - Paramount among Medicinal Mushrooms. Details · Vol 15, No 3 (2003) - Articles Editorial: Africa's Mushrooms: A neglected bioresource whose time has come

  18. Author Details

    African Journals Online (AJOL)

    Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads. ... Abstract PDF · Vol 3, No 6 (2011) - Articles Mixed convection flow and heat transfer in a vertical wavy channel containing porous and fluid layer with traveling thermal waves. Abstract PDF · Vol 3, No 8 ...

  19. Author Details

    African Journals Online (AJOL)

    Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads. ... Singh, J. Vol 3, No 2 (2011) - Articles Plane waves in a rotating generalized thermo-elastic solid with voids. Abstract PDF. ISSN: 2141-2839. AJOL African Journals Online. HOW TO USE AJOL.

  20. Author Details

    African Journals Online (AJOL)

    Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads. ... Vol 12 (2008) - Articles On the wave equations of shallow water with rough bottom topography. Abstract · Vol 14 (2009) - Articles Energy generation in a plant due to variable sunlight intensity

  1. Author Details

    African Journals Online (AJOL)

    Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads. ... Iliopsoas haematoma in a rugby player. Abstract PDF · Vol 29, No 1 (2017) - Articles The use of negative pressure wave treatment in athlete recovery. Abstract PDF. ISSN: 2078-516X. AJOL African ...

  2. Author Details

    African Journals Online (AJOL)

    Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads. ... Ismail, A. Vol 9, No 3S (2017): Special Issue - Articles Investigate of wave absorption performance for oil palm frond and empty fruit bunch at 5.8 GHz. Abstract PDF · Vol 9, No 3S (2017): Special Issue ...

  3. Author Details

    African Journals Online (AJOL)

    Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads. ... Isa, M.F.M.. Vol 9, No 3S (2017): Special Issue - Articles Experimental and numerical investigation on blast wave propagation in soil structure. Abstract PDF · Vol 9, No 3S (2017): Special Issue - ...

  4. Author Details

    African Journals Online (AJOL)

    Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads. ... No 3S (2017): Special Issue - Articles Experimental and numerical investigation on blast wave propagation in soil structure. Abstract PDF · Vol 9, No 3S (2017): Special Issue - Articles Simulation on ...

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    African Journals Online (AJOL)

    Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads. ... Duwa, S S. Vol 8 (2004) - Articles Lower hybrid waves instability in a velocity–sheared inhomogenous charged dust beam. Abstract · Vol 9 (2005) - Articles The slide away theory of lower hybrid bursts

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    African Journals Online (AJOL)

    Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads. ... Vol 45 (2016) - Articles From vectors to waves and streams: An alternative approach to semantic maps1. Abstract PDF · Vol 48 (2017) - Articles Introduction: 'n Klein ietsie for Johan Oosthuizen

  7. Author Details

    African Journals Online (AJOL)

    Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads. ... to blast loadings. Abstract PDF · Vol 9, No 3S (2017): Special Issue - Articles Experimental and numerical investigation on blast wave propagation in soil structure. Abstract PDF. ISSN: 1112-9867.

  8. Author Details

    African Journals Online (AJOL)

    Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads. ... The use of negative pressure wave treatment in athlete recovery. Abstract PDF · Vol 29, No 1 (2017) - Articles The prevalence, risk factors predicting injury and the severity of injuries sustained during ...

  9. Author Details

    African Journals Online (AJOL)

    Author Details. Journal Home > Advanced Search > Author Details. Log in or Register to get access to full text downloads. ... Vol 29, No 1 (2017) - Articles The use of negative pressure wave treatment in athlete recovery. Abstract PDF · Vol 29, No 1 (2017) - Articles The prevalence, risk factors predicting injury and the ...

  10. Modelling time-dependent mechanical behaviour of softwood using deformation kinetics

    DEFF Research Database (Denmark)

    Engelund, Emil Tang; Svensson, Staffan

    2010-01-01

    The time-dependent mechanical behaviour (TDMB) of softwood is relevant, e.g., when wood is used as building material where the mechanical properties must be predicted for decades ahead. The established mathematical models should be able to predict the time-dependent behaviour. However, these models...... are not always based on the actual physical processes causing time-dependent behaviour and the physical interpretation of their input parameters is difficult. The present study describes the TDMB of a softwood tissue and its individual tracheids. A model is constructed with a local coordinate system that follows...... macroscopic viscoelasticity, i.e., the time-dependent processes are to a significant degree reversible....

  11. Effect of Mg contents on the mechanical proprieties and precipitation kinetics in Al–3.3 wt.% Cu alloy

    Directory of Open Access Journals (Sweden)

    Messaoud Fatmi

    2018-01-01

    Full Text Available The effect of additional Mg on the microstructure, mechanical properties, and transformation kinetics during aging in Al–3.3 wt.% Cu alloy was studied. The compositions and microstructure were examined by X-ray diffraction, Differential scanning calorimetry (DSC and scanning electron microscope (SEM with energy dispersive X-ray spectroscopy (EDS. The results show that the Mg in the Al–Cu alloy mainly precipitated to the grain boundaries during the process of transformation and formed a ternary Al2CuMg metallic compound and the rate of discontinuous precipitation reaction decreases with increasing concentration of Mg. The activation energy of crystallization was evaluated by applying the Kissinger equation.

  12. Implication of low temperature and sonication on electrocrystallization mechanism of Cu thin films: a kinetics and structural correlation

    Directory of Open Access Journals (Sweden)

    Archana Mallik

    2013-04-01

    Full Text Available The effect of an ultrasonic environment during electrodeposition of copper on graphite at various electrolyte temperatures of 25, 20, 15, 10 and 5 °C is reported in this investigation. Resulting Cu deposits formed by potentiostatic deposition were characterized by electrochemical methods, scanning electron microscopy and atomic force microscopy. It was found that in presence of ultrasound the deposition kinetics was mainly dominated by the charge transfer. Copper nucleated according to 3D instantaneous mechanisms for all temperature ranges. The extent of nucleation was found to be increased at low temperatures. Diffusion coefficients and nuclei population density were calculated for each temperature range. Sonicated deposits with good surface coverage were found to consist of spherical copper agglomerates of nanosized particles.

  13. A study of the kinetics and mechanisms of electrocrystallization of indium oxide on an in situ prepared metallic indium electrode

    International Nuclear Information System (INIS)

    Omanovic, S.; Metikos-Hukovic, M.

    2004-01-01

    The mechanisms and kinetics of nucleation and growth of indium oxide film on an in situ prepared metallic indium electrode was studied in a borate buffer solution of pH 10.0 using cyclic voltammetry and chroanoamperometry techniques. It was shown that the initial stage of nucleation of the oxide film includes a three-dimensional progressive nucleation process, combined with a diffusion-controlled growth of the stable indium oxide crystals. The thermodynamic data obtained indicated a strong tendency of indium to form an indium oxide film on its surface in an aqueous solution. It was found that the rate-determining step in the nucleation and growth process is the surface diffusion of electroactive species. The nucleation rate constant, and the number of nucleation active sites were calculated independently. It was shown that between 2 and 15% of sites on the indium surface act as active nucleation centers, and that each active site represents a critical nucleus

  14. The kinetics and mechanism of methanol oxidation on Pt and PtRu catalysts in alkaline and acid media

    Directory of Open Access Journals (Sweden)

    JELENA LOVIC

    2007-07-01

    Full Text Available The kinetic of methanol electrochemical oxidation for a series of platinum and platinum–ruthenium catalysts was investigated. A correlation between the beginning of OHad adsorption and methanol oxidation was demonstarated on Pt single crystals and Pt nanocatalyst. The activity of the nano-structured Pt catalyst was compared with single crystal platinum electrodes assuming the Kinoshita model of nanoparticles. The ruthenium-containing catalysts shifted the onset of methanol oxidation to more negative potentials. The effect was more pronounced in acid than in alkaline media. Based on the established diagnostic criteria, the reaction between COad and OHad species according to the Langmuir–Hinshelwood mechanism was proposed as the rate determining step in alkaline and acid media on Pt and PtRu catalysts.

  15. Kinetic mechanism of molecular energy transfer and chemical reactions in low-temperature air-fuel plasmas.

    Science.gov (United States)

    Adamovich, Igor V; Li, Ting; Lempert, Walter R

    2015-08-13

    This work describes the kinetic mechanism of coupled molecular energy transfer and chemical reactions in low-temperature air, H2-air and hydrocarbon-air plasmas sustained by nanosecond pulse discharges (single-pulse or repetitive pulse burst). The model incorporates electron impact processes, state-specific N(2) vibrational energy transfer, reactions of excited electronic species of N(2), O(2), N and O, and 'conventional' chemical reactions (Konnov mechanism). Effects of diffusion and conduction heat transfer, energy coupled to the cathode layer and gasdynamic compression/expansion are incorporated as quasi-zero-dimensional corrections. The model is exercised using a combination of freeware (Bolsig+) and commercial software (ChemKin-Pro). The model predictions are validated using time-resolved measurements of temperature and N(2) vibrational level populations in nanosecond pulse discharges in air in plane-to-plane and sphere-to-sphere geometry; temperature and OH number density after nanosecond pulse burst discharges in lean H(2)-air, CH(4)-air and C(2)H(4)-air mixtures; and temperature after the nanosecond pulse discharge burst during plasma-assisted ignition of lean H2-mixtures, showing good agreement with the data. The model predictions for OH number density in lean C(3)H(8)-air mixtures differ from the experimental results, over-predicting its absolute value and failing to predict transient OH rise and decay after the discharge burst. The agreement with the data for C(3)H(8)-air is improved considerably if a different conventional hydrocarbon chemistry reaction set (LLNL methane-n-butane flame mechanism) is used. The results of mechanism validation demonstrate its applicability for analysis of plasma chemical oxidation and ignition of low-temperature H(2)-air, CH(4)-air and C(2)H(4)-air mixtures using nanosecond pulse discharges. Kinetic modelling of low-temperature plasma excited propane-air mixtures demonstrates the need for development of a more accurate

  16. Mechanism and kinetics of uranium adsorption onto soil around coal-fired power plant

    Science.gov (United States)

    Yasim, Nurzulaifa Shaheera Erne Mohd; Ariffin, Nik Azlin Nik; Mohammed, Noradila; Ayob, Syafina

    2017-11-01

    Coal is the largest source of energy in Malaysia providing approximately 80 % of all entire power needs. The combustion of coal concentrates a high content of heavy metals and radioactive elements in the ashes and sludge. Hazardous emissions from coal combustion were deposited into the soil and most likely transported into the groundwater system. The presence of radioactive materials in the ground water system can cause a wide range of environmental impacts and adverse health effects like cancer, impairment of neurological function and cardiovascular disease. However, the soil has a natural capability in adsorption of radioactive materials. Thus, this study was evaluated the adsorption capacity of Uranium onto the soil samples collected nearby the coal-fired power plants. In the batch experiment, parameters that were set constant include pH, the amount of soil and contact time. Various initial concentrations of radionuclides elements in the range of 2 mg/L - 10 mg/L were used. The equilibrium adsorption data was analyzed by the Freundlich isotherm and Langmuir isotherms. Then, the influences of solution pH, contact time and temperature on the adsorption process were investigated. The kinetics of radioactive materials was discussed by pseudo-first-order and pseudo-second-order rate equation. Thus, the data from this study could provide information about the potentiality of soil in sorption of radioactive materials that can be leached into groundwater. Besides that, this study could also be used as baseline data for future reference in the development of adsorption modeling in the calculation of distribution coefficient.

  17. Kinetics, isotope effects, and mechanism for the hydrogenation of carbon monoxide on supported nickel catalysts

    International Nuclear Information System (INIS)

    Mori, T.; Masuda, H.; Imai, H.; Miyamoto, A.; Baba, S.; Murakami, Y.

    1982-01-01

    Kinetics and hydrogen-deuterium isotope effects in the methanation of adsorbed CO molecules on a Ni/SiO 2 catalyst were precisely measured by using pulse surface reaction rate analysis (PSRA). When a CO pulse was injected into flowing hydrogen, it was immediately adsorbed on the catalyst and gradually hydrogenated to CH 4 and H 2 O. The amounts of CH 4 and H 2 O produced by the hydrogenation of the adsorbed CO were determined up to various times, and it was found that CH 4 and H 2 O were produced at the same rate. When O 2 instead of CO was injected, H 2 O was immediately produced. From these results, the rate-determining step of the reaction was found to be C-O bond dissociation of an adsorbed CO molecule or a partially hydrogenated CO species. By PSRA, the rate constant for the C-O bond dissocition process per adsorbed CO molecule (k/sub H/) was determined at various temperatures, and the Arrhenius parameters of the rate constant were obtained. The rate constant in flowing deuterium (k/sub D/) was also determined. it was found that k/sub D/ is considerably larger than k/sub H/, indicating an inverse isotope effect. The average value of k/sub H//k/sub D/ was 0.75. From these results, it was concluded that adsorbed CO is not directly dissociated to surface carbon and oxygen atoms but it is partially hydrogenated before C-O bond dissociation under the conditions of the PSRA experiment. 8 figures

  18. Impact of humic acid on the degradation of levofloxacin by aqueous permanganate: Kinetics and mechanism.

    Science.gov (United States)

    Xu, Ke; Ben, Weiwei; Ling, Wencui; Zhang, Yu; Qu, Jiuhui; Qiang, Zhimin

    2017-10-15

    Levofloxacin (LF) is a frequently detected fluoroquinolone in surface water, and permanganate (MnO 4 - ) is a commonly used oxidant in drinking water treatment. This study investigated the impact of humic acid (HA) on LF degradation by aqueous MnO 4 - from both kinetic and mechanistic aspects. In the absence of HA, the second-order rate constant (k) of LF degradation by MnO 4 - was determined to be 3.9 M -1  s -1 at pH 7.5, which increased with decreasing pH. In the presence of HA, the pseudo-first-order rate constant (k obs ) of LF degradation at pH 7.5 was significantly increased by 3.8- and 2.8-fold at [HA] o :[KMnO 4 ] o (mass ratio) = 0.5 and 1, respectively. Secondary oxidant scavenging and electron paramagnetic resonance tests indicated that HA could form a complex with Mn(III), a strongly oxidative intermediate produced in the reaction of MnO 4 - with HA, to induce the successive formation of superoxide radicals (O 2 - ) and hydroxyl radicals (OH). The resulting OH primarily contributed to the accelerated LF degradation, and the complex [HA-Mn(III)] could account for the rest of acceleration. The degradation of LF and its byproducts during MnO 4 - oxidation was mainly through hydroxylation, dehydrogenation and carboxylation, and the presence of HA led to a stronger destruction of LF. This study helps better understand the degradation of organic micropollutants by MnO 4 - in drinking water treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Cu(II)-catalyzed oxidation of dopamine in aqueous solutions: mechanism and kinetics.

    Science.gov (United States)

    Pham, A Ninh; Waite, T David

    2014-08-01

    Spontaneous oxidation of dopamine (DA) and the resultant formation of free radical species within dopamine neurons of the substantia nigra (SN) is thought to bestow a considerable oxidative load upon these neurons and may contribute to their vulnerability to degeneration in Parkinson's disease (PD). An understanding of DA oxidation under physiological conditions is thus critical to understanding the relatively selective vulnerability of these dopaminergic neurons in PD and may support the development of novel neuro-protective approaches for this disorder. In this study, the oxidation of dopamine (0.2-10μM) was investigated both in the absence and the presence of copper (0.01-0.4μM), a redox active metal that is present at considerable concentrations in the SN, over a range of background chloride concentrations (0.01-0.7M), different oxygen concentrations and at physiological pH7.4. DA was observed to oxidize extremely slowly in the absence of copper and at moderate rates only in the presence of copper but without chloride. The oxidation of DA however was significantly enhanced in the presence of both copper and chloride with the rate of DA oxidation greatest at intermediate chloride concentrations (0.05-0.2M). The variability of the catalytic effect of Cu(II) on DA oxidation at different chloride concentrations can be explained and successfully modeled by appropriate consideration of the reaction of Cu(II) species with DA and the conversion of Cu(I) to Cu(II) through oxygenation. This model suggests that the speciation of Cu(II) and Cu(I) is critically important to the kinetics of DA oxidation and thus the vulnerability to degradation of dopaminergic neuron in the brain milieu. Copyright © 2014 Elsevier Inc. All rights reserved.

  20. Kinetics and mechanism of thermal aging embrittlement of duplex stainless steels

    International Nuclear Information System (INIS)

    Chung, H.M.; Chopra, O.K.

    1987-06-01

    Microstructural characteristics of long-term-aged cast duplex stainless steel specimens from eight laboratory heats and an actual component from a commercial boiling water reactor have been investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), small angle neutron scattering (SANS), and atom probe field ion microscopy (APFIM) techniques. Three precipitate phases, i.e., Cr-rich α' and the Ni- and Si-rich G phase, and γ 2 austenite, have been identified in the ferrite matrix of the aged specimens. For CF-8 grade materials, M 23 C 6 carbides were identified on the austenite-ferrite boundaries as well as in the ferrite matrix for aging at ≥ 450 0 C. It has been shown that Si, C, and Mo contents are important factors that influence the kinetics of the G-phase precipitation. However, TEM and APFIM analyses indicate that the embrittlement for ≤400 0 C aging is primarily associated with Fe and Cr segregation in ferrite by spinodal decomposition. For extended aging, e.g., 6 to 8 years at 350 to 400 0 C, large platelike α' formed by nucleation and growth from the structure produced by the spinodal decomposition. The Cr content appears to play an important role either to promote the platelike α' (high Cr content) or to suppress the α' in favor of γ 2 precipitation (low Cr). Approximate TTT diagrams for the spinodal, α', G, γ 2 , and the in-ferrite M 23 C 6 have been constructed for 250 to 450 0 C aging. Microstructural modifications associated with a 550 0 C reannealing and a subsequent toughness restoration are also discussed. It is shown that the toughness restoration is associated primarily with the dissolution of the Cr-rich region in ferrite

  1. Photodegradation of gemfibrozil in aqueous solution under UV irradiation: kinetics, mechanism, toxicity, and degradation pathways.

    Science.gov (United States)

    Ma, Jingshuai; Lv, Wenying; Chen, Ping; Lu, Yida; Wang, Fengliang; Li, Fuhua; Yao, Kun; Liu, Guoguang

    2016-07-01

    The lipid regulator gemfibrozil (GEM) has been reported to be persistent in conventional wastewater treatment plants. This study investigated the photolytic behavior, toxicity of intermediate products, and degradation pathways of GEM in aqueous solutions under UV irradiation. The results demonstrated that the photodegradation of GEM followed pseudo-first-order kinetics, and the pseudo-first-order rate constant was decreased markedly with increasing initial concentrations of GEM and initial pH. The photodegradation of GEM included direct photolysis via (3)GEM(*) and self-sensitization via ROS, where the contribution rates of degradation were 0.52, 90.05, and 8.38 % for ·OH, (1)O2, and (3)GEM(*), respectively. Singlet oxygen ((1)O2) was evidenced by the molecular probe compound, furfuryl alcohol (FFA), and was identified as the primary reactive species in the photolytic process. The steady-state concentrations of (1)O2 increased from (0.324 ± 0.014) × 10(-12) to (1.021 ± 0.040) × 10(-12) mol L(-1), as the initial concentrations of GEM were increased from 5 to 20 mg L(-1). The second-order rate constant for the reaction of GEM with (1)O2 was calculated to be 2.55 × 10(6) M(-1) s(-1). The primary transformation products were identified using HPLC-MS/MS, and possible photodegradation pathways were proposed by hydroxylation, aldehydes reactions, as well as the cleavage of ether side chains. The toxicity of phototransformation product evaluation revealed that photolysis potentially provides a critical pathway for GEM toxicity reduction in potable water and wastewater treatment facilities.

  2. Kinetics of physico-chemical processes during intensive mechanical processing of ZnO-MnO{sub 2} powder mixture

    Energy Technology Data Exchange (ETDEWEB)

    Kakazey, M.; Vlasova, M.; Dominguez-Patino, M. [CIICAp-Universidad Autonoma del Estado de Morelos, Cuernavaca (Mexico); Juarez-Arellano, E.A., E-mail: eajuarez@unpa.edu.mx [Universidad del Papaloapan, Tuxtepec, Oaxaca (Mexico); Bykov, A. [Institute for Problems of Materials Science of NASU, Kyiv (Ukraine); Leon, I. [CIQ-Universidad Autonoma del Estado de Morelos, Cuernavaca (Mexico); Siqueiros-Diaz, A. [FCQI-Universidad Autonoma del Estado de Morelos, Cuernavaca (Mexico)

    2011-10-15

    Experimental results of electron paramagnetic resonance spectra, X-ray diffraction, scanning electron microscopy and infrared spectroscopy demonstrate that the kinetic of the physical and chemical processes that takes place during prolonged intensive mechanical processing (MP, 03120min) of powder mixtures of 50%wt ZnO+50%wt MnO{sub 2} can be described as a three stage process. (1) 030min, particles destruction, formation of superficial defects, fast increment of sample average temperature (from 290 to {approx}600K) and annealing of defects with the lowest energy of activation E{sub ac}. (2) 30390min, further particle destruction, slow increment of sample average temperature (from {approx}600 to {approx}700K), formation and growth of a very disordered layer of {beta}-MnO{sub 2} around ZnO particles, dehydration of MnO{sub 2}, formation of solid solution of Mn{sup 2+} ions in ZnO, formation of nano-quasiamorphous states in the ZnO-MnO{sub 2} mixture and onset of the formation of the ZnMnO{sub 3} phase. (3) 3903120min, the sample average temperature remains constant ({approx}700K), the reaction is completed and the spinel ZnMnO{sub 3} phase with a unit cell a=8.431(1) A and space group Fd3-barm is the only phase present in the sample. No ferromagnetism at room temperature was detected in this study. - Highlights: > The kinetics during mechanical processing of ZnO-MnO{sub 2} samples is a three stage process. > First stage, reduction of crystallites size and accumulation of defects. > Second stage, nano-quasiamorphous states formation and onset of the ZnMnO{sub 3} phase. > Third stage, complete reaction to the spinel ZnMnO{sub 3} phase.

  3. Kinetics of physico-chemical processes during intensive mechanical processing of ZnO-MnO2 powder mixture

    International Nuclear Information System (INIS)

    Kakazey, M.; Vlasova, M.; Dominguez-Patino, M.; Juarez-Arellano, E.A.; Bykov, A.; Leon, I.; Siqueiros-Diaz, A.

    2011-01-01

    Experimental results of electron paramagnetic resonance spectra, X-ray diffraction, scanning electron microscopy and infrared spectroscopy demonstrate that the kinetic of the physical and chemical processes that takes place during prolonged intensive mechanical processing (MP, 0 MP >3120min) of powder mixtures of 50%wt ZnO+50%wt MnO 2 can be described as a three stage process. (1) 0 MP >30min, particles destruction, formation of superficial defects, fast increment of sample average temperature (from 290 to ∼600K) and annealing of defects with the lowest energy of activation E ac . (2) 30 MP >390min, further particle destruction, slow increment of sample average temperature (from ∼600 to ∼700K), formation and growth of a very disordered layer of β-MnO 2 around ZnO particles, dehydration of MnO 2 , formation of solid solution of Mn 2+ ions in ZnO, formation of nano-quasiamorphous states in the ZnO-MnO 2 mixture and onset of the formation of the ZnMnO 3 phase. (3) 390 MP >3120min, the sample average temperature remains constant (∼700K), the reaction is completed and the spinel ZnMnO 3 phase with a unit cell a=8.431(1) A and space group Fd3-barm is the only phase present in the sample. No ferromagnetism at room temperature was detected in this study. - Highlights: → The kinetics during mechanical processing of ZnO-MnO 2 samples is a three stage process. → First stage, reduction of crystallites size and accumulation of defects. → Second stage, nano-quasiamorphous states formation and onset of the ZnMnO 3 phase. → Third stage, complete reaction to the spinel ZnMnO 3 phase.

  4. Phosphorus removal from aqueous solution in parent and aluminum-modified eggshells: thermodynamics and kinetics, adsorption mechanism, and diffusion process.

    Science.gov (United States)

    Guo, Ziyan; Li, Jiuhai; Guo, Zhaobing; Guo, Qingjun; Zhu, Bin

    2017-06-01

    Parent and aluminum-modified eggshells were prepared and characterized with X-ray diffraction, specific surface area measurements, infrared spectroscopy, zeta potential, and scanning electron microscope, respectively. Besides, phosphorus adsorptions in these two eggshells at different temperatures and solution pH were carried out to study adsorption thermodynamics and kinetics as well as the mechanisms of phosphorus adsorption and diffusion. The results indicated that high temperature was favorable for phosphorus adsorption in parent and aluminum-modified eggshells. Alkaline solution prompted phosphorus adsorption in parent eggshell, while the maximum adsorption amount was achievable at pH 4 in aluminum-modified eggshell. Adsorption isotherms of phosphorus in these eggshells could be well described by Langmuir and Freundlich models. Phosphorus adsorption amounts in aluminum-modified eggshell were markedly higher compared to those in parent eggshell. Adsorption heat indicated that phosphorus adsorption in parent eggshell was a typically physical adsorption process, while chemical adsorption mechanism of ion exchange between phosphorus and hydroxyl groups on the surface of eggshells was dominated in aluminum-modified eggshell. The time-resolved uptake curves showed phosphorus adsorption in aluminum-modified eggshell was significantly faster than that in parent eggshell. Moreover, there existed two clear steps in time-resolved uptake curves of phosphorus in parent eggshell. Based on pseudo-second order kinetic model and intraparticle diffusion model, we inferred more than one process affected phosphorus adsorption. The first process was the diffusion of phosphorus through water to external surface and the opening of pore channel in the eggshells, and the second process was mainly related to intraparticle diffusion.

  5. On the mechanism controlling the redox kinetics of Cu-based oxygen carriers

    NARCIS (Netherlands)

    San Pio Bordeje, M.A.; Gallucci, F.; Roghair, I.; van Sint Annaland, M.

    2017-01-01

    Copper oxide on alumina is often used as oxygen carrier for chemical looping combustion owing to its very high reduction rates at lower temperatures and its very good mechanical and chemical stability at temperatures below 1000 °C. In this work, the redox behaviour of CuO/Al2O3 has been studied in

  6. Mechanism and kinetics of the electrocatalytic reaction responsible for the high cost of hydrogen fuel cells.

    Science.gov (United States)

    Cheng, Tao; Goddard, William A; An, Qi; Xiao, Hai; Merinov, Boris; Morozov, Sergey

    2017-01-25

    The sluggish oxygen reduction reaction (ORR) is a major impediment to the economic use of hydrogen fuel cells in transportation. In this work, we report the full ORR reaction mechanism for Pt(111) based on Quantum Mechanics (QM) based Reactive metadynamics (RμD) simulations including explicit water to obtain free energy reaction barriers at 298 K. The lowest energy pathway for 4 e - water formation is: first, *OOH formation; second, *OOH reduction to H 2 O and O*; third, O* hydrolysis using surface water to produce two *OH and finally *OH hydration to water. Water formation is the rate-determining step (RDS) for potentials above 0.87 Volt, the normal operating range. Considering the Eley-Rideal (ER) mechanism involving protons from the solvent, we predict the free energy reaction barrier at 298 K for water formation to be 0.25 eV for an external potential below U = 0.87 V and 0.41 eV at U = 1.23 V, in good agreement with experimental values of 0.22 eV and 0.44 eV, respectively. With the mechanism now fully understood, we can use this now validated methodology to examine the changes upon alloying and surface modifications to increase the rate by reducing the barrier for water formation.

  7. Specific features of precipitation hardening of austenitic steels with various base. 2. Kinetics and mechanism of carbide precipitation

    International Nuclear Information System (INIS)

    Kositsyna, I.I.; Sagaradze, V.V.; Khakimova, O.N.

    1997-01-01

    Electron microscopic studies were carried out to determine the kinetics and mechanisms of precipitation hardening in Fe-Mn, Fe-Mn-Cr, Fe-Cr-Mn-N, Fe-Cr-Ni and Fe-Ni base stainless steels (45G20M2F2, 50Kh16G15N6M2F2, 45Kh18N10G10M2F2, 40Kh18Ni18M2F2, 45N26M2F2). The steels were heat treated under various conditions. It is revealed that in manganese steels the particles of vanadium carbide nucleate according to homogeneous mechanism at all aging temperatures (600-750 deg C). The presence of chromium in the matrix promotes the transition to heterogeneous mechanism of carbide nucleation and growth. With nickel content increasing the plasticity of precipitation hardened steels gets better due to more intense diffusion of atoms and vacancies to grain boundaries and, hence, the widening of near-boundary zones free of carbide particles

  8. Kinetics and mechanisms of reactions of CF, CHF, and CF2 radicals

    International Nuclear Information System (INIS)

    Hsu, D.S.Y.; Umstead, M.E.; Lin, M.C.

    1978-01-01

    This chapter reviews briefly methods for the production of CF, CHF and CF 2 , and inmore detail, the reactions of these interesting and important radicals. Although a considerable, but not extensive, amount of work has been done on the reactions of CF 2 , little of the chemistry of CF and CHF is known. This chapter also includes the preliminary results of some experiments carried out in this Laboratory on the dynamics of some of the reactions involving these radicals. These results were largely arrived at through investigations of the degree of vibrational excitation of the HF and CO reaction products, determined by HF and CO laser emission and CO laser resonance absorption measurements. The coverage of this review is restricted to the gas phase chemistry of these radicals, and does not include their addition reactions to olefins

  9. Optimization and analysis of large chemical kinetic mechanisms using the solution mapping method - Combustion of methane

    Science.gov (United States)

    Frenklach, Michael; Wang, Hai; Rabinowitz, Martin J.

    1992-01-01

    A method of systematic optimization, solution mapping, as applied to a large-scale dynamic model is presented. The basis of the technique is parameterization of model responses in terms of model parameters by simple algebraic expressions. These expressions are obtained by computer experiments arranged in a factorial design. The developed parameterized responses are then used in a joint multiparameter multidata-set optimization. A brief review of the mathematical background of the technique is given. The concept of active parameters is discussed. The technique is applied to determine an optimum set of parameters for a methane combustion mechanism. Five independent responses - comprising ignition delay times, pre-ignition methyl radical concentration profiles, and laminar premixed flame velocities - were optimized with respect to thirteen reaction rate parameters. The numerical predictions of the optimized model are compared to those computed with several recent literature mechanisms. The utility of the solution mapping technique in situations where the optimum is not unique is also demonstrated.

  10. Degradation kinetics and mechanism of penicillin G in aqueous matrices by ionizing radiation

    Science.gov (United States)

    Chu, Libing; Zhuang, Shuting; Wang, Jianlong

    2018-04-01

    The gamma radiation induced-degradation of a β-lactam antibiotic, penicillin G was investigated in aqueous solution. Special attention was paid to the effects of the organic substances such as peptone and glucose on penicillin G degradation, which can be found in the wastewater of the factories producing antibiotics. Results showed that gamma radiation was effective to degrade and deactivate penicillin G in pure water. With the initial concentrations of 0.27 mM, 1.34 mM and 2.68 mM, a complete removal of penicillin G could be achieved at the adsorbed doses of 2.5 kGy, 10 kGy and 20 kGy, respectively. Penicilloic acid from the β-lactam ring cleavage and a series of fragment compounds such as thiazolidine and penicillic acid were identified during gamma irradiation-induced degradation of penicillin G. Addition of Fe2+ was efficient to enhance the mineralization. The TOC removal efficiency of penicillin G was 21.7% using gamma irradiation alone at 10 kGy, which increased to 56.4% with 1.0 mM Fe2+ addition. The gamma radiation-induced degradation of penicillin G was inhibited in the presence of peptone and glucose and the inhibitive effect increased with increasing their concentrations. The rate constant, k of the pseudo first-order kinetics decreased by 74% and 64% in the presence of 1.0 g/L of peptone and glucose, respectively, and by 96% and 89% in the presence of 10 g/L of peptone and glucose, respectively. The ratio of k/k0 was increased by 1.3 times with H2O2 addition and by 3 times with Fe2+ addition, in the presence of 10 g/L of glucose. Adding Fe2+ was effective to improve the ionizing radiation induced degradation of penicillin G antibiotic in the glucose-containing wastewater.

  11. Oxidative degradation of triclosan by potassium permanganate: Kinetics, degradation products, reaction mechanism, and toxicity evaluation.

    Science.gov (United States)

    Chen, Jing; Qu, Ruijuan; Pan, Xiaoxue; Wang, Zunyao

    2016-10-15

    In this study, we systematically investigated the potential applicability of potassium permanganate for removal of triclosan (TCS) in water treatment. A series of kinetic experiments were carried out to study the influence of various factors, including the pH, oxidant doses, temperature, and presence of typical anions (Cl(-), SO4(2-), NO3(-)), humic acid (HA), and fulvic acid (FA) on triclosan removal. The optimal reaction conditions were: pH = 8.0, [TCS]0:[KMnO4]0 = 1:2.5, and T = 25 °C, where 20 mg/L of TCS could be completely degraded in 120 s. However, the rate of TCS (20 μg/L) oxidation by KMnO4 ([TCS]0:[KMnO4]0 = 1:2.5) was 1.64 × 10(-3) mg L(-1)·h(-1), lower than that at an initial concentration of 20 mg/L (2.24 × 10(3) mg L(-1)·h(-1)). A total of eleven products were detected by liquid chromatography-quadrupole-time-of-flight-mass spectrometry (LC-Q-TOF-MS) analysis, including phenol and its derivatives, benzoquinone, an organic acid, and aldehyde. Two main reaction pathways involving CO bond cleavage (-C(8)O(7)-) and benzene ring opening (in the less chlorinated benzene ring) were proposed, and were further confirmed based on frontier electron density calculations and point charges. Furthermore, the changes in the toxicity of the reaction solution during TCS oxidation by KMnO4 were evaluated by using both the luminescent bacteria Photobacterium phosphoreum and the water flea Daphnia magna. The toxicity of 20 mg/L triclosan to D. magna and P. phosphoreum after 60 min was reduced by 95.2% and 43.0%, respectively. Phenol and 1,4-benzoquinone, the two representative degradation products formed during permanganate oxidation, would yield low concentrations of DBPs (STHMFP, 20.99-278.97 μg/mg; SHAAFP, 7.86 × 10(-4)-45.77 μg/mg) after chlorination and chloramination. Overall, KMnO4 can be used as an effective oxidizing agent for TCS removal in water and wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Detailed Microstructural Characterization and Restoration Mechanisms of Duplex and Superduplex Stainless Steel Friction-Stir-Welded Joints

    Science.gov (United States)

    Santos, T. F. A.; Torres, E. A.; Lippold, J. C.; Ramirez, A. J.

    2016-12-01

    Duplex stainless steels are successfully used in a wide variety of applications in areas such as the food industry, petrochemical installations, and sea water desalination plants, where high corrosion resistance and high mechanical strength are required. However, during fusion welding operations, there can be changes to the favorable microstructure of these materials that compromise their performance. Friction stir welding with a non-consumable pin enables welded joints to be obtained in the solid state, which avoids typical problems associated with solidification of the molten pool, such as segregation of alloying elements and the formation of solidification and liquefaction cracks. In the case of superduplex stainless steels, use of the technique can avoid unbalanced proportions of ferrite and austenite, formation of deleterious second phases, or growth of ferritic grains in the heat-affected zone. Consolidated joints with full penetration were obtained for 6-mm-thick plates of UNS S32101 and S32205 duplex stainless steels, and S32750 and S32760 superduplex steels. The welding heat cycles employed avoided the conditions required for formation of deleterious phases, except in the case of the welded joint of the S32760 steel, where SEM images indicated the formation of secondary phases, as corroborated by decreased mechanical performance. Analysis using EBSD and transmission electron microscopy revealed continuous dynamic recrystallization by the formation of cellular arrays of dislocations in the ferrite and discontinuous dynamic recrystallization in the austenite. Microtexture evaluation indicated the presence of fibers typical of shear in the thermomechanically affected zone. These fibers were not obviously present in the stir zone, probably due to the intensity of microstructural reformulation to which this region was subjected.

  13. Kinetic model for the mechanical response of suspensions of sponge-like particles.

    Science.gov (United States)

    Hütter, Markus; Faber, Timo J; Wyss, Hans M

    2012-01-01

    A dynamic two-scale model is developed that describes the stationary and transient mechanical behavior of concentrated suspensions made of highly porous particles. Particularly, we are interested in particles that not only deform elastically, but also can swell or shrink by taking up or expelling the viscous solvent from their interior, leading to rate-dependent deformability of the particles. The fine level of the model describes the evolution of particle centers and their current sizes, while the shapes are at present not taken into account. The versatility of the model permits inclusion of density- and temperature-dependent particle interactions, and hydrodynamic interactions, as well as to implement insight into the mechanism of swelling and shrinking. The coarse level of the model is given in terms of macroscopic hydrodynamics. The two levels are mutually coupled, since the flow changes the particle configuration, while in turn the configuration gives rise to stress contributions, that eventually determine the macroscopic mechanical properties of the suspension. Using a thermodynamic procedure for the model development, it is demonstrated that the driving forces for position change and for size change are derived from the same potential energy. The model is translated into a form that is suitable for particle-based Brownian dynamics simulations for performing rheological tests. Various possibilities for connection with experiments, e.g. rheological and structural, are discussed.

  14. Take-Off Efficiency: Transformation of Mechanical Work Into Kinetic Energy During the Bosco Test

    Directory of Open Access Journals (Sweden)

    Jandova Sona

    2017-09-01

    Full Text Available Purpose. The aim of the study is to present a new method for determining the efficiency of take-off during a 60-s Bosco repeated vertical jump test. Method. The study involved 15 physical education students (age: 21.5 ± 2.4 years; height: 1.81 ± 0.08 m; mass: 76 ± 9 kg. The data were collected with the use of a pedobarographical system (Pedar-x; Novel, Munich, Germany. The statistical analysis utilized a simple linear regression model. Results. Owing to possible fatigue, flight time and flight height decreased. The average flight height was 0.260 ± 0.063 m, and the average contact time equalled 0.54 ± 0.16 s. The average anaerobic power values calculated for the 60-s work period had the mean value of 21.9 ± 6.7 W · kgBW-1; there was a statistically significant (p < 0.05 decrease in anaerobic power during the 60-s Bosco test. Conclusions. The efficiency of mechanical work was highest at the beginning of the test, reaching values of up to 50%. The efficiency of mechanical work conversion into mechanical energy seems to be an appropriate determinant of rising fatigue during the 60-s Bosco jumping test.

  15. Author Details

    African Journals Online (AJOL)

    Journal Home > Advanced Search > Author Details. Log in or Register ... (2013) - Articles Technical Note: Development of a Photobioreactor for Microalgae Culture ... Design, Construction and Evaluation of Motorized Okra Slicer Abstract PDF ...

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    Journal Home > Advanced Search > Author Details. Log in or Register to ... No 1 (2014) - Articles Knowledge and Attitudes towards Basic Cardiopulmonary Resuscitation (CPR) among Community Nurses in Remo Area of Ogun State, Nigeria

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    Journal Home > Advanced Search > Author Details. Log in or Register to get ... Optical bus of centralized relay protection and automation system of medium voltage switchgear for data collection and transmission. Abstract PDF. ISSN: 1112- ...

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    Journal Home > Advanced Search > Author Details. Log in or ... The prevention of mother-to-child HIV transmission programme and infant feeding practices ... Evaluation of a diagnostic algorithm for smear-negative pulmonary tuberculosis in ...

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    Journal Home > Advanced Search > Author Details ... Design and Implementation of an M/M/1 Queuing Model Algorithm and its Applicability in ... Vehicle Identification Technology to Intercept Small Arms and Ammunition on Nigeria Roads

  20. Predictions of NO{sub x} formation in an NH{sub 3}-doped syngas flame using CFD combined with a detailed reaction mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Brink, A; Norstroem, T; Kilpinen, P; Hupa, M [Aabo Akademi, Turku (Finland). Combustion Chemistry Research Group

    1998-12-31

    The formation of NO{sub x} in a CO/H{sub 2}/CH{sub 4}/NH{sub 3} jet in a co-flowing air stream was modeled by use of CFD combined with a comprehensive detailed reaction mechanism. The comprehensive mechanism involved 340 reversible elementary reactions between 55 species. Three different approaches to include the detailed reaction mechanism were tested. In approach I, all chemistry was described with the comprehensive mechanism. In approaches IIa and IIb the comprehensive mechanism was used in post-processing calculations of the nitrogen chemistry. In approach IIa, the temperatures of the reacting structures obtained in the main calculations were used, whereas in approach IIb, the inlet temperatures to the reacting structures were taken from the main calculation. In approach IIIa and IIIb, empirical reaction mechanisms describing the nitrogen chemistry were tested. The turbulence-chemistry interaction was accounted for with a new model, which combines the Eddy-Dissipation Concept with a model based on the `Exchange by Interaction with the Mean`. There was a clear difference between the computed results and the measured ones. The use of approach I resulted in an obvious overprediction of the lift-off height. The predicted molar NO{sub x} yield with the approaches IIa and IIb were 89 % and 85 %, respectively, whereas a yield of 23 % had been measured. With the empirical mechanisms used in approach IIIa, a similar NO{sub x} yield was predicted as with approaches IIa and IIb. With IIIb the predicted NO{sub x} yield was 40 %. However, in this case 67 % of the NH{sub 3} remained unreacted. The reason for the large difference between the calculated NO{sub x} yield and the measured one reported in the literature is a poor modeling of the initial part of the fuel jet. A possible reason for this is the coarse grid. (author) 15 refs.

  1. Predictions of NO{sub x} formation in an NH{sub 3}-doped syngas flame using CFD combined with a detailed reaction mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Brink, A.; Norstroem, T.; Kilpinen, P.; Hupa, M. [Aabo Akademi, Turku (Finland). Combustion Chemistry Research Group

    1997-12-31

    The formation of NO{sub x} in a CO/H{sub 2}/CH{sub 4}/NH{sub 3} jet in a co-flowing air stream was modeled by use of CFD combined with a comprehensive detailed reaction mechanism. The comprehensive mechanism involved 340 reversible elementary reactions between 55 species. Three different approaches to include the detailed reaction mechanism were tested. In approach I, all chemistry was described with the comprehensive mechanism. In approaches IIa and IIb the comprehensive mechanism was used in post-processing calculations of the nitrogen chemistry. In approach IIa, the temperatures of the reacting structures obtained in the main calculations were used, whereas in approach IIb, the inlet temperatures to the reacting structures were taken from the main calculation. In approach IIIa and IIIb, empirical reaction mechanisms describing the nitrogen chemistry were tested. The turbulence-chemistry interaction was accounted for with a new model, which combines the Eddy-Dissipation Concept with a model based on the `Exchange by Interaction with the Mean`. There was a clear difference between the computed results and the measured ones. The use of approach I resulted in an obvious overprediction of the lift-off height. The predicted molar NO{sub x} yield with the approaches IIa and IIb were 89 % and 85 %, respectively, whereas a yield of 23 % had been measured. With the empirical mechanisms used in approach IIIa, a similar NO{sub x} yield was predicted as with approaches IIa and IIb. With IIIb the predicted NO{sub x} yield was 40 %. However, in this case 67 % of the NH{sub 3} remained unreacted. The reason for the large difference between the calculated NO{sub x} yield and the measured one reported in the literature is a poor modeling of the initial part of the fuel jet. A possible reason for this is the coarse grid. (author) 15 refs.

  2. Kinetics and mechanism of heterogeneous oxidation of sulfur dioxide by ozone on surface of calcium carbonate

    Directory of Open Access Journals (Sweden)

    L. Li

    2006-01-01

    Full Text Available Sulfate particles play a key role in the air quality and the global climate, but the heterogeneous formation mechanism of sulfates on surfaces of atmospheric particles is not well established. Carbonates, which act as a reactive component in mineral dust due to their special chemical properties, may contribute significantly to the sulfate formation by heterogeneous processes. This paper presents a study on the oxidation of SO2 by O3 on CaCO3 particles. Using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS, the formation of sulfite and sulfate on the surface was identified, and the roles of O3 and water in oxidation processes were determined. The results showed that in the presence of O3, SO2can be oxidized to sulfate on the surface of CaCO3 particles. The reaction is first order in SO2 and zero order in O3. The reactive uptake coefficient for SO2 [(0.6–9.8×1014 molecule cm-3] oxidation by O3 [(1.2–12×1014 molecule cm-3] was determined to be (1.4±0.3×10-7 using the BET area as the reactive area and (7.7±1.6×10-4 using the geometric area. A two-stage mechanism that involves adsorption of SO2 followed by O3 oxidation is proposed and the adsorption of SO2 on the CaCO3 surface is the rate-determining step. The proposed mechanism can well explain the experiment results. The atmospheric implications were explored based on a box model calculation. It was found that the heterogeneous reaction might be an important pathway for sulfate formation in the atmosphere.

  3. Chemical stability of insulin. 4. Mechanisms and kinetics of chemical transformations in pharmaceutical formulation.

    Science.gov (United States)

    Brange, J

    1992-01-01

    Insulin decomposes by a multitude of chemical reactions [1-3]. It deamidates at two different residues by entirely different mechanisms. In acid, deamidation at AsnA21 is intramolecularly catalyzed by the protonated C-terminal, whereas above pH 6 an intermediate imide formation at residue AsnB3 leads to isoAsp and Asp derivatives. The imide formation requires a large rotation around the alpha-carbon/peptide carbonyl carbon bond at B3, corresponding to a 10 A movement of the B-chain N-terminal. The main determinant for the rate of B3 deamidation, as well as for the ratio between the two products formed, is the local conformational structure, which is highly influenced by various excipients and the physical state of the insulin. An amazing thermolysin-like, autoproteolytic cleavage of the A-chain takes place in rhombohedral insulin crystals, mediated by a concerted catalytic action by several, inter-hexameric functional groups and Zn2+. Intermolecular, covalent cross-linking of insulin molecules occurs via several mechanisms. The most prominent type of mechanism is aminolysis by the N-terminals, leading to isopeptide linkages with the A-chain side-chain amides of residues GlnA15, AsnA18 and AsnA21. The same type of reaction also leads to covalent cross-linking of the N-terminal in protamine with insulin. Disulfide exchange reactions, initiated by lysis of the A7-B7 disulfide bridge, lead mainly to formation of covalent oligo- and polymers. Activation energy (Ea) for the neutral deamidation and the aminolysis reactions was found to be 80 and 119 KJ/mol, respectively.

  4. Kinetics and mechanisms of low temperature deformation in high purity niobium single crystals

    International Nuclear Information System (INIS)

    Karam, N.H.

    1985-01-01

    This study included three main aspects: (1) an extensive examination of the temperature and strain rate dependence of the flow stress without any thermodynamic analysis; (2) detailed thermodynamic analysis of the experimental data with no specific models involved, and (3) testing the results against specific models as well as modification of Seeger's model (1981-1983) to account for the results. The temperature and strain rate dependence of the tau/sub f/, tau/sup */, and tau/sub μ/ was experimentally determined over the temperature range 300 to 4.2 K with intervals ΔT ≤ 20K. The value of tau/sub μ/(T/sub k/) was found experimentally by decremental unloading, stress relaxation, and back extrapolation techniques giving tau/sub μ/(T/sub k/) = 19 MPa in agreement with the analytical analysis. The knee temperature was found T/sub k/ = 300K and the Peierls stress was determined as taup = 370 MPa. The strain rate sensitivity λ was evaluated using both strain rate cycle and stress relaxation techniques which were in excellent agreement. λ reached its maximum at 77K. Experimental data are best described by double kink nucleation models where deformation occurs by the formation of double kinks on screw dislocations that are resisted by a lattice friction arising from the periodic lattice potential

  5. Photocatalytic degradation kinetics and mechanism of phenobarbital in TiO(2) aqueous solution.

    Science.gov (United States)

    Cao, Hua; Lin, Xiulian; Zhan, Haiying; Zhang, Hong; Lin, Jingxin

    2013-01-01

    5-Ethyl-5-phenylpyrimidine-2,4,6(1H, 3H, 5H)-trione is an anti-convulsant used to treat disorders of movement, e.g. tremors. This work deals with the transformation of phenobarbital by UV/TiO(2) heterogeneous photocatalysis, to assess the decomposition of the pharmaceutical compound, to identify intermediates, as well as to elucidate some mechanistic details of the degradation. The photocatalytic removal efficiency of 100 μm phenobarbital is about 80% within 60 min, while the degradation efficiency of phenobarbital was better in alkaline solution. The study on contribution of reactive oxidative species (ROSs) has shown that ()OH is responsible for the major degradation of phenobarbital, while the photohole, photoelectrons and the other ROSs have the minor contribution to the degradation. Finally, based on the identification of degradation intermediates, two main photocatalytic degradation pathways have been tentatively proposed, including the hydroxylation and cleavage of pyrimidine ring in the phenobarbital molecule respectively. Certainly, the phenobarbital can be mineralized when the photocatalytic reaction time prolongs. Copyright © 2012 Elsevier Ltd. All rights reserved.

  6. Electroanalysis of cardioselective beta-adrenoreceptor blocking agent acebutolol by disposable graphite pencil electrodes with detailed redox mechanism

    Directory of Open Access Journals (Sweden)

    Atmanand M. Bagoji

    2016-12-01

    Full Text Available A simple economic graphite pencil electrode (GPE was used for analysis of cardioselective, hydrophilic-adrenoreceptor blocking agent, acebutolol (ACBT using the cyclic voltammetric, linear sweep voltammetric, differential pulse voltammetric (DPV, and square-wave voltammetric (SWV techniques. The dependence of the current on pH, concentration, and scan rate was investigated to optimize the experimental condition for determination of ACBT. The electrochemical behavior of the ACBT at GPE was a diffusion-controlled process. A probable electro-redox mechanism was proposed. Under the optimal conditions, the anodic peak current was linearly proportional to the concentration of ACBT in the range from 1.00 to 15.0 μM with a limit of detection 1.26 × 10−8 M for DPV and 1.28 × 10−8 M for the SWV. This method was applied for quantitative determination of the ACBT levels in urine as real samples. The obtained recovery ranges for ACBT in urine were from 95.4 to101% as found by the standard addition technique. Further interference study was also carried with some common interfering substances.

  7. Mechanism and kinetics of LiX(X=H, D, T) + H2O reaction

    International Nuclear Information System (INIS)

    Lei Hongjie; Duan Hao; Xing Pifeng; Tang Yongjian

    2011-01-01

    The reaction mechanism of LiX(X=H, D, T) with H 2 O was investigated at MP2/6-311G (d) level using ab initio quantum chemistry in Gaussian 03 software. The equilibrium geometries, harmonic frequencies and energy of various stationary points on the potential energy surfaces were calculated in the lowest singlet states. Considering the quantum correction, the reaction rate constants were calculated using classical transition state theory. The results show the reaction of LiH (LiD, LiT) with H 2 O was considerably dependent on temperature that it is lower, the reaction rate constants are smaller. (authors)

  8. Kinetics and mechanism of the reaction of recombination of vinyl and hydroxyl radicals

    Science.gov (United States)

    Knyazev, Vadim D.

    2017-10-01

    The recombination of the vinyl (C2H3) and the hydroxyl (OH) radicals was studied computationally using quantum chemistry and master equation/RRKM. The reaction mechanism includes the initial addition, several isomerization steps, and decomposition via seven different channels. The spectrum of products demonstrates temperature dependence in the 300-3000 K range. At low temperatures (below 1600 K), CH3 + HCO products are dominant but at elevated temperatures vinoxy radical (CH2CHO) and hydrogen atom become more important. The acetyl (CH3CO) + H products and formation of vinylidene (CH2C:) and water products are minor but non-negligible.

  9. Kinetics and mechanism of reduction of cerium(IV) by ascorbic acid

    International Nuclear Information System (INIS)

    Bhatt, K.; Nand, K.C.

    1979-01-01

    The reduction of cerium(IV) has been studied in sulfuric acid medium using ascorbic acid as the reductant. The rate is found to be function of both Ce(IV) and AH 2 concentrations. Sulfuric acid retards the rate and the inverse order with respect to sulfuric acid is unity. The addition of chloride, bisulfate and sulfate of sodium show negative salt effect and an increase in the dielectric constant of the medium shows an accelerating effect on the reaction rate. Arrhenius parameters have been evaluated. A mechanism involving intermediate formation of ascorbate radical (AH) is proposed and the derived rate law agrees well with the experimental observations. (author)

  10. Mechanism and kinetics in reactions of caffeic acid with radicals by pulse radiolysis and calculation

    International Nuclear Information System (INIS)

    Li, Xifeng; Cai, Zhongli; Katsumura, Yosuke

    2000-01-01

    The interaction of caffeic acid with e aq - , (CH 3 ) 2 (OH) CCH 2 · , CO 2 ·- , H · , ·OH and N 3 · radicals were studied by γ-, pulse radiolysis and molecular orbital calculation. UV-visible spectra of electron/·OH adducts, semi-quinone radicals of caffeic ions, and the stable products from the reactions were derived. The rate constants were determined. The attacked sites and the most favorable structures of the transient radicals were predicted. Reaction mechanisms were proposed. (author)

  11. Continuum theory of fibrous tissue damage mechanics using bond kinetics: application to cartilage tissue engineering.

    Science.gov (United States)

    Nims, Robert J; Durney, Krista M; Cigan, Alexander D; Dusséaux, Antoine; Hung, Clark T; Ateshian, Gerard A

    2016-02-06

    This study presents a damage mechanics framework that employs observable state variables to describe damage in isotropic or anisotropic fibrous tissues. In this mixture theory framework, damage is tracked by the mass fraction of bonds that have broken. Anisotropic damage is subsumed in the assumption that multiple bond species may coexist in a material, each having its own damage behaviour. This approach recovers the classical damage mechanics formulation for isotropic materials, but does not appeal to a tensorial damage measure for anisotropic materials. In contrast with the classical approach, the use of observable state variables for damage allows direct comparison of model predictions to experimental damage measures, such as biochemical assays or Raman spectroscopy. Investigations of damage in discrete fibre distributions demonstrate that the resilience to damage increases with the number of fibre bundles; idealizing fibrous tissues using continuous fibre distribution models precludes the modelling of damage. This damage framework was used to test and validate the hypothesis that growth of cartilage constructs can lead to damage of the synthesized collagen matrix due to excessive swelling caused by synthesized glycosaminoglycans. Therefore, alternative strategies must be implemented in tissue engineering studies to prevent collagen damage during the growth process.

  12. Towards understanding the mechanisms and the kinetics of nanoparticle penetration through protective gloves

    International Nuclear Information System (INIS)

    Vinches, L; Boutrigue, N; Zemzem, M; Hallé, S; Peyrot, C; Lemarchand, L; Wilkinson, K J; Tufenkji, N

    2015-01-01

    Parallel to the increased use of engineered nanoparticles (ENP) in the formulation of commercial products or in medicine, numerous health and safety agencies have recommended the application of the precautionary principle to handle ENP; namely, the recommendation to use protective gloves against chemicals. However, recent studies reveal the penetration of titanium dioxide nanoparticles through nitrile rubber protective gloves in conditions simulating occupational use. This project is designed to understand the links between the penetration of gold nanoparticles (nAu) through nitrile rubber protective gloves and the mechanical and physical behaviour of the elastomer material subjected to conditions simulating occupational use (i.e., mechanical deformations (MD) and sweat). Preliminary analyses show that nAu suspensions penetrate selected glove materials after exposure to prolonged (3 hours) dynamic deformations. Significant morphological changes are observed on the outer surface of the glove sample; namely, the number and the surface of the micropores on the surface increase. Moreover, nitrile rubber protective gloves are also shown to be sensitive to the action of nAu suspension and to the action of the saline solution used to simulate sweat (swelling). (paper)

  13. A Multiscale Understanding of the Thermodynamic and Kinetic Mechanisms of Laser Additive Manufacturing

    Directory of Open Access Journals (Sweden)

    Dongdong Gu

    2017-10-01

    Full Text Available Selective laser melting (SLM additive manufacturing (AM technology has become an important option for the precise manufacturing of complex-shaped metallic parts with high performance. The SLM AM process involves complicated physicochemical phenomena, thermodynamic behavior, and phase transformation as a high-energy laser beam melts loose powder particles. This paper provides multiscale modeling and coordinated control for the SLM of metallic materials including an aluminum (Al-based alloy (AlSi10Mg, a nickel (Ni-based super-alloy (Inconel 718, and ceramic particle-reinforced Al-based and Ni-based composites. The migration and distribution mechanisms of aluminium nitride (AlN particles in SLM-processed Al-based nanocomposites and the in situ formation of a gradient interface between the reinforcement and the matrix in SLM-processed tungsten carbide (WC/Inconel 718 composites were studied in the microscale. The laser absorption and melting/densification behaviors of AlSi10Mg and Inconel 718 alloy powder were disclosed in the mesoscale. Finally, the stress development during line-by-line localized laser scanning and the parameter-dependent control methods for the deformation of SLM-processed composites were proposed in the macroscale. Multiscale numerical simulation and experimental verification methods are beneficial in monitoring the complicated powder-laser interaction, heat and mass transfer behavior, and microstructural and mechanical properties development during the SLM AM process.

  14. Size effects in tin-based lead-free solder joints: Kinetics of bond formation and mechanical characteristics

    Science.gov (United States)

    Abdelhadi, Ousama Mohamed Omer

    Continuous miniaturization of microelectronic interconnects demands smaller joints with comparable microstructural and structural sizes. As the size of joints become smaller, the volume of intermetallics (IMCs) becomes comparable with the joint size. As a result, the kinetics of bond formation changes and the types and thicknesses of IMC phases that form within the constrained region of the bond varies. This dissertation focuses on investigating combination effects of process parameters and size on kinetics of bond formation, resulting microstructure and the mechanical properties of joints that are formed under structurally constrained conditions. An experiment is designed where several process parameters such as time of bonding, temperature, and pressure, and bond thickness as structural chracteristic, are varied at multiple levels. The experiment is then implemented on the process. Scanning electron microscope (SEM) is then utilized to determine the bond thickness, IMC phases and their thicknesses, and morphology of the bonds. Electron backscatter diffraction (EBSD) is used to determine the grain size in different regions, including the bulk solder, and different IMC phases. Physics-based analytical models have been developed for growth kinetics of IMC compounds and are verified using the experimental results. Nanoindentation is used to determine the mechanical behavior of IMC phases in joints in different scales. Four-point bending notched multilayer specimen and four-point bending technique were used to determine fracture toughness of the bonds containing IMCs. Analytical modeling of peeling and shear stresses and fracture toughness in tri-layer four-point bend specimen containing intermetallic layer was developed and was verified and validated using finite element simulation and experimental results. The experiment is used in conjunction with the model to calculate and verify the fracture toughness of Cu6Sn5 IMC materials. As expected two different IMC phases

  15. Kinetics and mechanisms of the oxidation of iodide and bromide in aqueous solutions by a trans-dioxoruthenium(VI) complex.

    Science.gov (United States)

    Lam, William W Y; Man, Wai-Lun; Wang, Yi-Ning; Lau, Tai-Chu

    2008-08-04

    The kinetics and mechanisms of the oxidation of I (-) and Br (-) by trans-[Ru (VI)(N 2O 2)(O) 2] (2+) have been investigated in aqueous solutions. The reactions have the following stoichiometry: trans-[Ru (VI)(N 2O 2)(O) 2] (2+) + 3X (-) + 2H (+) --> trans-[Ru (IV)(N 2O 2)(O)(OH 2)] (2+) + X 3 (-) (X = Br, I). In the oxidation of I (-) the I 3 (-)is produced in two distinct phases. The first phase produces 45% of I 3 (-) with the rate law d[I 3 (-)]/dt = ( k a + k b[H (+)])[Ru (VI)][I (-)]. The remaining I 3 (-) is produced in the second phase which is much slower, and it follows first-order kinetics but the rate constant is independent of [I (-)], [H (+)], and ionic strength. In the proposed mechanism the first phase involves formation of a charge-transfer complex between Ru (VI) and I (-), which then undergoes a parallel acid-catalyzed oxygen atom transfer to produce [Ru (IV)(N 2O 2)(O)(OHI)] (2+), and a one electron transfer to give [Ru (V)(N 2O 2)(O)(OH)] (2+) and I (*). [Ru (V)(N 2O 2)(O)(OH)] (2+) is a stronger oxidant than [Ru (VI)(N 2O 2)(O) 2] (2+) and will rapidly oxidize another I (-) to I (*). In the second phase the [Ru (IV)(N 2O 2)(O)(OHI)] (2+) undergoes rate-limiting aquation to produce HOI which reacts rapidly with I (-) to produce I 2. In the oxidation of Br (-) the rate law is -d[Ru (VI)]/d t = {( k a2 + k b2[H (+)]) + ( k a3 + k b3[H (+)]) [Br (-)]}[Ru (VI)][Br (-)]. At 298.0 K and I = 0.1 M, k a2 = (2.03 +/- 0.03) x 10 (-2) M (-1) s (-1), k b2 = (1.50 +/- 0.07) x 10 (-1) M (-2) s (-1), k a3 = (7.22 +/- 2.19) x 10 (-1) M (-2) s (-1) and k b3 = (4.85 +/- 0.04) x 10 (2) M (-3) s (-1). The proposed mechanism involves initial oxygen atom transfer from trans-[Ru (VI)(N 2O 2)(O) 2] (2+) to Br (-) to give trans-[Ru (IV)(N 2O 2)(O)(OBr)] (+), which then undergoes parallel aquation and oxidation of Br (-), and both reactions are acid-catalyzed.

  16. Toxicological effects of multi-walled carbon nanotubes on Saccharomyces cerevisiae: The uptake kinetics and mechanisms and the toxic responses

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Song; Zhu, Bin; Huang, Aiguo [College of Animal Science and Technology, Northwest A& F University, Yangling 712100 (China); Hu, Yang [College of Science, Northwest A& F University, Yangling 712100 (China); Wang, Gaoxue, E-mail: wanggaoxue@126.com [College of Animal Science and Technology, Northwest A& F University, Yangling 712100 (China); Ling, Fei, E-mail: feiling@nwsuaf.edu.cn [College of Animal Science and Technology, Northwest A& F University, Yangling 712100 (China)

    2016-11-15

    Highlights: • MWCNTs (<100 mg/L) were not toxic to S. cerevisiae. • MWCNTs were internalized in S. cerevisiae cells by three pathways. • The uptake kinetics and the subcellular distribution of MWCNTs in S. cerevisiae cells were shown. • S. cerevisiae cells were undergoing apoptosis by mitochondrial impairment pathway. - Abstract: Using Saccharomyces cerevisiae as an experimental model, the potential toxicological effects of oxidized multi-walled carbon nanotubes (MWCNTs) were investigated following exposure to 0–600 mg/L for 24 h. Results indicated that MWCNTs (>100 mg/L) had adverse effects on the cell proliferation. MWCNTs were clearly visible in lysosome, vacuole, endosome, mitochondria, multivesicular body and localization in the perinuclear region. The uptake kinetics data demonstrated that the maximum MWCNTs content (209.61 mg/g) was reached at 3 h, and a steady state was reached after 18 h. Based on the combined results of transmission electron microscope, endocytosis inhibition experiments and endocytosis-related genes (END3, END6, Sla2 and Rsp5) expression analysis, we elucidated MWCNTs uptake mechanism: (i) via a direct penetration of single MWCNTs; (ii) via endocytosis of single MWCNTs; and (iii) via endocytosis of MWCNTs aggregates. The percentage of apoptosis was significant increased at 600 mg/L. The decrease of mitochondrial transmembrane potential and the leakage of cytochrome c shown dose-dependent manners. Interestingly, there was no significant increase of reactive oxygen species (ROS). The apoptosis-related genes (SOD1, SOD2, Yca1, Nma111 and Nuc1) were significant changed. These results obtained in our study demonstrated that oxidized MWCNTs induce Saccharomyces cerevisiae apoptosis via mitochondrial impairment pathway.

  17. Kinetics and Mechanism of Bioactivation via S-Oxygenation of Anti-Tubercular Agent Ethionamide by Peracetic Acid.

    Science.gov (United States)

    Chipiso, Kudzanai; Logan, Isabelle E; Eskew, Matthew W; Omondi, Benard; Simoyi, Reuben H

    2016-10-11

    The kinetics and mechanism of the oxidation of the important antitubercular agent, ethionamide, ETA (2-ethylthioisonicotinamide), by peracetic acid (PAA) have been studied. It is effectively a biphasic reaction with an initial rapid first phase of the reaction which is over in about 5 s and a second slower phase of the reaction which can run up to an hour. The first phase involves the addition of a single oxygen atom to ethionamide to form the S-oxide. The second phase involves further oxidation of the S-oxide to desulfurization of ETA to give 2-ethylisonicotinamide. In contrast to the stability of most organosulfur compounds, the S-oxide of ETA is relatively stable and can be isolated. In conditions of excess ETA, the stoichiometry of the reaction was strictly 1:1: CH 3 CO 3 H + Et(C 5 H 4 )C(═S)NH 2 → CH 3 CO 2 H + Et(C 5 H 4 )C(═NH)SOH. In this oxidation, it was apparent that only the sulfur center was the reactive site. Though ETA was ultimately desulfurized, only the S-oxide was stable. Electrospray ionization (ESI) spectral analysis did not detect any substantial formation of the sulfinic and sulfonic acids. This suggests that cleavage of the carbon-sulfur bond occurs at the sulfenic acid stage, resulting in the formation of an unstable sulfur species that can react further to form more stable sulfur species. In this oxidation, no sulfate formation was observed. ESI spectral analysis data showed a final sulfur species in the form of a dimeric sulfur monoxide species, H 3 S 2 O 2 . We derived a bimolecular rate constant for the formation of the S-oxide of (3.08 ± 0.72) × 10 2 M -1 s -1 . Oxidation of the S-oxide further to give 2-ethylisonicotinamide gave zero order kinetics.

  18. Photolysis of polycyclic aromatic hydrocarbons (PAHs) on Fe3+-montmorillonite surface under visible light: Degradation kinetics, mechanism, and toxicity assessments.

    Science.gov (United States)

    Zhao, Song; Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Wang, Chuanyi

    2017-10-01

    Photochemical behavior of various polycyclic aromatic hydrocarbons (PAHs) on Fe 3+ -modified montmorillonite was explored to determine their potential kinetics, pathways, and mechanism under visible light. Depending on the type of PAH molecules, the transformation rate follows the order of benzo[a]pyrene ≈ anthracene > benzo[a]anthracene > phenanthrene. Quantum simulation results confirm the crucial role of "cation-π" interaction between Fe 3+ and PAHs on their transformation kinetics. Primary intermediates, including quinones, ring-opening products and benzene derivatives, were identified by gas chromatography-mass spectrometer (GC-MS), and the possible photodegradation pathway of benzo[a]pyrene was proposed. Meanwhile, radical intermediates, such as reactive oxygen species (ROS) and free organic radicals, were detected by electron paramagnetic resonance (EPR) technique. The photolysis of selected PAHs, such as anthracene and benzo[a]pyrene, on clay surface firstly occurs by electron transfer from PAHs to Fe 3+ -montmorillonite, followed by degradation involving photo-induced ROS such as ·OH and ·O 2 - . To investigate the acute toxicity of photolysis products, the Microtox ® toxicity test was performed during the photodegradation processes of various PAHs. As a result, the photo-irradiation initially induces increased toxicity by generating reactive intermediates, such as free organic radicals, and then the toxicity gradually decreases with increasing of reaction time. Overall, the present study provides useful information to understand the fate and photo-transformation of PAHs in contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Experimental and theoretical understanding of the gas phase oxidation of atmospheric amides with OH radicals: kinetics, products, and mechanisms.

    Science.gov (United States)

    Borduas, Nadine; da Silva, Gabriel; Murphy, Jennifer G; Abbatt, Jonathan P D

    2015-05-14

    Atmospheric amides have primary and secondary sources and are present in ambient air at low pptv levels. To better assess the fate of amides in the atmosphere, the room temperature (298 ± 3 K) rate coefficients of five different amides with OH radicals were determined in a 1 m(3) smog chamber using online proton-transfer-reaction mass spectrometry (PTR-MS). Formamide, the simplest amide, has a rate coefficient of (4.44 ± 0.46) × 10(-12) cm(3) molec(-1) s(-1) against OH, translating to an atmospheric lifetime of ∼1 day. N-methylformamide, N-methylacetamide and propanamide, alkyl versions of formamide, have rate coefficients of (10.1 ± 0.6) × 10(-12), (5.42 ± 0.19) × 10(-12), and (1.78 ± 0.43) × 10(-12) cm(3) molec(-1) s(-1), respectively. Acetamide was also investigated, but due to its slow oxidation kinetics, we report a range of (0.4-1.1) × 10(-12) cm(3) molec(-1) s(-1) for its rate coefficient with OH radicals. Oxidation products were monitored and quantified and their time traces were fitted using a simple kinetic box model. To further probe the mechanism, ab initio calculations are used to identify the initial radical products of the amide reactions with OH. Our results indicate that N-H abstractions are negligible in all cases, in contrast to what is predicted by structure-activity relationships. Instead, the reactions proceed via C-H abstraction from alkyl groups and from formyl C(O)-H bonds when available. The latter process leads to radicals that can readily react with O2 to form isocyanates, explaining the detection of toxic compounds such as isocyanic acid (HNCO) and methyl isocyanate (CH3NCO). These contaminants of significant interest are primary oxidation products in the photochemical oxidation of formamide and N-methylformamide, respectively.

  20. Kinetics and mechanism of the biodegradation of PLA/clay nanocomposites during thermophilic phase of composting process.

    Science.gov (United States)

    Stloukal, Petr; Pekařová, Silvie; Kalendova, Alena; Mattausch, Hannelore; Laske, Stephan; Holzer, Clemens; Chitu, Livia; Bodner, Sabine; Maier, Guenther; Slouf, Miroslav; Koutny, Marek

    2015-08-01

    The degradation mechanism and kinetics of polylactic acid (PLA) nanocomposite films, containing various commercially available native or organo-modified montmorillonites (MMT) prepared by melt blending, were studied under composting conditions in thermophilic phase of process and during abiotic hydrolysis and compared to the pure polymer. Described first order kinetic models were applied on the data from individual experiments by using non-linear regression procedures to calculate parameters characterizing aerobic composting and abiotic hydrolysis, such as carbon mineralization, hydrolysis rate constants and the length of lag phase. The study showed that the addition of nanoclay enhanced the biodegradation of PLA nanocomposites under composting conditions, when compared with pure PLA, particularly by shortening the lag phase at the beginning of the process. Whereas the lag phase of pure PLA was observed within 27days, the onset of CO2 evolution for PLA with native MMT was detected after just 20days, and from 13 to 16days for PLA with organo-modified MMT. Similarly, the hydrolysis rate constants determined tended to be higher for PLA with organo-modified MMT, particularly for the sample PLA-10A with fastest degradation, in comparison with pure PLA. The acceleration of chain scission in PLA with nanoclays was confirmed by determining the resultant rate constants for the hydrolytical chain scission. The critical molecular weight for the hydrolysis of PLA was observed to be higher than the critical molecular weight for onset of PLA mineralization, suggesting that PLA chains must be further shortened so as to be assimilated by microorganisms. In conclusion, MMT fillers do not represent an obstacle to acceptance of the investigated materials in composting facilities. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. Photocatalytic degradation of bisphenol A in the presence of Ce–ZnO: Evolution of kinetics, toxicity and photodegradation mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Bechambi, Olfa [Université de Tunis El Manar, Faculté des Sciences de Tunis, Laboratoire de Chimie des Matériaux et Catalyse, 2092, Tunis (Tunisia); Jlaiel, Lobna [Laboratoire de Bioprocédés Environnementaux, Centre de Biotechnologie de Sfax, B.P. 1177, 3018 Sfax (Tunisia); Najjar, Wahiba, E-mail: najjarwahiba2014@gmail.com [Université de Tunis El Manar, Faculté des Sciences de Tunis, Laboratoire de Chimie des Matériaux et Catalyse, 2092, Tunis (Tunisia); Sayadi, Sami [Laboratoire de Bioprocédés Environnementaux, Centre de Biotechnologie de Sfax, B.P. 1177, 3018 Sfax (Tunisia)

    2016-04-15

    Ce–ZnO (2 mol %) and undoped ZnO catalysts have been synthesized through hydrothermal method and characterized by X-ray diffraction (XRD), Nitrogen physisorption at 77 K; Fourier transformed infrared spectroscopy (FTIR), UV–Visible spectroscopy, Photoluminescence spectra (PL), and Raman spectroscopy. Ce-doping reduces the average crystallite size, increases the BET surface area, shifts the absorption edge, reduces the electron–hole recombination and consequently improves photodegradation efficiency of Bisphenol A (BPA) in the presence of UV irradiation and hydrogen peroxide. The photocatalytic optimum conditions were established by studying the influence of various operational parameters including catalyst concentration, initial BPA concentration, H{sub 2}O{sub 2} concentration and initial pH. Under optimum conditions, Ce–ZnO (2%) achieved 100% BPA degradation and 61% BPA mineralization after 24 h of UV irradiation. BPA degradation reaction followed pseudo first-order kinetics according to the Langmuir–Hinshelwood model. Based on the identified intermediate products, the possible mechanism for BPA photodegradation is proposed. Toxicity under the optimum condition was also evaluated. - Graphical abstract: Proposed photocatalytic degradation pathway of BPA in the presence of Ce– ZnO (2%)/UV/H{sub 2}O{sub 2} system. - Highlights: • Influence of different parameters on the degradation and mineralization of BPA. • Identification of possible degradation products. • Toxicity tests conducted with Vibrio fischeri. • Simple and direct photodegradation mechanism of BPA is proposed.

  2. Growth kinetics and growth mechanism of ultrahigh mass density carbon nanotube forests on conductive Ti/Cu supports.

    Science.gov (United States)

    Sugime, Hisashi; Esconjauregui, Santiago; D'Arsié, Lorenzo; Yang, Junwei; Makaryan, Taron; Robertson, John

    2014-09-10

    We evaluate the growth kinetics and growth mechanism of ultrahigh mass density carbon nanotube forests. They are synthesized by chemical vapor deposition at 450 °C using a conductive Ti/Cu support and Co-Mo catalyst system. We find that Mo stabilizes Co particles preventing lift off during the initial growth stage, thus promoting the growth of ultrahigh mass density nanotube forests by the base growth mechanism. The morphology of the forest gradually changes with growth time, mostly because of a structural change of the catalyst particles. After 100 min growth, toward the bottom of the forest, the area density decreases from ∼ 3-6 × 10(11) cm(-2) to ∼ 5 × 10(10) cm(-2) and the mass density decreases from 1.6 to 0.38 g cm(-3). We also observe part of catalyst particles detached and embedded within nanotubes. The progressive detachment of catalyst particles results in the depletion of the catalyst metals on the substrate surfaces. This is one of the crucial reasons for growth termination and may apply to other catalyst systems where the same features are observed. Using the packed forest morphology, we demonstrate patterned forest growth with a pitch of ∼ 300 nm and a line width of ∼ 150 nm. This is one of the smallest patterning of the carbon nanotube forests to date.

  3. R7T7 glass alteration mechanism in an aqueous closed system: understanding and modelling the long term alteration kinetic

    International Nuclear Information System (INIS)

    Chave, T.

    2007-10-01

    The long term alteration rate of the French R7T7 nuclear glass has been investigated since many years because it will define the overall resistance of the radionuclide containment matrix. Recent studies have shown that the final rate remains constant or is slightly decreasing with time. It never reaches zero. Though this residual rate is very low, only 5 nm per year at 50 C, it would be the dominant alteration phenomenon in a geological repository. Two mechanisms are suggested for explaining such behaviour: diffusion in solution of elements from glass through an amorphous altered layer and precipitation of neo-formed phases. The diffusion processes are in agreement with a solid state diffusion mechanism and can lead to secondary phase precipitation due to solution concentration increases. Observed phases are mainly phyllosilicates and zeolites, in specific conditions. Phyllosilicates are expected to maintain the residual kinetic rate whereas alteration resumption could be observed in presence of zeolites at very high pH or temperature (10.5 at 90 C or temperature above 150 C). Both diffusion and neo-formed phase precipitation have been investigated in order to better understand their impact on the residual alteration rate and have then been modelled by a calculation code, coupling chemistry and transport, in order to be able to better anticipate the long term behaviour of the glass R7T7 in an aqueous closed system. (author)

  4. Mechanism and kinetics in reactions of caffeic acid with radicals by pulse radiolysis and calculation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xifeng; Cai, Zhongli; Katsumura, Yosuke [Tokyo Univ., Tokai, Ibaraki (Japan). Nuclear Engineering Research Lab

    2000-03-01

    The interaction of caffeic acid with e{sub aq}{sup -}, (CH{sub 3}){sub 2}(OH) CCH{sub 2}{sup {center_dot}}, CO{sub 2}{sup {center_dot}}{sup -}, H{sup {center_dot}}, {center_dot}OH and N{sub 3}{sup {center_dot}} radicals were studied by {gamma}-, pulse radiolysis and molecular orbital calculation. UV-visible spectra of electron/{center_dot}OH adducts, semi-quinone radicals of caffeic ions, and the stable products from the reactions were derived. The rate constants were determined. The attacked sites and the most favorable structures of the transient radicals were predicted. Reaction mechanisms were proposed. (author)

  5. Heterogeneous kinetics, products, and mechanisms of ferulic acid particles in the reaction with NO3 radicals

    Science.gov (United States)

    Liu, Changgeng; Zhang, Peng; Wen, Xiaoying; Wu, Bin

    2017-03-01

    Methoxyphenols, as an important component of wood burning, are produced by lignin pyrolysis and considered to be the potential tracers for wood smoke emissions. In this work, the heterogeneous reaction between ferulic acid particles and NO3 radicals was investigated. Six products including oxalic acid, 4-vinylguaiacol, vanillin, 5-nitrovanillin, 5-nitroferulic acid, and caffeic acid were confirmed by gas chromatography-mass spectrometry (GC-MS). In addition, the reaction mechanisms were proposed and the main pathways were NO3 electrophilic addition to olefin and the meta-position to the hydroxyl group. The uptake coefficient of NO3 radicals on ferulic acid particles was 0.17 ± 0.02 and the effective rate constant under experimental conditions was (1.71 ± 0.08) × 10-12 cm3 molecule-1 s-1. The results indicate that ferulic acid degradation by NO3 can be an important sink at night.

  6. Dissociative diffusion mechanism in vacancy-rich materials according to mass action kinetics

    Directory of Open Access Journals (Sweden)

    N. J. Biderman

    2016-05-01

    Full Text Available Two sets of diffusion-reaction numerical simulations using a finite difference method (FDM were conducted to investigate fast impurity diffusion via interstitial sites in vacancy-rich materials such as Cu(In,GaSe2 (CIGS and Cu2ZnSn(S, Se4 (CZTSSe or CZTS via the dissociative diffusion mechanism where the interstitial diffuser ultimately reacts with a vacancy to produce a substitutional. The first set of simulations extends the standard interstitial-limited dissociative diffusion theory to vacancy-rich material conditions where vacancies are annihilated in large amounts, introducing non-equilibrium vacancy concentration profiles. The second simulation set explores the vacancy-limited dissociative diffusion where impurity incorporation increases the equilibrium vacancy concentration. In addition to diffusion profiles of varying concentrations and shapes that were obtained in all simulations, some of the profiles can be fitted with the constant- and limited-source solutions of Fick’s second law despite the non-equilibrium condition induced by the interstitial-vacancy reaction. The first set of simulations reveals that the dissociative diffusion coefficient in vacancy-rich materials is inversely proportional to the initial vacancy concentration. In the second set of numerical simulations, impurity-induced changes in the vacancy concentration lead to distinctive diffusion profile shapes. The simulation results are also compared with published data of impurity diffusion in CIGS. According to the characteristic properties of diffusion profiles from the two set of simulations, experimental detection of the dissociative diffusion mechanism in vacancy-rich materials may be possible.

  7. Kinetics and the mass transfer mechanism of hydrogen sulfide removal by biochar derived from rice hull.

    Science.gov (United States)

    Shang, Guofeng; Liu, Liang; Chen, Ping; Shen, Guoqing; Li, Qiwu

    2016-05-01

    The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H2S) from gas phase. The surface area and pH of the biochar were compared. The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H2S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperature has great influence on the adsorption of H2S. At the different pyrolysis temperature, the H2S removal efficiency of rice hull-derived biochar was different. The adsorption capacities of biochar were 2.09 mg·g(-1), 2.65 mg·g(-1), 16.30 mg·g(-1), 20.80 mg·g(-1), and 382.70 mg·g(-1), which their pyrolysis temperatures were 100 °C, 200 °C, 300 °C, 400 °C and 500 °C respectively. Based on the Yoon-Nelson model, it analyzed the mass transfer mechanism of hydrogen sulfide adsorption by biochar. The paper focuses on the biochar derived from rice hull-removed hydrogen sulfide (H2S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperatures have great influence on the adsorption of H2S. At the different pyrolysis temperatures, the H2S removal efficiency of rice hull-derived biohar was different. The adsorption capacities of biochar were 2.09, 2.65, 16.30, 20.80, and 382.70 mg·g(-1), and their pyrolysis temperatures were 100, 200, 300, 400, and 500 °C, respectively. Based on the Yoon-Nelson model, the mass transfer mechanism of hydrogen sulfide adsorption by biochar was analyzed.

  8. Kinetics and mechanism investigation on the destruction of oxytetracycline by UV-254 nm activation of persulfate

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yiqing [Faculty of Geosciences and Environmental Engineering, Southwest Jiaotong University, Chengdu 611756 (China); Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, OH 45221-0012 (United States); He, Xuexiang [Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, OH 45221-0012 (United States); Fu, Yongsheng [Faculty of Geosciences and Environmental Engineering, Southwest Jiaotong University, Chengdu 611756 (China); Dionysiou, Dionysios D., E-mail: dionysios.d.dionysiou@uc.edu [Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, OH 45221-0012 (United States)

    2016-03-15

    Highlights: • The most effective destruction of OTC by UV/PS was achieved at near neutral pH. • Deprotonated HOTC{sup −} had the highest second-order rate constant with SO{sub 4}·{sup −}. • Presence of HCO{sub 3}{sup −} or Cu{sup 2+} enhanced the removal of OTC in UV/PS system. • Total organic carbon was degraded slowly during the mineralization of OTC. • Studies on the degradation mechanism revealed four different reaction pathways. - Abstract: Oxytetracycline (OTC), an important broad-spectrum antibiotic, has been detected extensively in various environmental systems, which may have a detrimental impact on ecosystem and human health through the development of drug resistant bacteria and pathogens. In this study, the degradation of OTC was evaluated by UV-254 nm activated persulfate (PS). The observed UV fluence based pseudo first-order rate constant (k{sub obs}) was found to be the highest at near neutral pH conditions (pH 5.5–8.5). Presence of various natural water constituents had different effects on OTC degradation, with a significant enhancement in the presence of bicarbonate or Cu{sup 2+}. Limited elimination of total organic carbon (TOC) and PS was observed during the mineralization of OTC. Transformation byproducts in the presence and absence of hydroxyl radical scavenging agent tert-butanol (t-BuOH) were identified using ultra-high definition accurate-mass quadrupole time-of-flight liquid chromatography/mass spectrometer (LC-QTOF/MS). Potential OTC degradation mechanism was subsequently proposed revealing four different reaction pathways by SO{sub 4}·{sup −} reaction including hydroxylation (+16 Da), demethylation (−14 Da), decarbonylation (−28 Da) and dehydration (−18 Da). This study suggests that UV-254 nm/PS is a promising treatment technology for the control of water pollution caused by emerging contaminants such as OTC.

  9. Kinetic studies of Candida parapsilosis phagocytosis by macrophages and detection of intracellular survival mechanisms

    Directory of Open Access Journals (Sweden)

    Renata eToth

    2014-11-01

    Full Text Available Even though the number of Candida infections due to non-albicans species like C. parapsilosis has been increasing, little is known about their pathomechanisms. Certain aspects of C. parapsilosis and host interactions have already been investigated; however we lack information about the innate cellular responses towards this species. The aim of our project was to dissect and compare the phagocytosis of C. parapsilosis to C. albicans and to another Candida species C. glabrata by murine and human macrophages by live cell video microscopy. We broke down the phagocytic process into three stages: macrophage migration, engulfment of fungal cells and host cell killing after the uptake. Our results showed increased macrophage migration towards C. parapsilosis and we observed differences during the engulfment processes when comparing the three species. The engulfment time of C. parapsilosis was comparable to that of C. albicans regardless of the pseudohypha length and spatial orientation relative to phagocytes, while the rate of host cell killing and the overall uptake regarding C. parapsilosis showed similarities mainly with C. glabrata. Furthermore, we observed difference between human and murine phagocytes in the uptake of C. parapsilosis. UV-treatment of fungal cells had varied effects on phagocytosis dependent upon which Candida strain was used. Besides statistical analysis, live cell imaging videos showed that this species similarly to the other two also has the ability to survive in host cells via the following mechanisms: yeast replication, and pseudohypha growth inside of phagocytes, exocytosis of fungal cells and also abortion of host cell mitosis following the uptake. According to our knowledge this is the first study that provides a thorough examination of C. parapsilosis phagocytosis and reports intracellular survival mechanisms associated with this species.

  10. Kinetics and mechanism investigation on the destruction of oxytetracycline by UV-254 nm activation of persulfate

    International Nuclear Information System (INIS)

    Liu, Yiqing; He, Xuexiang; Fu, Yongsheng; Dionysiou, Dionysios D.

    2016-01-01

    Highlights: • The most effective destruction of OTC by UV/PS was achieved at near neutral pH. • Deprotonated HOTC"− had the highest second-order rate constant with SO_4·"−. • Presence of HCO_3"− or Cu"2"+ enhanced the removal of OTC in UV/PS system. • Total organic carbon was degraded slowly during the mineralization of OTC. • Studies on the degradation mechanism revealed four different reaction pathways. - Abstract: Oxytetracycline (OTC), an important broad-spectrum antibiotic, has been detected extensively in various environmental systems, which may have a detrimental impact on ecosystem and human health through the development of drug resistant bacteria and pathogens. In this study, the degradation of OTC was evaluated by UV-254 nm activated persulfate (PS). The observed UV fluence based pseudo first-order rate constant (k_o_b_s) was found to be the highest at near neutral pH conditions (pH 5.5–8.5). Presence of various natural water constituents had different effects on OTC degradation, with a significant enhancement in the presence of bicarbonate or Cu"2"+. Limited elimination of total organic carbon (TOC) and PS was observed during the mineralization of OTC. Transformation byproducts in the presence and absence of hydroxyl radical scavenging agent tert-butanol (t-BuOH) were identified using ultra-high definition accurate-mass quadrupole time-of-flight liquid chromatography/mass spectrometer (LC-QTOF/MS). Potential OTC degradation mechanism was subsequently proposed revealing four different reaction pathways by SO_4·"− reaction including hydroxylation (+16 Da), demethylation (−14 Da), decarbonylation (−28 Da) and dehydration (−18 Da). This study suggests that UV-254 nm/PS is a promising treatment technology for the control of water pollution caused by emerging contaminants such as OTC.

  11. Treatment of statin compounds by advanced oxidation processes: Kinetic considerations and destruction mechanisms

    Science.gov (United States)

    Razavi, Behnaz; Song, Weihua; Santoke, Hanoz; Cooper, William J.

    2011-03-01

    This study examined the use of advanced oxidation/reduction processes (AO/RPs) for the destruction of cholesterol lowering statin pharmaceuticals. AO/RPs which utilize the oxidizing hydroxyl radical ( rad OH) and reducing aqueous electron (e -aq), to degrade chemical contaminants are alternatives to traditional water treatment methods, and are alternatives as water reuse becomes more generally implemented. Four major statin pharmaceuticals, fluvastatin, lovastatin, pravastatin and simvastatin, were studied, and the absolute bimolecular reaction rate constants with rad OH determined, (6.96±0.16)×10 9, (2.92±0.06)×10 9, (4.16±0.13)×10 9, and (3.13±0.15)×10 9 M -1 s -1, and for e -aq (2.31±0.06)×10 9, (0.45±0.01)×10 9, (1.26±0.01)×10 9, and (0.69±0.02)×10 9 M -1 s -1, respectively. To provide additional information on the radicals formed upon oxidation, transient spectra were measured and the overall reaction efficiency determined. Radical-based destruction mechanisms for destruction of the statins are proposed based on the LC-MS determination of the stable reaction by-products formed using 137Cs γ-irradiation of statin solutions. Knowing the reaction rates, reaction efficiencies and destruction mechanisms of these compounds is essential for the consideration of the use of advanced oxidation/reduction processes for the destruction of statins in aqueous systems.

  12. Treatment of statin compounds by advanced oxidation processes: Kinetic considerations and destruction mechanisms

    International Nuclear Information System (INIS)

    Razavi, Behnaz; Song Weihua; Santoke, Hanoz; Cooper, William J.

    2011-01-01

    This study examined the use of advanced oxidation/reduction processes (AO/RPs) for the destruction of cholesterol lowering statin pharmaceuticals. AO/RPs which utilize the oxidizing hydroxyl radical ( · OH) and reducing aqueous electron (e - aq ), to degrade chemical contaminants are alternatives to traditional water treatment methods, and are alternatives as water reuse becomes more generally implemented. Four major statin pharmaceuticals, fluvastatin, lovastatin, pravastatin and simvastatin, were studied, and the absolute bimolecular reaction rate constants with · OH determined, (6.96±0.16)x10 9 , (2.92±0.06)x10 9 , (4.16±0.13)x10 9 , and (3.13±0.15)x10 9 M -1 s -1 , and for e - aq (2.31±0.06)x10 9 , (0.45±0.01)x10 9 , (1.26±0.01)x10 9 , and (0.69±0.02)x10 9 M -1 s -1 , respectively. To provide additional information on the radicals formed upon oxidation, transient spectra were measured and the overall reaction efficiency determined. Radical-based destruction mechanisms for destruction of the statins are proposed based on the LC-MS determination of the stable reaction by-products formed using 137 Cs γ-irradiation of statin solutions. Knowing the reaction rates, reaction efficiencies and destruction mechanisms of these compounds is essential for the consideration of the use of advanced oxidation/reduction processes for the destruction of statins in aqueous systems.

  13. Treatment of statin compounds by advanced oxidation processes: Kinetic considerations and destruction mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Razavi, Behnaz, E-mail: brazavi@uci.ed [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Song Weihua, E-mail: wsong@uci.ed [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Santoke, Hanoz, E-mail: hsantoke@uci.ed [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Cooper, William J., E-mail: wcooper@uci.ed [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States)

    2011-03-15

    This study examined the use of advanced oxidation/reduction processes (AO/RPs) for the destruction of cholesterol lowering statin pharmaceuticals. AO/RPs which utilize the oxidizing hydroxyl radical ({sup {center_dot}O}H) and reducing aqueous electron (e{sup -}{sub aq}), to degrade chemical contaminants are alternatives to traditional water treatment methods, and are alternatives as water reuse becomes more generally implemented. Four major statin pharmaceuticals, fluvastatin, lovastatin, pravastatin and simvastatin, were studied, and the absolute bimolecular reaction rate constants with {sup {center_dot}O}H determined, (6.96{+-}0.16)x10{sup 9}, (2.92{+-}0.06)x10{sup 9}, (4.16{+-}0.13)x10{sup 9}, and (3.13{+-}0.15)x10{sup 9} M{sup -1} s{sup -1}, and for e{sup -}{sub aq} (2.31{+-}0.06)x10{sup 9}, (0.45{+-}0.01)x10{sup 9}, (1.26{+-}0.01)x10{sup 9}, and (0.69{+-}0.02)x10{sup 9} M{sup -1} s{sup -1}, respectively. To provide additional information on the radicals formed upon oxidation, transient spectra were measured and the overall reaction efficiency determined. Radical-based destruction mechanisms for destruction of the statins are proposed based on the LC-MS determination of the stable reaction by-products formed using {sup 137}Cs {gamma}-irradiation of statin solutions. Knowing the reaction rates, reaction efficiencies and destruction mechanisms of these compounds is essential for the consideration of the use of advanced oxidation/reduction processes for the destruction of statins in aqueous systems.

  14. Mechanism and kinetics for ammonium dinitramide (ADN) sublimation: a first-principles study.

    Science.gov (United States)

    Zhu, R S; Chen, Hui-Lung; Lin, M C

    2012-11-08

    The mechanism for sublimation of NH(4)N(NO(2))(2) (ADN) has been investigated quantum-mechanically with generalized gradient approximation plane-wave density functional theory calculations; the solid surface is represented by a slab model and the periodic boundary conditions are applied. The calculated lattice constants for the bulk ADN, which were found to consist of NH(4)(+)[ON(O)NNO(2)](-) units, instead of NH(4)(+)[N(NO(2))(2)](-), agree quite well with experimental values. Results show that three steps are involved in the sublimation/decomposition of ADN. The first step is the relaxation of the surface layer with 1.6 kcal/mol energy per NH(4)ON(O)NNO(2) unit; the second step is the sublimation of the surface layer to form a molecular [NH(3)]-[HON(O)NNO(2)] complex with a 29.4 kcal/mol sublimation energy, consistent with the experimental observation of Korobeinichev et al. (10) The last step is the dissociation of the [H(3)N]-[HON(O)NNO(2)] complex to give NH(3) and HON(O)NNO(2) with the dissociation energy of 13.9 kcal/mol. Direct formation of NO(2) (g) from solid ADN costs a much higher energy, 58.3 kcal/mol. Our calculated total sublimation enthalpy for ADN(s) → NH(3)(g) + HON(O)NNO(2)) (g), 44.9 kcal/mol via three steps, is in good agreement with the value, 42.1 kcal/mol predicted for the one-step sublimation process in this work and the value 44.0 kcal/mol computed by Politzer et al. (11) using experimental thermochemical data. The sublimation rate constant for the rate-controlling step 2 can be represented as k(sub) = 2.18 × 10(12) exp (-30.5 kcal/mol/RT) s(-1), which agrees well with available experimental data within the temperature range studied. The high pressure limit decomposition rate constant for the molecular complex H(3)N···HON(O)NNO(2) can be expressed by k(dec) = 3.18 × 10(13) exp (-15.09 kcal/mol/RT) s(-1). In addition, water molecules were found to increase the sublimation enthalpy of ADN, contrary to that found in the ammonium

  15. Kinetics and mechanism investigation on the destruction of oxytetracycline by UV-254nm activation of persulfate.

    Science.gov (United States)

    Liu, Yiqing; He, Xuexiang; Fu, Yongsheng; Dionysiou, Dionysios D

    2016-03-15

    Oxytetracycline (OTC), an important broad-spectrum antibiotic, has been detected extensively in various environmental systems, which may have a detrimental impact on ecosystem and human health through the development of drug resistant bacteria and pathogens. In this study, the degradation of OTC was evaluated by UV-254nm activated persulfate (PS). The observed UV fluence based pseudo first-order rate constant (kobs) was found to be the highest at near neutral pH conditions (pH 5.5-8.5). Presence of various natural water constituents had different effects on OTC degradation, with a significant enhancement in the presence of bicarbonate or Cu(2+). Limited elimination of total organic carbon (TOC) and PS was observed during the mineralization of OTC. Transformation byproducts in the presence and absence of hydroxyl radical scavenging agent tert-butanol (t-BuOH) were identified using ultra-high definition accurate-mass quadrupole time-of-flight liquid chromatography/mass spectrometer (LC-QTOF/MS). Potential OTC degradation mechanism was subsequently proposed revealing four different reaction pathways by SO4(-) reaction including hydroxylation (+16Da), demethylation (-14Da), decarbonylation (-28Da) and dehydration (-18Da). This study suggests that UV-254nm/PS is a promising treatment technology for the control of water pollution caused by emerging contaminants such as OTC. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Mechanism and kinetics of thermal decomposition of ammoniacal complex of copper oxalate

    International Nuclear Information System (INIS)

    Prasad, R.

    2003-01-01

    A complex precursor has been synthesized by dissolving copper oxalate in liquor ammonia followed by drying. The thermal decomposition of the precursor has been studied in different atmospheres, air/nitrogen. The mechanism of decomposition of the precursor in air is not as simple one as in nitrogen. In nitrogen, it involves endothermic deammoniation followed by decomposition to finely divided elemental particles of copper. Whereas in air, decomposition and simultaneous oxidation of the residual products (oxidative decomposition), make the process complex and relatively bigger particle of cupric oxide are obtained as final product. The products of decomposition in different atmospheres have been characterized by X-ray diffraction and particle size analysis. The stoichiometric formula, Cu(NH 3 ) 2 C 2 O 4 of the precursor is established from elemental analysis and TG measurements, and it is designated as copper amino oxalate (CAO). In nitrogen atmosphere, the deammoniation and decomposition have been found to be zero and first order, respectively. The values of activation energy have been found to be 102.52 and 95.38 kJ/mol for deammoniation and decomposition, respectively

  17. Kinetics and Mechanism of Metal Retention/Release in Geochemical Processes in Soil - Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, Robert W.

    2000-12-29

    Effective, remediation of soils contaminated with heavy metals requires a better understanding of the mechanisms by which the metals are retained/released in soils over a long period of time. Studies on reaction of Cr(VI) with iron-rich clays indicated that structural iron (II) in these surfaces is capable of reducing chromate to chromium (III). We found that iron (II) either found naturally or produced by treatment of clay with sodium dithionite, effectively reduced Cr (VI) to Cr (III). Thus, in situ remediation of chromium combines reduction of Cr (VI) to Cr (III) and immobilization of chromium on mineral surfaces. During this study, lead sorption on a kaolin surface was found to be a rapid and a pH dependant process in which lead sorption significantly increased with the amount of phosphate on the clay surface. This study verifies that methylmercury cation remains intact when it binds to humic acids, forming a monodentate complex with some sub-population of humic thiol ligands .

  18. Author Details

    African Journals Online (AJOL)

    Njubi, Francis. Vol 15, No 1 (2001): Media Freedom and Human Rights - Articles New Media, Old Struggles: Pan Africanism, Anti-racism and Information Technology Details. ISSN: 0256-004. AJOL African Journals Online. HOW TO USE AJOL... for Researchers · for Librarians · for Authors · FAQ's · More about AJOL · AJOL's ...

  19. Author Details

    African Journals Online (AJOL)

    Radwan M.D, Mona Ahmed. Vol 12, No 1 (2000) - Articles RELAPSING REMITTING MULTIPLE SCLEROSIS: CT AND MRI IMAGING VS CLINICAL FINDINGIN THE DIAGNOSIS AND DETERMINATION OF DISEASE ACTIVITY. Details. ISSN: 1110-5607. AJOL African Journals Online. HOW TO USE AJOL... for Researchers ...

  20. Author Details

    African Journals Online (AJOL)

    Comarof, Jean. Vol 1999, No 3-4 (1999) - Articles Alien-Nation: Zombies, Immigrants and Millennial Capitalism Details. ISSN: 0850-8712. AJOL African Journals Online. HOW TO USE AJOL... for Researchers · for Librarians · for Authors · FAQ's · More about AJOL · AJOL's Partners · Terms and Conditions of Use · Contact ...