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Sample records for michaelis-menten reaction kinetics

  1. Reexamining Michaelis-Menten Enzyme Kinetics for Xanthine Oxidase

    Science.gov (United States)

    Bassingthwaighte, James B.; Chinn, Tamara M.

    2013-01-01

    Abbreviated expressions for enzyme kinetic expressions, such as the Michaelis-Menten (M-M) equations, are based on the premise that enzyme concentrations are low compared with those of the substrate and product. When one does progress experiments, where the solute is consumed during conversion to form a series of products, the idealized conditions…

  2. Dynamic disorder in single-molecule Michaelis-Menten kinetics: The reaction-diffusion formalism in the Wilemski-Fixman approximation

    Science.gov (United States)

    Chaudhury, Srabanti; Cherayil, Binny J.

    2007-09-01

    Single-molecule equations for the Michaelis-Menten [Biochem. Z. 49, 333 (1913)] mechanism of enzyme action are analyzed within the Wilemski-Fixman [J. Chem. Phys. 58, 4009 (1973); 60, 866 (1974)] approximation after the effects of dynamic disorder—modeled by the anomalous diffusion of a particle in a harmonic well—are incorporated into the catalytic step of the reaction. The solution of the Michaelis-Menten equations is used to calculate the distribution of waiting times between successive catalytic turnovers in the enzyme β-galactosidase. The calculated distribution is found to agree qualitatively with experimental results on this enzyme obtained at four different substrate concentrations. The calculations are also consistent with measurements of correlations in the fluctuations of the fluorescent light emitted during the course of catalysis, and with measurements of the concentration dependence of the randomness parameter.

  3. Classical Michaelis-Menten and system theory approach to modeling metabolite formation kinetics.

    Science.gov (United States)

    Popović, Jovan

    2004-01-01

    When single doses of drug are administered and kinetics are linear, techniques, which are based on the compartment approach and the linear system theory approach, in modeling the formation of the metabolite from the parent drug are proposed. Unlike the purpose-specific compartment approach, the methodical, conceptual and computational uniformity in modeling various linear biomedical systems is the dominant characteristic of the linear system approach technology. Saturation of the metabolic reaction results in nonlinear kinetics according to the Michaelis-Menten equation. The two compartment open model with Michaelis-Menten elimination kinetics is theorethicaly basic when single doses of drug are administered. To simulate data or to fit real data using this model, one must resort to numerical integration. A biomathematical model for multiple dosage regimen calculations of nonlinear metabolic systems in steady-state and a working example with phenytoin are presented. High correlation between phenytoin steady-state serum levels calculated from individual Km and Vmax values in the 15 adult epileptic outpatients and the observed levels at the third adjustment of phenytoin daily dose (r=0.961, p<0.01) were found.

  4. Diffusion influence on Michaelis Menten kinetics: II. The low substrate concentration limit

    Science.gov (United States)

    Kim, Hyojoon; Shin, Kook Joe

    2007-02-01

    The diffusion-influenced Michaelis-Menten kinetics in the low substrate concentration limit is studied in one and three dimensions. For the initial pair distribution of enzyme and substrate, we obtain the exact analytical results. We find that at short times the diffusion effect can make the reaction rate faster. The concentration deviations of the substrate and enzyme show t-1/2 and t-3/2 power-law behaviours in one and three dimensions, respectively, at long times. On the other hand, the average lifetime of the intermediate is independent of the initial state in one dimension, while it depends on the initial state in three dimensions. The ultimate production yield approaches unity in one dimension but it reaches a different value depending on other parameters in three dimensions. We also obtain the analytical results for the initial random distribution.

  5. Diffusion influence on Michaelis-Menten kinetics: II. The low substrate concentration limit

    International Nuclear Information System (INIS)

    Kim, Hyojoon; Shin, Kook Joe

    2007-01-01

    The diffusion-influenced Michaelis-Menten kinetics in the low substrate concentration limit is studied in one and three dimensions. For the initial pair distribution of enzyme and substrate, we obtain the exact analytical results. We find that at short times the diffusion effect can make the reaction rate faster. The concentration deviations of the substrate and enzyme show t -1/2 and t -3/2 power-law behaviours in one and three dimensions, respectively, at long times. On the other hand, the average lifetime of the intermediate is independent of the initial state in one dimension, while it depends on the initial state in three dimensions. The ultimate production yield approaches unity in one dimension but it reaches a different value depending on other parameters in three dimensions. We also obtain the analytical results for the initial random distribution

  6. Biphasic character of ribosomal translocation and non-Michaelis-Menten kinetics of translation

    Science.gov (United States)

    Xie, Ping

    2014-12-01

    We study theoretically the kinetics of mRNA translocation in the wild-type (WT) Escherichia coli ribosome, which is composed of a small 30 S and large 50 S subunit, and the ribosomes with mutations to some intersubunit bridges such as B1a, B4, B7a, and B8. The theoretical results reproduce well the available in vitro experimental data on the biphasic kinetics of the forward mRNA translocation catalyzed by elongation factor G (EF-G) hydrolyzing GTP, which can be best fit by the sum of two exponentials, and the monophasic kinetics of the spontaneous reverse mRNA translocation in the absence of the elongation factor, which can be best fit by a single-exponential function, in both the WT and mutant ribosomes. We show that both the mutation-induced increase in the maximal rate of the slow phase for the forward mRNA translocation and that in the rate of the spontaneous reverse mRNA translocation result from a reduction in the intrinsic energy barrier to resist the rotational movements between the two subunits, giving the same degree of increase in the two rates. The mutation-induced increase in the maximal rate of the fast phase for the forward mRNA translocation results mainly from the increase in the rate of the ribosomal unlocking, a conformational change in the ribosome that widens the mRNA channel for the mRNA translocation to take place, which could be partly due to the effect of the mutation on the intrasubunit 30S head rotation. Moreover, we study the translation rate of the WT and mutant ribosomes. It is shown that the translation rate versus the concentration of EF-G-GTP does not follow the Michaelis-Menten (MM) kinetics, which is in sharp contrast to the general property of other enzymes that the rate of the enzymatic reaction versus the concentration of a substrate follows the MM kinetics. The physical origin of this non-MM kinetics for the ribosome is revealed.

  7. Stability estimation of autoregulated genes under Michaelis-Menten-type kinetics

    Science.gov (United States)

    Arani, Babak M. S.; Mahmoudi, Mahdi; Lahti, Leo; González, Javier; Wit, Ernst C.

    2018-06-01

    Feedback loops are typical motifs appearing in gene regulatory networks. In some well-studied model organisms, including Escherichia coli, autoregulated genes, i.e., genes that activate or repress themselves through their protein products, are the only feedback interactions. For these types of interactions, the Michaelis-Menten (MM) formulation is a suitable and widely used approach, which always leads to stable steady-state solutions representative of homeostatic regulation. However, in many other biological phenomena, such as cell differentiation, cancer progression, and catastrophes in ecosystems, one might expect to observe bistable switchlike dynamics in the case of strong positive autoregulation. To capture this complex behavior we use the generalized family of MM kinetic models. We give a full analysis regarding the stability of autoregulated genes. We show that the autoregulation mechanism has the capability to exhibit diverse cellular dynamics including hysteresis, a typical characteristic of bistable systems, as well as irreversible transitions between bistable states. We also introduce a statistical framework to estimate the kinetics parameters and probability of different stability regimes given observational data. Empirical data for the autoregulated gene SCO3217 in the SOS system in Streptomyces coelicolor are analyzed. The coupling of a statistical framework and the mathematical model can give further insight into understanding the evolutionary mechanisms toward different cell fates in various systems.

  8. Occurrence of dead core in catalytic particles containing immobilized enzymes: analysis for the Michaelis-Menten kinetics and assessment of numerical methods.

    Science.gov (United States)

    Pereira, Félix Monteiro; Oliveira, Samuel Conceição

    2016-11-01

    In this article, the occurrence of dead core in catalytic particles containing immobilized enzymes is analyzed for the Michaelis-Menten kinetics. An assessment of numerical methods is performed to solve the boundary value problem generated by the mathematical modeling of diffusion and reaction processes under steady state and isothermal conditions. Two classes of numerical methods were employed: shooting and collocation. The shooting method used the ode function from Scilab software. The collocation methods included: that implemented by the bvode function of Scilab, the orthogonal collocation, and the orthogonal collocation on finite elements. The methods were validated for simplified forms of the Michaelis-Menten equation (zero-order and first-order kinetics), for which analytical solutions are available. Among the methods covered in this article, the orthogonal collocation on finite elements proved to be the most robust and efficient method to solve the boundary value problem concerning Michaelis-Menten kinetics. For this enzyme kinetics, it was found that the dead core can occur when verified certain conditions of diffusion-reaction within the catalytic particle. The application of the concepts and methods presented in this study will allow for a more generalized analysis and more accurate designs of heterogeneous enzymatic reactors.

  9. Utilization of integrated Michaelis-Menten equations for enzyme inhibition diagnosis and determination of kinetic constants using Solver supplement of Microsoft Office Excel.

    Science.gov (United States)

    Bezerra, Rui M F; Fraga, Irene; Dias, Albino A

    2013-01-01

    Enzyme kinetic parameters are usually determined from initial rates nevertheless, laboratory instruments only measure substrate or product concentration versus reaction time (progress curves). To overcome this problem we present a methodology which uses integrated models based on Michaelis-Menten equation. The most severe practical limitation of progress curve analysis occurs when the enzyme shows a loss of activity under the chosen assay conditions. To avoid this problem it is possible to work with the same experimental points utilized for initial rates determination. This methodology is illustrated by the use of integrated kinetic equations with the well-known reaction catalyzed by alkaline phosphatase enzyme. In this work nonlinear regression was performed with the Solver supplement (Microsoft Office Excel). It is easy to work with and track graphically the convergence of SSE (sum of square errors). The diagnosis of enzyme inhibition was performed according to Akaike information criterion. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

  10. Use of Mushroom Tyrosinase to Introduce Michaelis-Menten Enzyme Kinetics to Biochemistry Students

    Science.gov (United States)

    Flurkey, William H.; Inlow, Jennifer K.

    2017-01-01

    An inexpensive enzyme kinetics laboratory exercise for undergraduate biochemistry students is described utilizing tyrosinase from white button mushrooms. The exercise can be completed in one or two three-hour lab sessions. The optimal amounts of enzyme, substrate (catechol), and inhibitor (kojic acid) are first determined, and then kinetic data is…

  11. The Michaelis-Menten-Stueckelberg Theorem

    Directory of Open Access Journals (Sweden)

    Alexander N. Gorban

    2011-05-01

    Full Text Available We study chemical reactions with complex mechanisms under two assumptions: (i intermediates are present in small amounts (this is the quasi-steady-state hypothesis or QSS and (ii they are in equilibrium relations with substrates (this is the quasiequilibrium hypothesis or QE. Under these assumptions, we prove the generalized mass action law together with the basic relations between kinetic factors, which are sufficient for the positivity of the entropy production but hold even without microreversibility, when the detailed balance is not applicable. Even though QE and QSS produce useful approximations by themselves, only the combination of these assumptions can render the possibility beyond the “rarefied gas” limit or the “molecular chaos” hypotheses. We do not use any a priori form of the kinetic law for the chemical reactions and describe their equilibria by thermodynamic relations. The transformations of the intermediate compounds can be described by the Markov kinetics because of their low density (low density of elementary events. This combination of assumptions was introduced by Michaelis and Menten in 1913. In 1952, Stueckelberg used the same assumptions for the gas kinetics and produced the remarkable semi-detailed balance relations between collision rates in the Boltzmann equation that are weaker than the detailed balance conditions but are still sufficient for the Boltzmann H-theorem to be valid. Our results are obtained within the Michaelis-Menten-Stueckelbeg conceptual framework.

  12. Determination of the Michaelis-Menten kinetics and the genes expression involved in phyto-degradation of cyanide and ferri-cyanide.

    Science.gov (United States)

    Yu, Xiao-Zhang; Zhang, Xue-Hong

    2016-07-01

    Hydroponic experiments were conducted with different species of plants (rice, maize, soybean and willow) exposed to ferri-cyanide to investigate the half-saturation constant (K M ) and the maximal metabolic capacity (v max ) involved in phyto-assimilation. Three varieties for each testing species were collected from different origins. Measured concentrations show that the uptake rates responded biphasically to ferri-cyanide treatments by showing increases linearly at low and almost constant at high concentrations from all treatments, indicating that phyto-assimilation of ferri-cyanide followed the Michaelis-Menten kinetics. Using non-linear regression, the highest v max was by rice, followed by willows. The lowest v max was found for soybean. All plants, except maize (DY26) and rice (XJ12), had a similar K M value, suggesting the same enzyme was active in phyto-assimilation of ferri-cyanide. Transcript level, by real-time quantitative PCR, of enzymes involved in degradation of cyanides showed that the analyzed genes were differently expressed during different cyanides exposure. The expression of CAS and ST genes responded positively to KCN exposure, suggesting that β-CAS and ST pathways were two possible pathways for cyanide detoxification in rice. The transcript level of NIT and ASPNASE genes also showed a remarkable up-regulation to KCN, implying the contribution to the pool of amino acid aspartate, which is an end product of CN metabolism. Up-regulation of GS genes suggests that acquisition of ammonium released from cyanide degradation may be an additional nitrogen source for plant nutrition. Results also revealed that the expressions of these genes, except for GS, were relatively constant during iron cyanide exposure, suggesting that they are likely metabolized by plants through a non-defined pathway rather than the β-CAS pathway.

  13. Exact and approximate solutions for the decades-old Michaelis-Menten equation: Progress-curve analysis through integrated rate equations.

    Science.gov (United States)

    Goličnik, Marko

    2011-01-01

    The Michaelis-Menten rate equation can be found in most general biochemistry textbooks, where the time derivative of the substrate is a hyperbolic function of two kinetic parameters (the limiting rate V, and the Michaelis constant K(M) ) and the amount of substrate. However, fundamental concepts of enzyme kinetics can be difficult to understand fully, or can even be misunderstood, by students when based only on the differential form of the Michaelis-Menten equation, and the variety of methods available to calculate the kinetic constants from rate versus substrate concentration "textbook data." Consequently, enzyme kinetics can be confusing if an analytical solution of the Michaelis-Menten equation is not available. Therefore, the still rarely known exact solution to the Michaelis-Menten equation is presented here through the explicit closed-form equation in terms of the Lambert W(x) function. Unfortunately, as the W(x) is not available in standard curve-fitting computer programs, the practical use of this direct solution is limited for most life-science students. Thus, the purpose of this article is to provide analytical approximations to the equation for modeling Michaelis-Menten kinetics. The elementary and explicit nature of these approximations can provide students with direct and simple estimations of kinetic parameters from raw experimental time-course data. The Michaelis-Menten kinetics studied in the latter context can provide an ideal alternative to the 100-year-old problems of data transformation, graphical visualization, and data analysis of enzyme-catalyzed reactions. Hence, the content of the course presented here could gradually become an important component of the modern biochemistry curriculum in the 21st century. Copyright © 2011 Wiley Periodicals, Inc.

  14. Real-Time Enzyme Kinetics by Quantitative NMR Spectroscopy and Determination of the Michaelis-Menten Constant Using the Lambert-W Function

    Science.gov (United States)

    Her, Cheenou; Alonzo, Aaron P.; Vang, Justin Y.; Torres, Ernesto; Krishnan, V. V.

    2015-01-01

    Enzyme kinetics is an essential part of a chemistry curriculum, especially for students interested in biomedical research or in health care fields. Though the concept is routinely performed in undergraduate chemistry/biochemistry classrooms using other spectroscopic methods, we provide an optimized approach that uses a real-time monitoring of the…

  15. Stability in a Simple Food Chain System with Michaelis-Menten Functional Response and Nonlocal Delays

    Directory of Open Access Journals (Sweden)

    Wenzhen Gan

    2013-01-01

    Full Text Available This paper is concerned with the asymptotical behavior of solutions to the reaction-diffusion system under homogeneous Neumann boundary condition. By taking food ingestion and species' moving into account, the model is further coupled with Michaelis-Menten type functional response and nonlocal delay. Sufficient conditions are derived for the global stability of the positive steady state and the semitrivial steady state of the proposed problem by using the Lyapunov functional. Our results show that intraspecific competition benefits the coexistence of prey and predator. Furthermore, the introduction of Michaelis-Menten type functional response positively affects the coexistence of prey and predator, and the nonlocal delay is harmless for stabilities of all nonnegative steady states of the system. Numerical simulations are carried out to illustrate the main results.

  16. More Nuts and Bolts of Michaelis-Menten Enzyme Kinetics

    Science.gov (United States)

    Lechner, Joseph H.

    2011-01-01

    Several additions to a classroom activity are proposed in which an "enzyme" (the student) converts "substrates" (nut-bolt assemblies) into "products" (separated nuts and bolts) by unscrewing them. (Contains 1 table.)

  17. Michaelis - Menten equation for degradation of insoluble substrate

    DEFF Research Database (Denmark)

    Andersen, Morten; Kari, Jeppe; Borch, Kim

    2017-01-01

    substrate it is difficult to assess whether the requirement of the MM equation is met. In this paper we study a simple kinetic model, where removal of attack sites expose new ones which preserve the total accessible substrate, and denote this approach the substrate conserving model. The kinetic equations...... are solved in closed form, both steady states and progress curves, for any admissible values of initial conditions and rate constants. The model is shown to merge with the MM equation and the reverse MM equation when these are valid. The relation between available molar concentration of attack sites and mass...

  18. At the centennial of Michaelis and Menten, competing Michaelis-Menten steps explain effect of GLP-1 on blood-brain transfer and metabolism of glucose.

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    Gejl, Michael; Rungby, Jørgen; Brock, Birgitte; Gjedde, Albert

    2014-08-01

    Glucagon-like peptide-1 (GLP-1) is a potent insulinotropic incretin hormone with both pancreatic and extrapancreatic effects. Studies of GLP-1 reveal significant effects in regions of brain tissue that regulate appetite and satiety. GLP-1 mimetics are used for the treatment of type 2 diabetes mellitus. GLP-1 interacts with peripheral functions in which the autonomic nervous system plays an important role, and emerging pre-clinical findings indicate a potential neuroprotective role of the peptide, for example in models of stroke and in neurodegenerative disorders. A century ago, Leonor Michaelis and Maud Menten described the steady-state enzyme kinetics that still apply to the multiple receptors, transporters and enzymes that define the biochemical reactions of the brain, including the glucose-dependent impact of GLP-1 on blood-brain glucose transfer and metabolism. This MiniReview examines the potential of GLP-1 as a molecule of interest for the understanding of brain energy metabolism and with reference to the impact on brain metabolism related to appetite and satiety regulation, stroke and neurodegenerative disorders. These effects can be understood only by reference to the original formulation of the Michaelis-Menten equation as applied to a chain of kinetically controlled steps. Indeed, the effects of GLP-1 receptor activation on blood-brain glucose transfer and brain metabolism of glucose depend on the glucose concentration and relative affinities of the steps both in vitro and in vivo, as in the pancreas. © 2014 Nordic Association for the Publication of BCPT (former Nordic Pharmacological Society).

  19. Why plankton modellers should reconsider using rectangular hyperbolic (Michaelis-Menten, Monod descriptions of predator-prey interactions

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    Kevin John Flynn

    2016-09-01

    Full Text Available Rectangular hyperbolic type 2 (RHt2; Michaelis-Menten or Monod -like functions are commonly used to describe predation kinetics in plankton models, either alone or together with a prey selectivity algorithm deploying the same half-saturation constant for all prey types referenced to external prey biomass abundance. We present an analysis that indicates that such descriptions are liable to give outputs that are not plausible according to encounter theory. This is especially so for multi-prey type applications or where changes are made to the maximum feeding rate during a simulation. The RHt2 approach also gives no or limited potential for descriptions of events such as true de-selection of prey, effects of turbulence on encounters, or changes in grazer motility with satiation. We present an alternative, which carries minimal parameterisation effort and computational cost, linking allometric algorithms relating prey abundance and encounter rates to a prey-selection function controlled by satiation. The resultant Satiation-Controlled-Encounter-Based (SCEB function provides a flexible construct describing numeric predator-prey interactions with biomass-feedback control of grazing. The SCEB function includes an attack component similar to that in the Holling disk equation but SCEB differs in having only a single (satiation-based handling constant and an explicit maximum grazing rate. We argue that there is no justification for continuing to deploy RHt2 functions to describe plankton predator-prey interactions.

  20. Evaluation of rate law approximations in bottom-up kinetic models of metabolism

    DEFF Research Database (Denmark)

    Du, Bin; Zielinski, Daniel C.; Kavvas, Erol S.

    2016-01-01

    mass action rate law that removes the role of the enzyme from the reaction kinetics. We utilized in vivo data for the human red blood cell to compare the effect of rate law choices against the backdrop of physiological flux and concentration differences. We found that the Michaelis-Menten rate law......Background: The mechanistic description of enzyme kinetics in a dynamic model of metabolism requires specifying the numerical values of a large number of kinetic parameters. The parameterization challenge is often addressed through the use of simplifying approximations to form reaction rate laws....... These approximate rate laws were: 1) a Michaelis-Menten rate law with measured enzyme parameters, 2) a Michaelis-Menten rate law with approximated parameters, using the convenience kinetics convention, 3) a thermodynamic rate law resulting from a metabolite saturation assumption, and 4) a pure chemical reaction...

  1. 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 ...

  2. Patterns induced by super cross-diffusion in a predator-prey system with Michaelis-Menten type harvesting.

    Science.gov (United States)

    Liu, Biao; Wu, Ranchao; Chen, Liping

    2018-04-01

    Turing instability and pattern formation in a super cross-diffusion predator-prey system with Michaelis-Menten type predator harvesting are investigated. Stability of equilibrium points is first explored with or without super cross-diffusion. It is found that cross-diffusion could induce instability of equilibria. To further derive the conditions of Turing instability, the linear stability analysis is carried out. From theoretical analysis, note that cross-diffusion is the key mechanism for the formation of spatial patterns. By taking cross-diffusion rate as bifurcation parameter, we derive amplitude equations near the Turing bifurcation point for the excited modes by means of weakly nonlinear theory. Dynamical analysis of the amplitude equations interprets the structural transitions and stability of various forms of Turing patterns. Furthermore, the theoretical results are illustrated via numerical simulations. Copyright © 2018. Published by Elsevier Inc.

  3. Transient competitive complexation in biological kinetic isotope fractionation explains non-steady isotopic effects: Theory and application to denitrification in soils

    Energy Technology Data Exchange (ETDEWEB)

    Maggi, F.M.; Riley, W.J.

    2009-06-01

    The theoretical formulation of biological kinetic reactions in isotopic applications often assume first-order or Michaelis-Menten-Monod kinetics under the quasi-steady-state assumption to simplify the system kinetics. However, isotopic e ects have the same order of magnitude as the potential error introduced by these simpli cations. Both formulations lead to a constant fractionation factor which may yield incorrect estimations of the isotopic effect and a misleading interpretation of the isotopic signature of a reaction. We have analyzed the isotopic signature of denitri cation in biogeochemical soil systems by Menyailo and Hungate [2006], where high {sup 15}N{sub 2}O enrichment during N{sub 2}O production and inverse isotope fractionation during N{sub 2}O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with the quasi-steady-state Michaelis-Menten-Monod kinetics. When the quasi-steady-state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observations and aided in interpretation of experimental isotopic signatures. These results may imply a substantial revision in using the Rayleigh equation for interpretation of isotopic signatures and in modeling biological kinetic isotope fractionation with first-order kinetics or quasi-steady-state Michaelis-Menten-Monod kinetics.

  4. Stability in a diffusive food chain model with Michaelis-Menten functional response

    DEFF Research Database (Denmark)

    Lin, Zhigui; Pedersen, Michael

    2004-01-01

    This paper deals with the behavior of positive solutions to a reaction-diffusion system with homogeneous Neumann boundary conditions describing a three species food chain. A sufficient condition for the local asymptotical stability is given by linearization and also a sufficient condition...... for the global asymptotical stability is given by a Lyapunov function. Our result shows that the equilibrium solution is globally asymptotically stable if the net birth rate of the first species is big enough and the net death rate of the third species is neither too big nor too small. (C) 2004 Elsevier Ltd. All...

  5. Thermodynamic Activity-Based Progress Curve Analysis in Enzyme Kinetics.

    Science.gov (United States)

    Pleiss, Jürgen

    2018-03-01

    Macrokinetic Michaelis-Menten models based on thermodynamic activity provide insights into enzyme kinetics because they separate substrate-enzyme from substrate-solvent interactions. Kinetic parameters are estimated from experimental progress curves of enzyme-catalyzed reactions. Three pitfalls are discussed: deviations between thermodynamic and concentration-based models, product effects on the substrate activity coefficient, and product inhibition. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Complex dynamics of a stochastic discrete modified Leslie-Gower predator-prey model with Michaelis-Menten type prey harvesting

    Directory of Open Access Journals (Sweden)

    A. Elhassanein

    2014-06-01

    Full Text Available This paper introduced a stochastic discretized version of the modified Leslie-Gower predator-prey model with Michaelis-Menten type prey harvesting. The dynamical behavior of the proposed model was investigated. The existence and stability of the equilibria of the skeleton were studied. Numerical simulations were employed to show the model's complex dynamics by means of the largest Lyapunov exponents, bifurcations, time series diagrams and phase portraits. The effects of noise intensity on its dynamics and the intermittency phenomenon were also discussed via simulation.

  7. New types of experimental data shape the use of enzyme kinetics for dynamic network modeling.

    Science.gov (United States)

    Tummler, Katja; Lubitz, Timo; Schelker, Max; Klipp, Edda

    2014-01-01

    Since the publication of Leonor Michaelis and Maude Menten's paper on the reaction kinetics of the enzyme invertase in 1913, molecular biology has evolved tremendously. New measurement techniques allow in vivo characterization of the whole genome, proteome or transcriptome of cells, whereas the classical enzyme essay only allows determination of the two Michaelis-Menten parameters V and K(m). Nevertheless, Michaelis-Menten kinetics are still commonly used, not only in the in vitro context of enzyme characterization but also as a rate law for enzymatic reactions in larger biochemical reaction networks. In this review, we give an overview of the historical development of kinetic rate laws originating from Michaelis-Menten kinetics over the past 100 years. Furthermore, we briefly summarize the experimental techniques used for the characterization of enzymes, and discuss web resources that systematically store kinetic parameters and related information. Finally, describe the novel opportunities that arise from using these data in dynamic mathematical modeling. In this framework, traditional in vitro approaches may be combined with modern genome-scale measurements to foster thorough understanding of the underlying complex mechanisms. © 2013 FEBS.

  8. A stochastic model of enzyme kinetics

    Science.gov (United States)

    Stefanini, Marianne; Newman, Timothy; McKane, Alan

    2003-10-01

    Enzyme kinetics is generally modeled by deterministic rate equations, and in the simplest case leads to the well-known Michaelis-Menten equation. It is plausible that stochastic effects will play an important role at low enzyme concentrations. We have addressed this by constructing a simple stochastic model which can be exactly solved in the steady-state. Throughout a wide range of parameter values Michaelis-Menten dynamics is replaced by a new and simple theoretical result.

  9. Microscale Measurements of Michaelis-Menten Constants of Neuraminidase with Nanogel Capillary Electrophoresis for the Determination of the Sialic Acid Linkage.

    Science.gov (United States)

    Gattu, Srikanth; Crihfield, Cassandra L; Holland, Lisa A

    2017-01-03

    Phospholipid nanogels enhance the stability and performance of the exoglycosidase enzyme neuraminidase and are used to create a fixed zone of enzyme within a capillary. With nanogels, there is no need to covalently immobilize the enzyme, as it is physically constrained. This enables rapid quantification of Michaelis-Menten constants (K M ) for different substrates and ultimately provides a means to quantify the linkage (i.e., 2-3 versus 2-6) of sialic acids. The fixed zone of enzyme is inexpensive and easily positioned in the capillary to support electrophoresis mediated microanalysis using neuraminidase to analyze sialic acid linkages. To circumvent the limitations of diffusion during static incubation, the incubation period is reproducibly achieved by varying the number of forward and reverse passes the substrate makes through the stationary fixed zone using in-capillary electrophoretic mixing. A K M value of 3.3 ± 0.8 mM (V max , 2100 ± 200 μM/min) was obtained for 3'-sialyllactose labeled with 2-aminobenzoic acid using neuraminidase from Clostridium perfringens that cleaves sialic acid monomers with an α2-3,6,8,9 linkage, which is similar to values reported in the literature that required benchtop analyses. The enzyme cleaves the 2-3 linkage faster than the 2-6, and a K M of 2 ± 1 mM (V max , 400 ± 100 μM/min) was obtained for the 6'-sialyllactose substrate. An alternative neuraminidase selective for 2-3 sialic acid linkages generated a K M value of 3 ± 2 mM (V max , 900 ± 300 μM/min) for 3'-sialyllactose. With a knowledge of V max , the method was applied to a mixture of 2-3 and 2-6 sialyllactose as well as 2-3 and 2-6 sialylated triantennary glycan. Nanogel electrophoresis is an inexpensive, rapid, and simple alternative to current technologies used to distinguish the composition of 3' and 6' sialic acid linkages.

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

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    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.

  11. Solution of non-steady-state substrate concentration in the action of biosensor response at mixed enzyme kinetics

    Science.gov (United States)

    Senthamarai, R.; Jana Ranjani, R.

    2018-04-01

    In this paper, a mathematical model of an amperometric biosensor at mixed enzyme kinetics and diffusion limitation in the case of substrate inhibition has been developed. The model is based on time dependent reaction diffusion equation containing a non -linear term related to non -Michaelis - Menten kinetics of the enzymatic reaction. Solution for the concentration of the substrate has been derived for all values of parameters using the homotopy perturbation method. All the approximate analytic expressions of substrate concentration are compared with simulation results using Scilab/Matlab program. Finally, we have given a satisfactory agreement between them.

  12. Kinetics of Single-Enzyme Reactions on Vesicles: Role of Substrate Aggregation

    Science.gov (United States)

    Zhdanov, Vladimir P.

    2015-03-01

    Enzymatic reactions occurring in vivo on lipid membranes can be influenced by various factors including macromolecular crowding in general and substrate aggregation in particular. In academic studies, the role of these factors can experimentally be clarified by tracking single-enzyme kinetics occurring on individual lipid vesicles. To extend the conceptual basis for such experiments, we analyze herein the corresponding kinetics mathematically with emphasis on the role of substrate aggregation. In general, the aggregation may occur on different length scales. Small aggregates may e.g. contain a few proteins or peptides while large aggregates may be mesoscopic as in the case of lipid domains which can be formed in the membranes composed of different lipids. We present a kinetic model describing comprehensively the effect of aggregation of the former type on the dependence of the reaction rate on substrate membrane concentration. The results obtained with physically reasonable parameters indicate that the aggregation-related deviations from the conventional Michaelis-Menten kinetics may be appreciable. Special Issue Comments: This theoretical article is focused on single-enzyme reactions occurring in parallel with substrate aggregation on individual vesicles. This subject is related to a few Special Issue articles concerning enzyme dynamics6,7 and function8 and mathematical aspects of stochastic kinetics.9

  13. Solvent 1H/2H isotopic effects in the reaction of the L-Tyrosine oxidation catalyzed by Tyrosinase

    International Nuclear Information System (INIS)

    Kozlowska, M.; Kanska, M.

    2006-01-01

    Tyrosinase is well known catalyst in the oxidation of L-Tyrosine to L-DOPA and following oxidation of L-DOPA to dopachinone. The aim of communication is to present the results of studies on the solvent isotopic effects (SIE) in the above reactions for the 1 H/ 2 H in the 3',5' and 2',6' substituted tyrosine. Obtained dependence of the reaction rate on the substrate concentration were applied for optimization of the kinetic parameters, k cat and k cat /K m , in the Michaelis-Menten equation. As a result - better understanding of the L-DOPA creation can be achieved

  14. Emergence of dynamic cooperativity in the stochastic kinetics of fluctuating enzymes

    International Nuclear Information System (INIS)

    Kumar, Ashutosh; Chatterjee, Sambarta; Nandi, Mintu; Dua, Arti

    2016-01-01

    Dynamic co-operativity in monomeric enzymes is characterized in terms of a non-Michaelis-Menten kinetic behaviour. The latter is believed to be associated with mechanisms that include multiple reaction pathways due to enzymatic conformational fluctuations. Recent advances in single-molecule fluorescence spectroscopy have provided new fundamental insights on the possible mechanisms underlying reactions catalyzed by fluctuating enzymes. Here, we present a bottom-up approach to understand enzyme turnover kinetics at physiologically relevant mesoscopic concentrations informed by mechanisms extracted from single-molecule stochastic trajectories. The stochastic approach, presented here, shows the emergence of dynamic co-operativity in terms of a slowing down of the Michaelis-Menten (MM) kinetics resulting in negative co-operativity. For fewer enzymes, dynamic co-operativity emerges due to the combined effects of enzymatic conformational fluctuations and molecular discreteness. The increase in the number of enzymes, however, suppresses the effect of enzymatic conformational fluctuations such that dynamic co-operativity emerges solely due to the discrete changes in the number of reacting species. These results confirm that the turnover kinetics of fluctuating enzyme based on the parallel-pathway MM mechanism switches over to the single-pathway MM mechanism with the increase in the number of enzymes. For large enzyme numbers, convergence to the exact MM equation occurs in the limit of very high substrate concentration as the stochastic kinetics approaches the deterministic behaviour.

  15. Emergence of dynamic cooperativity in the stochastic kinetics of fluctuating enzymes

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Ashutosh; Chatterjee, Sambarta; Nandi, Mintu; Dua, Arti, E-mail: arti@iitm.ac.in [Department of Chemistry, Indian Institute of Technology, Madras, Chennai 600036 (India)

    2016-08-28

    Dynamic co-operativity in monomeric enzymes is characterized in terms of a non-Michaelis-Menten kinetic behaviour. The latter is believed to be associated with mechanisms that include multiple reaction pathways due to enzymatic conformational fluctuations. Recent advances in single-molecule fluorescence spectroscopy have provided new fundamental insights on the possible mechanisms underlying reactions catalyzed by fluctuating enzymes. Here, we present a bottom-up approach to understand enzyme turnover kinetics at physiologically relevant mesoscopic concentrations informed by mechanisms extracted from single-molecule stochastic trajectories. The stochastic approach, presented here, shows the emergence of dynamic co-operativity in terms of a slowing down of the Michaelis-Menten (MM) kinetics resulting in negative co-operativity. For fewer enzymes, dynamic co-operativity emerges due to the combined effects of enzymatic conformational fluctuations and molecular discreteness. The increase in the number of enzymes, however, suppresses the effect of enzymatic conformational fluctuations such that dynamic co-operativity emerges solely due to the discrete changes in the number of reacting species. These results confirm that the turnover kinetics of fluctuating enzyme based on the parallel-pathway MM mechanism switches over to the single-pathway MM mechanism with the increase in the number of enzymes. For large enzyme numbers, convergence to the exact MM equation occurs in the limit of very high substrate concentration as the stochastic kinetics approaches the deterministic behaviour.

  16. Emergence of dynamic cooperativity in the stochastic kinetics of fluctuating enzymes

    Science.gov (United States)

    Kumar, Ashutosh; Chatterjee, Sambarta; Nandi, Mintu; Dua, Arti

    2016-08-01

    Dynamic co-operativity in monomeric enzymes is characterized in terms of a non-Michaelis-Menten kinetic behaviour. The latter is believed to be associated with mechanisms that include multiple reaction pathways due to enzymatic conformational fluctuations. Recent advances in single-molecule fluorescence spectroscopy have provided new fundamental insights on the possible mechanisms underlying reactions catalyzed by fluctuating enzymes. Here, we present a bottom-up approach to understand enzyme turnover kinetics at physiologically relevant mesoscopic concentrations informed by mechanisms extracted from single-molecule stochastic trajectories. The stochastic approach, presented here, shows the emergence of dynamic co-operativity in terms of a slowing down of the Michaelis-Menten (MM) kinetics resulting in negative co-operativity. For fewer enzymes, dynamic co-operativity emerges due to the combined effects of enzymatic conformational fluctuations and molecular discreteness. The increase in the number of enzymes, however, suppresses the effect of enzymatic conformational fluctuations such that dynamic co-operativity emerges solely due to the discrete changes in the number of reacting species. These results confirm that the turnover kinetics of fluctuating enzyme based on the parallel-pathway MM mechanism switches over to the single-pathway MM mechanism with the increase in the number of enzymes. For large enzyme numbers, convergence to the exact MM equation occurs in the limit of very high substrate concentration as the stochastic kinetics approaches the deterministic behaviour.

  17. Modeling networks of coupled enzymatic reactions using the total quasi-steady state approximation.

    Directory of Open Access Journals (Sweden)

    Andrea Ciliberto

    2007-03-01

    Full Text Available In metabolic networks, metabolites are usually present in great excess over the enzymes that catalyze their interconversion, and describing the rates of these reactions by using the Michaelis-Menten rate law is perfectly valid. This rate law assumes that the concentration of enzyme-substrate complex (C is much less than the free substrate concentration (S0. However, in protein interaction networks, the enzymes and substrates are all proteins in comparable concentrations, and neglecting C with respect to S0 is not valid. Borghans, DeBoer, and Segel developed an alternative description of enzyme kinetics that is valid when C is comparable to S0. We extend this description, which Borghans et al. call the total quasi-steady state approximation, to networks of coupled enzymatic reactions. First, we analyze an isolated Goldbeter-Koshland switch when enzymes and substrates are present in comparable concentrations. Then, on the basis of a real example of the molecular network governing cell cycle progression, we couple two and three Goldbeter-Koshland switches together to study the effects of feedback in networks of protein kinases and phosphatases. Our analysis shows that the total quasi-steady state approximation provides an excellent kinetic formalism for protein interaction networks, because (1 it unveils the modular structure of the enzymatic reactions, (2 it suggests a simple algorithm to formulate correct kinetic equations, and (3 contrary to classical Michaelis-Menten kinetics, it succeeds in faithfully reproducing the dynamics of the network both qualitatively and quantitatively.

  18. Transient competitive complexation in biological kinetic isotope fractionation explains nonsteady isotopic effects: Theory and application to denitrification in soils

    Science.gov (United States)

    Maggi, Federico; Riley, William J.

    2009-12-01

    The theoretical formulation of biological kinetic isotope fractionation often assumes first-order or Michaelis-Menten kinetics, the latter solved under the quasi-steady state assumption. Both formulations lead to a constant isotope fractionation factor, therefore they may return incorrect estimations of isotopic effects and misleading interpretations of isotopic signatures when fractionation is not a steady process. We have analyzed the isotopic signature of denitrification in biogeochemical soil systems by Menyailo and Hungate (2006) in which high and variable 15N-N2O enrichment during N2O production and inverse isotope fractionation during N2O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with Michaelis-Menten kinetics. When Michaelis-Menten kinetics were coupled to Monod kinetics to describe biomass and enzyme dynamics, and the quasi-steady state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observed concentrations, and variable and inverse isotope fractionations. These results imply a substantial revision in modeling isotopic effects, suggesting that steady state kinetics such as first-order, Rayleigh, and classic Michaelis-Menten kinetics should be superseded by transient kinetics in conjunction with biomass and enzyme dynamics.

  19. A century of enzyme kinetic analysis, 1913 to 2013.

    Science.gov (United States)

    Johnson, Kenneth A

    2013-09-02

    This review traces the history and logical progression of methods for quantitative analysis of enzyme kinetics from the 1913 Michaelis and Menten paper to the application of modern computational methods today. Following a brief review of methods for fitting steady state kinetic data, modern methods are highlighted for fitting full progress curve kinetics based upon numerical integration of rate equations, including a re-analysis of the original Michaelis-Menten full time course kinetic data. Finally, several illustrations of modern transient state kinetic methods of analysis are shown which enable the elucidation of reactions occurring at the active sites of enzymes in order to relate structure and function. Copyright © 2013 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

  20. 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.

  1. The Non-Linear Child: Ontogeny, Isoniazid Concentration, and NAT2 Genotype Modulate Enzyme Reaction Kinetics and Metabolism.

    Science.gov (United States)

    Rogers, Zoe; Hiruy, Hiwot; Pasipanodya, Jotam G; Mbowane, Chris; Adamson, John; Ngotho, Lihle; Karim, Farina; Jeena, Prakash; Bishai, William; Gumbo, Tawanda

    2016-09-01

    N-acetyltransferase 2 (NAT2) catalyzes the acetylation of isoniazid to N-acetylisoniazid. NAT2 polymorphism explains 88% of isoniazid clearance variability in adults. We examined the effects of clinical and genetic factors on Michaelis-Menten reaction kinetic constants of maximum velocity (V max ) and affinity (K m ) in children 0-10years old. We measured the rates of isoniazid elimination and N-acetylisoniazid production in the blood of 30 children. Since maturation effects could be non-linear, we utilized a pharmacometric approach and the artificial intelligence method, multivariate adaptive regression splines (MARS), to identify factors predicting NAT2 V max and K m by examining clinical, genetic, and laboratory factors in toto. Isoniazid concentration predicted both V max and K m and superseded the contribution of NAT2 genotype. Age non-linearly modified the NAT2 genotype contribution until maturation at ≥5.3years. Thus, enzyme efficiency was constrained by substrate concentration, genes, and age. Since MARS output is in the form of basis functions and equations, it allows multiscale systems modeling from the level of cellular chemical reactions to whole body physiological parameters, by automatic selection of significant predictors by the algorithm. Copyright © 2016 Forschungsgesellschaft für Arbeitsphysiologie und Arbeitschutz e.V. Published by Elsevier B.V. All rights reserved.

  2. The Non-Linear Child: Ontogeny, Isoniazid Concentration, and NAT2 Genotype Modulate Enzyme Reaction Kinetics and Metabolism

    Directory of Open Access Journals (Sweden)

    Zoe Rogers

    2016-09-01

    Full Text Available N-acetyltransferase 2 (NAT2 catalyzes the acetylation of isoniazid to N-acetylisoniazid. NAT2 polymorphism explains 88% of isoniazid clearance variability in adults. We examined the effects of clinical and genetic factors on Michaelis-Menten reaction kinetic constants of maximum velocity (Vmax and affinity (Km in children 0–10 years old. We measured the rates of isoniazid elimination and N-acetylisoniazid production in the blood of 30 children. Since maturation effects could be non-linear, we utilized a pharmacometric approach and the artificial intelligence method, multivariate adaptive regression splines (MARS, to identify factors predicting NAT2 Vmax and Km by examining clinical, genetic, and laboratory factors in toto. Isoniazid concentration predicted both Vmax and Km and superseded the contribution of NAT2 genotype. Age non-linearly modified the NAT2 genotype contribution until maturation at ≥5.3 years. Thus, enzyme efficiency was constrained by substrate concentration, genes, and age. Since MARS output is in the form of basis functions and equations, it allows multiscale systems modeling from the level of cellular chemical reactions to whole body physiological parameters, by automatic selection of significant predictors by the algorithm.

  3. Kinetic modeling of electron transfer reactions in photosystem I complexes of various structures with substituted quinone acceptors.

    Science.gov (United States)

    Milanovsky, Georgy E; Petrova, Anastasia A; Cherepanov, Dmitry A; Semenov, Alexey Yu

    2017-09-01

    The reduction kinetics of the photo-oxidized primary electron donor P 700 in photosystem I (PS I) complexes from cyanobacteria Synechocystis sp. PCC 6803 were analyzed within the kinetic model, which considers electron transfer (ET) reactions between P 700 , secondary quinone acceptor A 1 , iron-sulfur clusters and external electron donor and acceptors - methylviologen (MV), 2,3-dichloro-naphthoquinone (Cl 2 NQ) and oxygen. PS I complexes containing various quinones in the A 1 -binding site (phylloquinone PhQ, plastoquinone-9 PQ and Cl 2 NQ) as well as F X -core complexes, depleted of terminal iron-sulfur F A /F B clusters, were studied. The acceleration of charge recombination in F X -core complexes by PhQ/PQ substitution indicates that backward ET from the iron-sulfur clusters involves quinone in the A 1 -binding site. The kinetic parameters of ET reactions were obtained by global fitting of the P 700 + reduction with the kinetic model. The free energy gap ΔG 0 between F X and F A /F B clusters was estimated as -130 meV. The driving force of ET from A 1 to F X was determined as -50 and -220 meV for PhQ in the A and B cofactor branches, respectively. For PQ in A 1A -site, this reaction was found to be endergonic (ΔG 0  = +75 meV). The interaction of PS I with external acceptors was quantitatively described in terms of Michaelis-Menten kinetics. The second-order rate constants of ET from F A /F B , F X and Cl 2 NQ in the A 1 -site of PS I to external acceptors were estimated. The side production of superoxide radical in the A 1 -site by oxygen reduction via the Mehler reaction might comprise ≥0.3% of the total electron flow in PS I.

  4. Catalytic Activity of μ-Carbido-Dimeric Iron(IV) Octapropylporphyrazinate in the 3,5,7,2',4'-Pentahydroxyflavone Oxidation Reaction with tert-Butyl Hydroperoxide

    Science.gov (United States)

    Tyurin, D. V.; Zaitseva, S. V.; Kudrik, E. V.

    2018-05-01

    It is found for the first time that μ-carbido-dimeric iron(IV) octapropylporphyrazinate displays catalytic activity in the oxidation reaction of natural flavonol morin with tert-butyl hydroperoxide, with the catalyst being stable under conditions of the reaction. The kinetics of this reaction are studied. It is shown the reaction proceeds via tentative formation of a complex between the catalyst and the oxidant, followed by O‒O bond homolytic cleavage. The kinetics of the reaction is described in the coordinates of the Michaelis-Menten equation. A linear dependence of the apparent reaction rate constant on the concentration of the catalyst is observed, testifying to its participation in the limiting reaction step. The equilibrium constants and rates of interaction are found. A mechanism is proposed for the reaction on the basis of the experimental data.

  5. Spectral Quasi-Equilibrium Manifold for Chemical Kinetics.

    Science.gov (United States)

    Kooshkbaghi, Mahdi; Frouzakis, Christos E; Boulouchos, Konstantinos; Karlin, Iliya V

    2016-05-26

    The Spectral Quasi-Equilibrium Manifold (SQEM) method is a model reduction technique for chemical kinetics based on entropy maximization under constraints built by the slowest eigenvectors at equilibrium. The method is revisited here and discussed and validated through the Michaelis-Menten kinetic scheme, and the quality of the reduction is related to the temporal evolution and the gap between eigenvalues. SQEM is then applied to detailed reaction mechanisms for the homogeneous combustion of hydrogen, syngas, and methane mixtures with air in adiabatic constant pressure reactors. The system states computed using SQEM are compared with those obtained by direct integration of the detailed mechanism, and good agreement between the reduced and the detailed descriptions is demonstrated. The SQEM reduced model of hydrogen/air combustion is also compared with another similar technique, the Rate-Controlled Constrained-Equilibrium (RCCE). For the same number of representative variables, SQEM is found to provide a more accurate description.

  6. Kinetic characterisation of primer mismatches in allele-specific PCR: a quantitative assessment.

    Science.gov (United States)

    Waterfall, Christy M; Eisenthal, Robert; Cobb, Benjamin D

    2002-12-20

    A novel method of estimating the kinetic parameters of Taq DNA polymerase during rapid cycle PCR is presented. A model was constructed using a simplified sigmoid function to represent substrate accumulation during PCR in combination with the general equation describing high substrate inhibition for Michaelis-Menten enzymes. The PCR progress curve was viewed as a series of independent reactions where initial rates were accurately measured for each cycle. Kinetic parameters were obtained for allele-specific PCR (AS-PCR) amplification to examine the effect of mismatches on amplification. A high degree of correlation was obtained providing evidence of substrate inhibition as a major cause of the plateau phase that occurs in the later cycles of PCR.

  7. Reaction and catalyst engineering to exploit kinetically controlled whole-cell multistep biocatalysis for terminal FAME oxyfunctionalization.

    Science.gov (United States)

    Schrewe, Manfred; Julsing, Mattijs K; Lange, Kerstin; Czarnotta, Eik; Schmid, Andreas; Bühler, Bruno

    2014-09-01

    The oxyfunctionalization of unactivated C−H bonds can selectively and efficiently be catalyzed by oxygenase-containing whole-cell biocatalysts. Recombinant Escherichia coli W3110 containing the alkane monooxygenase AlkBGT and the outer membrane protein AlkL from Pseudomonas putida GPo1 have been shown to efficiently catalyze the terminal oxyfunctionalization of renewable fatty acid methyl esters yielding bifunctional products of interest for polymer synthesis. In this study, AlkBGTL-containing E. coli W3110 is shown to catalyze the multistep conversion of dodecanoic acid methyl ester (DAME) via terminal alcohol and aldehyde to the acid, exhibiting Michaelis-Menten-type kinetics for each reaction step. In two-liquid phase biotransformations, the product formation pattern was found to be controlled by DAME availability. Supplying DAME as bulk organic phase led to accumulation of the terminal alcohol as the predominant product. Limiting DAME availability via application of bis(2-ethylhexyl)phthalate (BEHP) as organic carrier solvent enabled almost exclusive acid accumulation. Furthermore, utilization of BEHP enhanced catalyst stability by reducing toxic effects of substrate and products. A further shift towards the overoxidized products was achieved by co-expression of the gene encoding the alcohol dehydrogenase AlkJ, which was shown to catalyze efficient and irreversible alcohol to aldehyde oxidation in vivo. With DAME as organic phase, the aldehyde accumulated as main product using resting cells containing AlkBGT, AlkL, as well as AlkJ. This study highlights the versatility of whole-cell biocatalysis for synthesis of industrially relevant bifunctional building blocks and demonstrates how integrated reaction and catalyst engineering can be implemented to control product formation patterns in biocatalytic multistep reactions. © 2014 Wiley Periodicals, Inc.

  8. Elimination of intermediate species in multiscale stochastic reaction networks

    DEFF Research Database (Denmark)

    Cappelletti, Daniele; Wiuf, Carsten

    2016-01-01

    such as the substrate-enzyme complex in the Michaelis-Menten mechanism. Such species are virtually in all real-world networks, they are typically short-lived, degraded at a fast rate and hard to observe experimentally. We provide conditions under which the Markov process of a multiscale reaction network...

  9. 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.

  10. Quantification of in vivo metabolic kinetics of hyperpolarized pyruvate in rat kidneys using dynamic 13C MRSI.

    Science.gov (United States)

    Xu, Tao; Mayer, Dirk; Gu, Meng; Yen, Yi-Fen; Josan, Sonal; Tropp, James; Pfefferbaum, Adolf; Hurd, Ralph; Spielman, Daniel

    2011-10-01

    With signal-to-noise ratio enhancements on the order of 10,000-fold, hyperpolarized MRSI of metabolically active substrates allows the study of both the injected substrate and downstream metabolic products in vivo. Although hyperpolarized [1-(13)C]pyruvate, in particular, has been used to demonstrate metabolic activities in various animal models, robust quantification and metabolic modeling remain important areas of investigation. Enzyme saturation effects are routinely seen with commonly used doses of hyperpolarized [1-(13)C]pyruvate; however, most metrics proposed to date, including metabolite ratios, time-to-peak of metabolic products and single exchange rate constants, fail to capture these saturation effects. In addition, the widely used small-flip-angle excitation approach does not correctly model the inflow of fresh downstream metabolites generated proximal to the target slice, which is often a significant factor in vivo. In this work, we developed an efficient quantification framework employing a spiral-based dynamic spectroscopic imaging approach. The approach overcomes the aforementioned limitations and demonstrates that the in vivo (13)C labeling of lactate and alanine after a bolus injection of [1-(13)C]pyruvate is well approximated by saturatable kinetics, which can be mathematically modeled using a Michaelis-Menten-like formulation, with the resulting estimated apparent maximal reaction velocity V(max) and apparent Michaelis constant K(M) being unbiased with respect to critical experimental parameters, including the substrate dose, bolus shape and duration. Although the proposed saturatable model has a similar mathematical formulation to the original Michaelis-Menten kinetics, it is conceptually different. In this study, we focus on the (13)C labeling of lactate and alanine and do not differentiate the labeling mechanism (net flux or isotopic exchange) or the respective contribution of various factors (organ perfusion rate, substrate transport

  11. The steady-state kinetics of the NADH-dependent nitrite reductase from Escherichia coli K 12. Nitrite and hydroxylamine reduction.

    Science.gov (United States)

    Jackson, R H; Cole, J A; Cornish-Bowden, A

    1981-01-01

    The reduction of both NO2- and hydroxylamine by the NADH-dependent nitrite reductase of Escherichia coli K 12 (EC 1.6.6.4) appears to follow Michaelis-Menten kinetics over a wide range of NADH concentrations. Substrate inhibition can, however, be detected at low concentrations of the product NAD+. In addition, NAD+ displays mixed product inhibition with respect to NADH and mixed or uncompetitive inhibition with respect to hydroxylamine. These inhibition characteristics are consistent with a mechanism in which hydroxylamine binds during catalysis to a different enzyme form from that generated when NAD+ is released. The apparent maximum velocity with NADH as varied substrate increases as the NAD+ concentration increases from 0.05 to 0.7 mM with 1 mM-NO2- or 100 mM-hydroxylamine as oxidized substrate. This increase is more marked for hydroxylamine reduction than for NO2- reduction. Models incorporating only one binding site for NAD can account for the variation in the Michaelis-Menten parameters for both NADH and hydroxylamine with [NAD+] for hydroxylamine reduction. According to these models, activation of the reaction occurs by reversal of an over-reduction of the enzyme by NADH. If the observed activation of the enzyme by NAD+ derives both from activation of the generation of the enzyme-hydroxylamine complex from the enzyme-NO2- complex during NO2- reduction and from activation of the reduction of the enzyme-hydroxylamine complex to form NH4+, then the variation of Vapp. for NO2- or hydroxylamine with [NAD+] is consistent with the occurrence of the same enzyme-hydroxylamine complex as an intermediate in both reactions. PMID:6279095

  12. Chemical kinetics of gas reactions

    CERN Document Server

    Kondrat'Ev, V N

    2013-01-01

    Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema

  13. Kinetics of Butyrate, Acetate, and Hydrogen Metabolism in a Thermophilic, Anaerobic, Butyrate-Degrading Triculture

    OpenAIRE

    Ahring, Birgitte K.; Westermann, Peter

    1987-01-01

    Kinetics of butyrate, acetate, and hydrogen metabolism were determined with butyrate-limited, chemostat-grown tricultures of a thermophilic butyrate-utilizing bacterium together with Methanobacterium thermoautotrophicum and the TAM organism, a thermophilic acetate-utilizing methanogenic rod. Kinetic parameters were determined from progress curves fitted to the integrated form of the Michaelis-Menten equation. The apparent half-saturation constants, Km, for butyrate, acetate, and dissolved hyd...

  14. Modular rate laws for enzymatic reactions: thermodynamics, elasticities and implementation.

    Science.gov (United States)

    Liebermeister, Wolfram; Uhlendorf, Jannis; Klipp, Edda

    2010-06-15

    Standard rate laws are a key requisite for systematically turning metabolic networks into kinetic models. They should provide simple, general and biochemically plausible formulae for reaction velocities and reaction elasticities. At the same time, they need to respect thermodynamic relations between the kinetic constants and the metabolic fluxes and concentrations. We present a family of reversible rate laws for reactions with arbitrary stoichiometries and various types of regulation, including mass-action, Michaelis-Menten and uni-uni reversible Hill kinetics as special cases. With a thermodynamically safe parameterization of these rate laws, parameter sets obtained by model fitting, sampling or optimization are guaranteed to lead to consistent chemical equilibrium states. A reformulation using saturation values yields simple formulae for rates and elasticities, which can be easily adjusted to the given stationary flux distributions. Furthermore, this formulation highlights the role of chemical potential differences as thermodynamic driving forces. We compare the modular rate laws to the thermodynamic-kinetic modelling formalism and discuss a simplified rate law in which the reaction rate directly depends on the reaction affinity. For automatic handling of modular rate laws, we propose a standard syntax and semantic annotations for the Systems Biology Markup Language. An online tool for inserting the rate laws into SBML models is freely available at www.semanticsbml.org. Supplementary data are available at Bioinformatics online.

  15. Kinetic analysis of enzyme systems with suicide substrate in the presence of a reversible competitive inhibitor, tested by simulated progress curves.

    Science.gov (United States)

    Moruno-Dávila, M A; Garrido-del Solo, C; García-Moreno, M; Havsteen, B H; Garcia-Sevilla, F; Garcia-Cánovas, F; Varón, R

    2001-02-01

    The use of suicide substrates remains a very important and useful method in enzymology for studying enzyme mechanisms and designing potential drugs. Suicide substrates act as modified substrates for the target enzymes and bind to the active site. Therefore the presence of a competitive reversible inhibitor decreases the rate of substrate-induced inactivation and protects the enzyme from this inactivation. This lowering on the inactivation rate has evident physiological advantages, since it allows the easy acquisition of experimental data and facilitates kinetic data analysis by providing another variable (inhibitor concentration). However despite the importance of the simultaneous action of a suicide substrate and a competitive reversible inhibition, to date no corresponding kinetic analysis has been carried out. Therefore we present a general kinetic analysis of a Michaelis-Menten reaction mechanism with double inhibition caused by both, a suicide substrate and a competitive reversible inhibitor. We assume rapid equilibrium of the reversible reaction steps involved, while the time course equations for the reaction product have been derived with the assumption of a limiting enzyme. The goodness of the analytical solutions has been tested by comparison with the simulated curves obtained by numerical integration. A kinetic data analysis to determine the corresponding kinetic parameters from the time progress curve of the product is suggested. In conclusion, we present a complete kinetic analysis of an enzyme reaction mechanism as described above in an attempt to fill a gap in the theoretical treatment of this type of system.

  16. Lipase-catalyzed synthesis of palmitanilide: Kinetic model and antimicrobial activity study.

    Science.gov (United States)

    Liu, Kuan-Miao; Liu, Kuan-Ju

    2016-01-01

    Enzymatic syntheses of fatty acid anilides are important owing to their wide range of industrial applications in detergents, shampoo, cosmetics, and surfactant formulations. The amidation reaction of Mucor miehei lipase Lipozyme IM20 was investigated for direct amidation of triacylglycerol in organic solvents. The process parameters (reaction temperature, substrate molar ratio, enzyme amount) were optimized to achieve the highest yield of anilide. The maximum yield of palmitanilide (88.9%) was achieved after 24 h of reaction at 40 °C at an enzyme concentration of 1.4% (70 mg). Kinetics of lipase-catalyzed amidation of aniline with tripalmitin has been investigated. The reaction rate could be described in terms of the Michaelis-Menten equation with a Ping-Pong Bi-Bi mechanism and competitive inhibition by both the substrates. The kinetic constants were estimated by using non-linear regression method using enzyme kinetic modules. The enzyme operational stability study showed that Lipozyme IM20 retained 38.1% of the initial activity for the synthesis of palmitanilide (even after repeated use for 48 h). Palmitanilide, a fatty acid amide, exhibited potent antimicrobial activity toward Bacillus cereus. Copyright © 2015 Elsevier Inc. All rights reserved.

  17. Kinetics of Oxidation of Metochlopramide withChloramine-T in HClO4 Medium

    Directory of Open Access Journals (Sweden)

    K. M. Meenakshi

    2009-01-01

    Full Text Available The kinetics of oxidation of metochlopramide hydrochloride (MCP with sodium N-chloro p-toluenesulfonamide (CAT in perchloric acid solution has been studied at 313K. The reaction rate shows a first order dependence on [CAT], fractional order on [MCP] and inverse fractional order on [H+]. There is a negative effect of dielectric constant of the solvent. The addition of the reduction product of CAT has no significant effect on the rate. The rate remained unchanged with the variation in the ionic strength of the medium. The reaction fails to induce the polymerization of acrylonitrile. Thermodynamic parameters have been computed by Arrhenius plot. The stoichiometry of the reaction was found to be 1:2 and oxidation products were identified. The Michaelis-Menten type of kinetics has been proposed. CH3C6H4SO2NHCl have been assumed to be the reactive oxidizing species. Thermodynamic parameters were computed by studying reactions at different temperatures. A mechanism consistent with observed kinetics is proposed.

  18. THE KINETICS OF THE REACTIONS CATALYZED BY AN ENZYMATIC PREPARATION PRODUCED BY A BACILLUS LICHENIFORMIS STRAIN

    Directory of Open Access Journals (Sweden)

    MONICA DRAGOMIRESCU

    2007-05-01

    Full Text Available Robust immobilization techniques that preserve the activity of biomolecules have manypotential applications. In recent years, a number of new bioimobilisation methods in solgel-derived materials were reported. The interactions between the biomolecule and theinorganic material determine the degree to which the biomolecule retains its nativeproperties. The newer technological developments in the field of immobilizedbiocatalysts can offer the possibility of a wider and more economical exploitation ofbiocatalysts in biological applications, food and feed industry, medicine, and in thedevelopment of bioprocess monitoring devices, like the biosensors.The aim of this study was to obtain immobilized enzymatic preparations by methodswhich affect enzyme conformations and kinetic parameters as less as possible. Weimmobilized the enzymatic preparation with protease activity produced by a Bacilluslicheniformis B 40 local strain by physical bonding on ceramics and entrapment into solgel-derived glasses obtained from tetraethyl orthosilicate (TEOS, deposited in thin layeron a ceramic support (entrapment/deposition. Both physically adsorbed andentrapped/deposited enzymes follow Michaelis-Menten kinetics, similar with the solubleenzyme. In the case of immobilized enzymes, the apparent Michaelis constant, Km, wasgreater than that of the native one, as it was expected. The kinetic parameters indicatethat the enzymatic preparations adsorbed on ceramic support and entrapped/depositedshow less affinity for the substrate, Km being 1.3 and 2.1 times higher than that of thenative enzyme, respectively. The maximum velocity increased also by 3.5 and 7.9 timesrespectively, compared with the free counterpart (according to Lineweaver-Burklinearization.

  19. Kinetics of Bio-Reactions

    DEFF Research Database (Denmark)

    Villadsen, John

    2015-01-01

    his chapter predicts the specific rates of reaction by means of a mathematical expression, the kinetics of the reaction. This expression can be derived through a mechanistic interpretation of an enzymatically catalyzed reaction, but it is essentially of empirical nature for cell reactions. The mo...

  20. Tracer kinetics: Modelling of tracer behaviour in nonlinear and nonsteady state systems exemplified by the evaluation of protein turnover in plant organs

    International Nuclear Information System (INIS)

    Winkler, E.

    1991-01-01

    If nonlinear biological processes are investigated by means of tracer experiments they can be modelled with linear kinetic equations (compartment equations) as long as the total system is in a stationary state. But if nonstationary behaviour is included considerations on the kinetics of the individual processes are necessary. Within the range of biological and agricultural investigations especially first order reactions (constant fraction processes), zero order reactions (constant amount process) and saturation reactions (Michaelis-Menten-kinetics) are to be taken into account. A rigorous treatment of data based on system theory can be preceeded by graphic-algebraic procedure which may be more or less uncertain in its results but which can easily be handled. An example is given of methodological considerations concerning the combination of evaluation procedures and the discrimination between different reaction mechanisms. It treats protein turnover in 2 different parts of growing wheat plants investigated by means of an 15 N-tracer experiment. Whereas in a stationary system (upper stalk section) linear tracer equations were sufficient irrespective of the true reaction mechanism, for protein synthesis in the upper leaf as a nonstationary system it was necessary to decide between the hypotheses of a zero order and a first order reaction. In accordance with statements in the literature the unambiguous result was a combination of protein synthesis as a zero order process and of protein degradation as a first order process. (orig.) [de

  1. Enzymatic oxidation of rutin by horseradish peroxidase: kinetic mechanism and identification of a dimeric product by LC-Orbitrap mass spectrometry.

    Science.gov (United States)

    Savic, Sasa; Vojinovic, Katarina; Milenkovic, Sanja; Smelcerovic, Andrija; Lamshoeft, Marc; Petronijevic, Zivomir

    2013-12-15

    Flavonoid oxidation is important issue in food processing and quality. The kinetic mechanism of enzymatic oxidation of rutin by horseradish peroxidase (HRP) was studied. Rutin oxidation reaction was followed by recording of spectral changes over the time at 360 nm. The studied oxidation is mostly enzymatic and less part non-enzymatic. The reaction with HRP has a higher rate compared with the reaction without of HRP, whereby is part of non-enzymatic reaction about 10% of the total reaction. Kinetic parameters were determined from graphics of linear Michaelis-Menten equation, and it was found that investigated reactions of rutin oxidation by HRP take place in a ping-pong kinetic mechanism. High resolution HPLC-MS analysis of the mixture of oxidized products of rutin revealed the presence of rutin dimer. Because of widely distribution of rutin as well as presence of peroxidases and hydrogen peroxide in fresh foods identification of this enzymatic modification product can be beneficial for foods quality and safety. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. Hydrodynamic chronoamperometry for probing kinetics of anaerobic microbial metabolism--case study of Faecalibacterium prausnitzii.

    Science.gov (United States)

    Prévoteau, Antonin; Geirnaert, Annelies; Arends, Jan B A; Lannebère, Sylvain; Van de Wiele, Tom; Rabaey, Korneel

    2015-07-01

    Monitoring in vitro the metabolic activity of microorganisms aids bioprocesses and enables better understanding of microbial metabolism. Redox mediators can be used for this purpose via different electrochemical techniques that are either complex or only provide non-continuous data. Hydrodynamic chronoamperometry using a rotating disc electrode (RDE) can alleviate these issues but was seldom used and is poorly characterized. The kinetics of Faecalibacterium prausnitzii A2-165, a beneficial gut microbe, were determined using a RDE with riboflavin as redox probe. This butyrate producer anaerobically ferments glucose and reduces riboflavin whose continuous monitoring on a RDE provided highly accurate kinetic measurements of its metabolism, even at low cell densities. The metabolic reaction rate increased linearly over a broad range of cell concentrations (9 × 10(4) to 5 × 10(7) cells.mL(-1)). Apparent Michaelis-Menten kinetics was observed with respect to riboflavin (KM = 6 μM; kcat = 5.3 × 10(5) s(-1), at 37 °C) and glucose (KM = 6 μM; kcat = 2.4 × 10(5) s(-1)). The short temporal resolution allows continuous monitoring of fast cellular events such as kinetics inhibition with butyrate. Furthermore, we detected for the first time riboflavin reduction by another potential probiotic, Butyricicoccus pullicaecorum. The ability of the RDE for fast, accurate, simple and continuous measurements makes it an ad hoc tool for assessing bioprocesses at high resolution.

  3. The steady-state kinetics of the NADH-dependent nitrite reductase from Escherichia coli K 12. Nitrite and hydroxylamine reduction.

    OpenAIRE

    Jackson, R H; Cole, J A; Cornish-Bowden, A

    1981-01-01

    The reduction of both NO2- and hydroxylamine by the NADH-dependent nitrite reductase of Escherichia coli K 12 (EC 1.6.6.4) appears to follow Michaelis-Menten kinetics over a wide range of NADH concentrations. Substrate inhibition can, however, be detected at low concentrations of the product NAD+. In addition, NAD+ displays mixed product inhibition with respect to NADH and mixed or uncompetitive inhibition with respect to hydroxylamine. These inhibition characteristics are consistent with a m...

  4. Estimating Reaction Rate Coefficients Within a Travel-Time Modeling Framework

    Energy Technology Data Exchange (ETDEWEB)

    Gong, R [Georgia Institute of Technology; Lu, C [Georgia Institute of Technology; Luo, Jian [Georgia Institute of Technology; Wu, Wei-min [Stanford University; Cheng, H. [Stanford University; Criddle, Craig [Stanford University; Kitanidis, Peter K. [Stanford University; Gu, Baohua [ORNL; Watson, David B [ORNL; Jardine, Philip M [ORNL; Brooks, Scott C [ORNL

    2011-03-01

    A generalized, efficient, and practical approach based on the travel-time modeling framework is developed to estimate in situ reaction rate coefficients for groundwater remediation in heterogeneous aquifers. The required information for this approach can be obtained by conducting tracer tests with injection of a mixture of conservative and reactive tracers and measurements of both breakthrough curves (BTCs). The conservative BTC is used to infer the travel-time distribution from the injection point to the observation point. For advection-dominant reactive transport with well-mixed reactive species and a constant travel-time distribution, the reactive BTC is obtained by integrating the solutions to advective-reactive transport over the entire travel-time distribution, and then is used in optimization to determine the in situ reaction rate coefficients. By directly working on the conservative and reactive BTCs, this approach avoids costly aquifer characterization and improves the estimation for transport in heterogeneous aquifers which may not be sufficiently described by traditional mechanistic transport models with constant transport parameters. Simplified schemes are proposed for reactive transport with zero-, first-, nth-order, and Michaelis-Menten reactions. The proposed approach is validated by a reactive transport case in a two-dimensional synthetic heterogeneous aquifer and a field-scale bioremediation experiment conducted at Oak Ridge, Tennessee. The field application indicates that ethanol degradation for U(VI)-bioremediation is better approximated by zero-order reaction kinetics than first-order reaction kinetics.

  5. Role of conformational dynamics in kinetics of an enzymatic cycle in a nonequilibrium steady state

    Science.gov (United States)

    Min, Wei; Xie, X. Sunney; Bagchi, Biman

    2009-08-01

    Enzyme is a dynamic entity with diverse time scales, ranging from picoseconds to seconds or even longer. Here we develop a rate theory for enzyme catalysis that includes conformational dynamics as cycling on a two-dimensional (2D) reaction free energy surface involving an intrinsic reaction coordinate (X) and an enzyme conformational coordinate (Q). The validity of Michaelis-Menten (MM) equation, i.e., substrate concentration dependence of enzymatic velocity, is examined under a nonequilibrium steady state. Under certain conditions, the classic MM equation holds but with generalized microscopic interpretations of kinetic parameters. However, under other conditions, our rate theory predicts either positive (sigmoidal-like) or negative (biphasic-like) kinetic cooperativity due to the modified effective 2D reaction pathway on X-Q surface, which can explain non-MM dependence previously observed on many monomeric enzymes that involve slow or hysteretic conformational transitions. Furthermore, we find that a slow conformational relaxation during product release could retain the enzyme in a favorable configuration, such that enzymatic turnover is dynamically accelerated at high substrate concentrations. The effect of such conformation retainment in a nonequilibrium steady state is evaluated.

  6. Global Kinetic Analysis of Mammalian E3 Reveals pH-dependent NAD+/NADH Regulation, Physiological Kinetic Reversibility, and Catalytic Optimum*

    Science.gov (United States)

    Moxley, Michael A.; Beard, Daniel A.; Bazil, Jason N.

    2016-01-01

    Mammalian E3 is an essential mitochondrial enzyme responsible for catalyzing the terminal reaction in the oxidative catabolism of several metabolites. E3 is a key regulator of metabolic fuel selection as a component of the pyruvate dehydrogenase complex (PDHc). E3 regulates PDHc activity by altering the affinity of pyruvate dehydrogenase kinase, an inhibitor of the enzyme complex, through changes in reduction and acetylation state of lipoamide moieties set by the NAD+/NADH ratio. Thus, an accurate kinetic model of E3 is needed to predict overall mammalian PDHc activity. Here, we have combined numerous literature data sets and new equilibrium spectroscopic experiments with a multitude of independently collected forward and reverse steady-state kinetic assays using pig heart E3. The latter kinetic assays demonstrate a pH-dependent transition of NAD+ activation to inhibition, shown here, to our knowledge, for the first time in a single consistent data set. Experimental data were analyzed to yield a thermodynamically constrained four-redox-state model of E3 that simulates pH-dependent activation/inhibition and active site redox states for various conditions. The developed model was used to determine substrate/product conditions that give maximal E3 rates and show that, due to non-Michaelis-Menten behavior, the maximal flux is different compared with the classically defined kcat. PMID:26644471

  7. Enzymatic Synthesis of Furfuryl Alcohol Ester with Oleic Acid by Candida antarctica Lipase B and Its Kinetic Study

    Science.gov (United States)

    Sengupta, Avery; Dey, Tanmoy; Ghosh, Mahua; Ghosh, Jaydip; Ghosh, Santinath

    2012-08-01

    This study investigated the successful enzymatic production of furfuryl oleate and its detailed kinetic study by Michaelis-Menten model. Esterification of oleic acid and furfuryl alcohol by Candida antarctica lipase B (Novozym 435 preparation) in a solvent free system was studied in the present work at 1:1 molar ratio of furfuryl alcohol and oleic acid. About 99 % conversion (on the basis of oleic acid) has been achieved within 6 h at 5 % enzyme concentration. Ping-pong bi-bi mechanism (inhibition phenomenon taken into account) was applied to describe the ratios as a complex kinetic model. The kinetic parameters were determined using MATLAB language programme. The two initial rate constants KA and KB respectively were found out by different progress curves plotted with the help of MATLAB language programme. It was concluded from the results that furfuryl alcohol considerably inhibited the enzymatic reaction while oleic acid had negligible inhibitory effect. It was clearly seen that the initial rate was increased with the increase in the furfuryl alcohol concentration until 2 M/L after which there was a drop in the initial rate depicting the inhibitory effect of furfuryl alcohol. Surprisingly, it has been observed that addition of 0.1 mol of product activated the esterification reaction. Finally, the model was found to be statistically fitting well with the experimental data.

  8. Exploring between the extremes: conversion-dependent kinetics of phosphite-modified hydroformylation catalysis.

    Science.gov (United States)

    Kubis, Christoph; Selent, Detlef; Sawall, Mathias; Ludwig, Ralf; Neymeyr, Klaus; Baumann, Wolfgang; Franke, Robert; Börner, Armin

    2012-07-09

    The kinetics of the hydroformylation of 3,3-dimethyl-1-butene with a rhodium monophosphite catalyst has been studied in detail. Time-dependent concentration profiles covering the entire olefin conversion range were derived from in situ high-pressure FTIR spectroscopic data for both, pure organic components and catalytic intermediates. These profiles fit to Michaelis-Menten-type kinetics with competitive and uncompetitive side reactions involved. The characteristics found for the influence of the hydrogen concentration verify that the pre-equilibrium towards the catalyst substrate complex is not established. It has been proven experimentally that the hydrogenolysis of the intermediate acyl complex remains rate limiting even at high conversions when the rhodium hydride is the predominant resting state and the reaction is nearly of first order with respect to the olefin. Results from in situ FTIR and high-pressure (HP) NMR spectroscopy and from DFT calculations support the coordination of only one phosphite ligand in the dominating intermediates and a preferred axial position of the phosphite in the electronically saturated, trigonal bipyramidal (tbp)-structured acyl rhodium complex. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Reaction kinetics of polybutylene terephthalate polycondensation reaction

    NARCIS (Netherlands)

    Darda, P. J.; Hogendoorn, J. A.; Versteeg, G. F.; Souren, F.

    2005-01-01

    The kinetics of the forward polycondensation reaction of polybutylene terephthalate (PBT) has been investigated using thermogravimetric analysis (TGA). PBT - prepolymer with an initial degree of polymerization of 5.5 was used as starting material. The PBT prepolymer was prepared from dimethyl

  10. A kinetic model for the penicillin biosynthetic pathway in

    DEFF Research Database (Denmark)

    Nielsen, Jens; Jørgensen, Henrik

    1996-01-01

    A kinetic model for the first two steps in the penicillin biosynthetic pathway, i.e. the ACV synthetase (ACVS) and the isopenicillin N synthetase (IPNS) is proposed. The model is based on Michaelis-Menten type kinetics with non-competitive inhibition of the ACVS by ACV, and competitive inhibition...... of the IPNS by glutathione. The model predicted flux through the pathway corresponds well with the measured rate of penicillin biosynthesis. From the kinetic model the elasticity coefficients and the flux control coefficients are calculated throughout a fed-batch cultivation, and it is found...

  11. On enzyme kinetic parameters modification of gamma irradiation

    International Nuclear Information System (INIS)

    Ferdes, O.S.; Ferdes, M.; Turcu, G.R.

    1993-01-01

    To elucidate the molecular mechanisms of gamma-ray action on biomolecules there were investigated the modifications in activity and other kinetic parameters for some enzymes irradiated in pure dry state at relative high doses. There were considered bacterial and fungal α-amylases, glucoamylase and Mucor sp. protease irradiated by a 60 Co gamma-ray source in the dose range 1.0-30.0 kGy, at different dose-rates between 0.5-2.0 kGy/h, at room temperature. Considering the enzyme inactivation in this dose range, the dose-effect relationships have an expected form and depend on the irradiation conditions but not significantly on the dose rate. The catalytic properties of enzymes were modified by irradiation. By usual methods it is evidenced a direct correlation between the enzymatic activities, Michaelis-Menten constant, K m , reaction velocities, v, and the irradiation dose. These experimental findings can support a self-consistent theoretical approach on biophysical radiation action on biological active molecules like enzymes. At the same time, some enzyme behaviour to irradiation could be considered like a good biological indicator of radiation response. (Author) 4 Figs., 19 Refs

  12. Kinetic study of enzymatic hydrolysis of potato starch

    Directory of Open Access Journals (Sweden)

    Óscar Fernando Castellanos Domínguez

    2004-01-01

    Full Text Available This article describes the kinetic study of potato starch enzymatic hydrolysis using soluble enzymes (Novo Nordisk. Different assays divided into four groups were used: reaction time (with which it was possible to reduce the 48-72 hour duration reported in the literature to 16 hours with comparable productivity levels; selecting the set of enzymes to be used (different types were evaluated - BAN and Termamyl as alfa-amylases during dextrinisation stage, and AMG, Promozyme and Fungamyl for sacarification reaction- identifying those presenting the best performance during hydrolysis.Reaction conditions were optimised for the process's two stages (destrinisation and sacarification. Enzyme dose, calcium cofactor concentration, pH, temperature and agitation speed were studied for the first stage. Enzyme ratio, pH and agitation speed were studied for sacarification; the latter parameter reported values having no antecedents in the literature (60 rpm and 30 rpm for first and second reactions, respectively. Michaelis Menten kinetics were calculated once conditions had been optimised, varying substrate from 10-50% P/V, obtaining km and Vmax kinetic parameters for each reaction. A kinetic model was found according to local working conditions which was able to explain potato starch conversion to glucose syrup, achieving 96 dextrose equivalents by the end of the reaction, being well within the maximum range reported in the literature (94-98.Laboratory equipment was constructed prior to carrying out assays which was able to reproduce and improve the conditions reported in the literature, making it a useful, reliable tool for use in assays returning good results.

  13. Thermo-kinetics of lipase-catalyzed synthesis of 6-O-glucosyldecanoate.

    Science.gov (United States)

    Gumel, A M; Annuar, M S M; Heidelberg, T; Chisti, Y

    2011-10-01

    Lipase-catalyzed synthesis of 6-O-glucosyldecanoate from d-glucose and decanoic acid was performed in dimethyl sulfoxide (DMSO), a mixture of DMSO and tert-butanol and tert-butanol alone with a decreasing order of polarity. The highest conversion yield (> 65%) of decanoic acid was obtained in the blended solvent of intermediate polarity mainly because it could dissolve relatively large amounts of both the reactants. The reaction obeyed Michaelis-Menten type of kinetics. The affinity of the enzyme towards the limiting substrate (decanoic acid) was not affected by the polarity of the solvent, but increased significantly with temperature. The esterification reaction was endothermic with activation energy in the range of 60-67 kJ mol⁻¹. Based on the Gibbs energy values, in the solvent blend of DMSO and tert-butanol the position of the equilibrium was shifted more towards the products compared to the position in pure solvents. Monoester of glucose was the main product of the reaction. Copyright © 2011 Elsevier Ltd. All rights reserved.

  14. Kinetics of butyrate, acetate, and hydrogen metabolism in a thermophilic, anaerobic, butyrate-degrading triculture.

    Science.gov (United States)

    Ahring, B K; Westermann, P

    1987-02-01

    Kinetics of butyrate, acetate, and hydrogen metabolism were determined with butyrate-limited, chemostat-grown tricultures of a thermophilic butyrate-utilizing bacterium together with Methanobacterium thermoautotrophicum and the TAM organism, a thermophilic acetate-utilizing methanogenic rod. Kinetic parameters were determined from progress curves fitted to the integrated form of the Michaelis-Menten equation. The apparent half-saturation constants, K(m), for butyrate, acetate, and dissolved hydrogen were 76 muM, 0.4 mM, and 8.5 muM, respectively. Butyrate and hydrogen were metabolized to a concentration of less than 1 muM, whereas acetate uptake usually ceased at a concentration of 25 to 75 muM, indicating a threshold level for acetate uptake. No significant differences in K(m) values for butyrate degradation were found between chemostat- and batch-grown tricultures, although the maximum growth rate was somewhat higher in the batch cultures in which the medium was supplemented with yeast extract. Acetate utilization was found to be the rate-limiting reaction for complete degradation of butyrate to methane and carbon dioxide in continuous culture. Increasing the dilution rate resulted in a gradual accumulation of acetate. The results explain the low concentrations of butyrate and hydrogen normally found during anaerobic digestion and the observation that acetate is the first volatile fatty acid to accumulate upon a decrease in retention time or increase in organic loading of a digestor.

  15. Kinetics of glucose transport in rat muscle

    DEFF Research Database (Denmark)

    Ploug, Thorkil; Galbo, Henrik; Vinten, Jørgen

    1987-01-01

    The effects of insulin and prior muscle contractions, respectively, on 3-O-methylglucose (3-O-MG) transport in skeletal muscle were studied in the perfused rat hindquarter. Initial rates of entry of 3-O-MG in red gastrocnemius, soleus, and white gastrocnemius muscles as a function of perfusate 3-O-MG...... concentration exhibited Michaelis-Menten kinetics. Uptake by simple diffusion could not be detected. The maximum 3-O-MG transport velocity (Vmax) was increased more by maximum isometric contractions (10- to 40-fold, depending on fiber type) than by insulin (20,000 microU/ml; 3- to 20-fold) in both red and white...

  16. The single-process biochemical reaction of Rubisco: a unified theory and model with the effects of irradiance, CO₂ and rate-limiting step on the kinetics of C₃ and C₄ photosynthesis from gas exchange.

    Science.gov (United States)

    Farazdaghi, Hadi

    2011-02-01

    Photosynthesis is the origin of oxygenic life on the planet, and its models are the core of all models of plant biology, agriculture, environmental quality and global climate change. A theory is presented here, based on single process biochemical reactions of Rubisco, recognizing that: In the light, Rubisco activase helps separate Rubisco from the stored ribulose-1,5-bisphosphate (RuBP), activates Rubisco with carbamylation and addition of Mg²(+), and then produces two products, in two steps: (Step 1) Reaction of Rubisco with RuBP produces a Rubisco-enediol complex, which is the carboxylase-oxygenase enzyme (Enco) and (Step 2) Enco captures CO₂ and/or O₂ and produces intermediate products leading to production and release of 3-phosphoglycerate (PGA) and Rubisco. PGA interactively controls (1) the carboxylation-oxygenation, (2) electron transport, and (3) triosephosphate pathway of the Calvin-Benson cycle that leads to the release of glucose and regeneration of RuBP. Initially, the total enzyme participates in the two steps of the reaction transitionally and its rate follows Michaelis-Menten kinetics. But, for a continuous steady state, Rubisco must be divided into two concurrently active segments for the two steps. This causes a deviation of the steady state from the transitional rate. Kinetic models are developed that integrate the transitional and the steady state reactions. They are tested and successfully validated with verifiable experimental data. The single-process theory is compared to the widely used two-process theory of Farquhar et al. (1980. Planta 149, 78-90), which assumes that the carboxylation rate is either Rubisco-limited at low CO₂ levels such as CO₂ compensation point, or RuBP regeneration-limited at high CO₂. Since the photosynthesis rate cannot increase beyond the two-process theory's Rubisco limit at the CO₂ compensation point, net photosynthesis cannot increase above zero in daylight, and since there is always respiration at

  17. Relationship among reaction rate, release rate and efficiency of nanomachine-based targeted drug delivery.

    Science.gov (United States)

    Zhao, Qingying; Li, Min; Luo, Jun

    2017-12-04

    In nanomachine applications towards targeted drug delivery, drug molecules released by nanomachines propagate and chemically react with tumor cells in aqueous environment. If the nanomachines release drug molecules faster than the tumor cells react, it will result in loss and waste of drug molecules. It is a potential issue associated with the relationship among reaction rate, release rate and efficiency. This paper aims to investigate the relationship among reaction rate, release rate and efficiency based on two drug reception models. We expect to pave a way for designing a control method of drug release. We adopted two analytical methods that one is drug reception process based on collision with tumors and another is based on Michaelis Menten enzymatic kinetics. To evaluate the analytical formulations, we used the well-known simulation framework N3Sim to establish simulations. The analytical results of the relationship among reaction rate, release rate and efficiency is obtained, which match well with the numerical simulation results in a 3-D environment. Based upon two drug reception models, the results of this paper would be beneficial for designing a control method of nanomahine-based drug release.

  18. 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.

  19. Combustion kinetics and reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Klemm, R.B.; Sutherland, J.W. [Brookhaven National Laboratory, Upton, NY (United States)

    1993-12-01

    This project is focused on the fundamental chemistry of combustion. The overall objectives are to determine rate constants for elementary reactions and to elucidate the pathways of multichannel reactions. A multitechnique approach that features three independent experiments provides unique capabilities in performing reliable kinetic measurements over an exceptionally wide range in temperature, 300 to 2500 K. Recent kinetic work has focused on experimental studies and theoretical calculations of the methane dissociation system (CH{sub 4} + Ar {yields} CH{sub 3} + H + Ar and H + CH{sub 4} {yields} CH{sub 3} + H{sub 2}). Additionally, a discharge flow-photoionization mass spectrometer (DF-PIMS) experiment is used to determine branching fractions for multichannel reactions and to measure ionization thresholds of free radicals. Thus, these photoionization experiments generate data that are relevant to both reaction pathways studies (reaction dynamics) and fundamental thermochemical research. Two distinct advantages of performing PIMS with high intensity, tunable vacuum ultraviolet light at the National Synchrotron Light Source are high detection sensitivity and exceptional selectivity in monitoring radical species.

  20. A graphical user interface for a method to infer kinetics and network architecture (MIKANA).

    Science.gov (United States)

    Mourão, Márcio A; Srividhya, Jeyaraman; McSharry, Patrick E; Crampin, Edmund J; Schnell, Santiago

    2011-01-01

    One of the main challenges in the biomedical sciences is the determination of reaction mechanisms that constitute a biochemical pathway. During the last decades, advances have been made in building complex diagrams showing the static interactions of proteins. The challenge for systems biologists is to build realistic models of the dynamical behavior of reactants, intermediates and products. For this purpose, several methods have been recently proposed to deduce the reaction mechanisms or to estimate the kinetic parameters of the elementary reactions that constitute the pathway. One such method is MIKANA: Method to Infer Kinetics And Network Architecture. MIKANA is a computational method to infer both reaction mechanisms and estimate the kinetic parameters of biochemical pathways from time course data. To make it available to the scientific community, we developed a Graphical User Interface (GUI) for MIKANA. Among other features, the GUI validates and processes an input time course data, displays the inferred reactions, generates the differential equations for the chemical species in the pathway and plots the prediction curves on top of the input time course data. We also added a new feature to MIKANA that allows the user to exclude a priori known reactions from the inferred mechanism. This addition improves the performance of the method. In this article, we illustrate the GUI for MIKANA with three examples: an irreversible Michaelis-Menten reaction mechanism; the interaction map of chemical species of the muscle glycolytic pathway; and the glycolytic pathway of Lactococcus lactis. We also describe the code and methods in sufficient detail to allow researchers to further develop the code or reproduce the experiments described. The code for MIKANA is open source, free for academic and non-academic use and is available for download (Information S1).

  1. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel

    2014-01-01

    This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

  2. Kinetics of the removal of mono-chlorobenzene vapour from waste gases using a trickle bed air biofilter.

    Science.gov (United States)

    Mathur, Anil K; Sundaramurthy, J; Balomajumder, C

    2006-10-11

    The performance of a trickle bed air biofilter (TBAB) in the removal of mono-chlorobenzene (MCB) was evaluated in concentrations varying from 0.133 to 7.187 g m(-3) and at empty bed residence time (EBRT) varying from 37.7 to 188.52 s. More than 90% removal efficiency in the trickle bed air biofilter was achieved for the inlet MCB concentration up to 1.069 g m(-3) and EBRT less than 94.26 s. The trickle bed air biofilter was constructed with coal packing material, inoculated with a mixed consortium of activated sludge obtained from sewage treatment plant. The continuous performance of the removal of MCB in the trickle bed air biofilter was monitored for various gas concentrations, gas flow rates, and empty bed residence time. The experiment was conducted for a period of 75 days. The trickle bed air biofilter degrading MCB with an average elimination capacity of 80 g m(-3) h(-1) was obtained. The effect of starvation was also studied. After starvation period of 8 days, the degradation was low but recovered within a short period of time. Using macrokinetic determination method, the Michaelis-Menten kinetic constant K(m) and maximum reaction rate, r(max) evaluated as 0.121 g m(-3) s(-1) and 7.45 g m(-3), respectively.

  3. Sub-minute kinetics of human red cell fumarase: 1 H spin-echo NMR spectroscopy and 13 C rapid-dissolution dynamic nuclear polarization.

    Science.gov (United States)

    Shishmarev, Dmitry; Wright, Alan J; Rodrigues, Tiago B; Pileio, Giuseppe; Stevanato, Gabriele; Brindle, Kevin M; Kuchel, Philip W

    2018-03-01

    Fumarate is an important probe of metabolism in hyperpolarized magnetic resonance imaging and spectroscopy. It is used to detect the release of fumarase in cancer tissues, which is associated with necrosis and drug treatment. Nevertheless, there are limited reports describing the detailed kinetic studies of this enzyme in various cells and tissues. Thus, we aimed to evaluate the sub-minute kinetics of human red blood cell fumarase using nuclear magnetic resonance (NMR) spectroscopy, and to provide a quantitative description of the enzyme that is relevant to the use of fumarate as a probe of cell rupture. The fumarase reaction was studied using time courses of 1 H spin-echo and 13 C-NMR spectra. 1 H-NMR experiments showed that the fumarase reaction in hemolysates is sufficiently rapid to make its kinetics amenable to study in a period of approximately 3 min, a timescale characteristic of hyperpolarized 13 C-NMR spectroscopy. The rapid-dissolution dynamic nuclear polarization (RD-DNP) technique was used to hyperpolarize [1,4- 13 C]fumarate, which was injected into concentrated hemolysates. The kinetic data were analyzed using recently developed FmR α analysis and modeling of the enzymatic reaction using Michaelis-Menten equations. In RD-DNP experiments, the decline in the 13 C-NMR signal from fumarate, and the concurrent rise and fall of that from malate, were captured with high spectral resolution and signal-to-noise ratio, which allowed the robust quantification of fumarase kinetics. The kinetic parameters obtained indicate the potential contribution of hemolysis to the overall rate of the fumarase reaction when 13 C-NMR RD-DNP is used to detect necrosis in animal models of implanted tumors. The analytical procedures developed will be applicable to studies of other rapid enzymatic reactions using conventional and hyperpolarized substrate NMR spectroscopy. Copyright © 2018 John Wiley & Sons, Ltd.

  4. Modeling uptake kinetics of cadmium by field-grown lettuce

    Energy Technology Data Exchange (ETDEWEB)

    Chen Weiping [Department of Environmental Sciences, University of California, 900 University Avenue, Riverside, CA 92521 (United States)], E-mail: chenweip@yahoo.com.cn; Li Lianqing [Institute of Resources, Ecosystem and Environment of Agriculture, Nanjing Agricultural University, Nanjing 210095 (China); Chang, Andrew C.; Wu Laosheng [Department of Environmental Sciences, University of California, 900 University Avenue, Riverside, CA 92521 (United States); Kwon, Soon-Ik [Agricultural Environmental and Ecology Division, National Institute of Agricultural Science and Technology, Suwon 441-707 (Korea, Republic of); Bottoms, Rick [Desert Research and Extension Center, 1004 East Holton Road, El Centro, CA 92243 (United States)

    2008-03-15

    Cadmium uptake by field grown Romaine lettuce treated with P-fertilizers of different Cd levels was investigated over an entire growing season. Results indicated that the rate of Cd uptake at a given time of the season can be satisfactorily described by the Michaelis-Menten kinetics, that is, plant uptake increases as the Cd concentration in soil solution increases, and it gradually approaches a saturation level. However, the rate constant of the Michaelis-Menten kinetics changes over the growing season. Under a given soil Cd level, the cadmium content in plant tissue decreases exponentially with time. To account for the dynamic nature of Cd uptake, a kinetic model integrating the time factor was developed to simulate Cd plant uptake over the growing season: C{sub Plant} = C{sub Solution} . PUF{sub max} . exp[-b . t], where C{sub Plant} and C{sub Solution} refer to the Cd content in plant tissue and soil solution, respectively, PUF{sub max} and b are kinetic constants. - A kinetic model was developed to evaluate the uptake of Cd under field conditions.

  5. Modeling uptake kinetics of cadmium by field-grown lettuce

    International Nuclear Information System (INIS)

    Chen Weiping; Li Lianqing; Chang, Andrew C.; Wu Laosheng; Kwon, Soon-Ik; Bottoms, Rick

    2008-01-01

    Cadmium uptake by field grown Romaine lettuce treated with P-fertilizers of different Cd levels was investigated over an entire growing season. Results indicated that the rate of Cd uptake at a given time of the season can be satisfactorily described by the Michaelis-Menten kinetics, that is, plant uptake increases as the Cd concentration in soil solution increases, and it gradually approaches a saturation level. However, the rate constant of the Michaelis-Menten kinetics changes over the growing season. Under a given soil Cd level, the cadmium content in plant tissue decreases exponentially with time. To account for the dynamic nature of Cd uptake, a kinetic model integrating the time factor was developed to simulate Cd plant uptake over the growing season: C Plant = C Solution . PUF max . exp[-b . t], where C Plant and C Solution refer to the Cd content in plant tissue and soil solution, respectively, PUF max and b are kinetic constants. - A kinetic model was developed to evaluate the uptake of Cd under field conditions

  6. Chemistry and reaction kinetics of biowaste torrefaction

    NARCIS (Netherlands)

    Stelt, van der M.J.C.

    2011-01-01

    This thesis addresses the question of how the chemistry and reaction kinetics of torrefaction are influenced by reaction conditions and the effects occuring during the reaction. This research question can be specified by questions such as, what controls their kinetics during torrefaction and what

  7. A KDE-Based Random Walk Method for Modeling Reactive Transport With Complex Kinetics in Porous Media

    Science.gov (United States)

    Sole-Mari, Guillem; Fernà ndez-Garcia, Daniel; Rodríguez-Escales, Paula; Sanchez-Vila, Xavier

    2017-11-01

    In recent years, a large body of the literature has been devoted to study reactive transport of solutes in porous media based on pure Lagrangian formulations. Such approaches have also been extended to accommodate second-order bimolecular reactions, in which the reaction rate is proportional to the concentrations of the reactants. Rather, in some cases, chemical reactions involving two reactants follow more complicated rate laws. Some examples are (1) reaction rate laws written in terms of powers of concentrations, (2) redox reactions incorporating a limiting term (e.g., Michaelis-Menten), or (3) any reaction where the activity coefficients vary with the concentration of the reactants, just to name a few. We provide a methodology to account for complex kinetic bimolecular reactions in a fully Lagrangian framework where each particle represents a fraction of the total mass of a specific solute. The method, built as an extension to the second-order case, is based on the concept of optimal Kernel Density Estimator, which allows the concentrations to be written in terms of particle locations, hence transferring the concept of reaction rate to that of particle location distribution. By doing so, we can update the probability of particles reacting without the need to fully reconstruct the concentration maps. The performance and convergence of the method is tested for several illustrative examples that simulate the Advection-Dispersion-Reaction Equation in a 1-D homogeneous column. Finally, a 2-D application example is presented evaluating the need of fully describing non-bilinear chemical kinetics in a randomly heterogeneous porous medium.

  8. Kinetic study of enzymatic hydrolysis of acid-pretreated coconut coir

    Science.gov (United States)

    Fatmawati, Akbarningrum; Agustriyanto, Rudy

    2015-12-01

    Biomass waste utilization for biofuel production such as bioethanol, has become more prominent currently. Coconut coir is one of lignocellulosic food wastes, which is abundant in Indonesia. Bioethanol production from such materials consists of more than one step. Pretreatment and enzymatic hydrolysis is crucial steps to produce sugar which can then be fermented into bioethanol. In this research, ground coconut coir was pretreated using dilute sulfuric acid at 121°C. This pretreatment had increased the cellulose content and decreased the lignin content of coconut coir. The pretreated coconut coir was hydrolyzed using a mix of two commercial cellulase enzymes at pH of 4.8 and temperature of 50°C. The enzymatic hydrolysis was conducted at several initial coconut coir slurry concentrations (0.1-2 g/100 mL) and reaction times (2-72 hours). The reducing sugar concentration profiles had been produced and can be used to obtain reaction rates. The highest reducing sugar concentration obtained was 1,152.567 mg/L, which was produced at initial slurry concentration of 2 g/100 mL and 72 hours reaction time. In this paper, the reducing sugar concentrations were empirically modeled as a function of reaction time using power equations. Michaelis-Menten kinetic model for enzymatic hydrolysis reaction is adopted. The kinetic parameters of that model for sulfuric acid-pretreated coconut coir enzymatic hydrolysis had been obtained which are Vm of 3.587×104 mg/L.h, and KM of 130.6 mg/L.

  9. The kinetics of phagocytosis of 198Au colloids ''in vitro''

    International Nuclear Information System (INIS)

    Astorri, N.L.; Bergoc, R.M.; Bianchin, A.M.; Caro, R.A.; Ihlo, J.E.; Rivera, E.S.

    1982-01-01

    The kinetics of the phagocytosis of 198-Au colloids by macrophages ''in vitro'' was studied by incubating during 5 hours phagocytic cells from the liver and the spleen of Wistar rats with colloidal radiogold particles, in the presence of an adequate culture medium (TC-199 with 10 per cent of Bovine Fetal Serum). In each experiment, the number of colloidal gold particles offered to each phatocytic cell, (Au) 0 and the mean rate of phagocytosis v, were calculated. The latter value was determined by measuring the radioactivity incorporated into the phagocytic cells during the incubation; it was expressed as the number of phagocytized colloidal gold particles per cell per minute. The values of log v = f [log (Au) 0 ] were plotted. The Lineweaver-Burk analysis of the results demonstrates that the kinetics of the phagocytosis of colloidal radiogold particles ''in vitro'' follows a model similar to Michaelis-Menten equations for enzyme reactions. The values of the substratum constant Ks and maximun velocity Vm were obtained by the regression analysis of the 1/v vs. 1/(Au) 0 graph. Vm was equal to 9.44 x 10 and 1.63 x 10 phagocytized colloidal gold particles per cell per minute for liver and spleen macrophages, respectively. Ks was equal to 6.01 x 10 9 and 8.02 x 10 8 colloidal gold particles per cell for liver and spleen macrophages, respectively. The significance of these differences is discussed and attributed mainly to a change of the specific engulfment rate constant. (author) [es

  10. Diffusion-controlled interface kinetics-inclusive system-theoretic propagation models for molecular communication systems

    Science.gov (United States)

    Chude-Okonkwo, Uche A. K.; Malekian, Reza; Maharaj, B. T.

    2015-12-01

    Inspired by biological systems, molecular communication has been proposed as a new communication paradigm that uses biochemical signals to transfer information from one nano device to another over a short distance. The biochemical nature of the information transfer process implies that for molecular communication purposes, the development of molecular channel models should take into consideration diffusion phenomenon as well as the physical/biochemical kinetic possibilities of the process. The physical and biochemical kinetics arise at the interfaces between the diffusion channel and the transmitter/receiver units. These interfaces are herein termed molecular antennas. In this paper, we present the deterministic propagation model of the molecular communication between an immobilized nanotransmitter and nanoreceiver, where the emission and reception kinetics are taken into consideration. Specifically, we derived closed-form system-theoretic models and expressions for configurations that represent different communication systems based on the type of molecular antennas used. The antennas considered are the nanopores at the transmitter and the surface receptor proteins/enzymes at the receiver. The developed models are simulated to show the influence of parameters such as the receiver radius, surface receptor protein/enzyme concentration, and various reaction rate constants. Results show that the effective receiver surface area and the rate constants are important to the system's output performance. Assuming high rate of catalysis, the analysis of the frequency behavior of the developed propagation channels in the form of transfer functions shows significant difference introduce by the inclusion of the molecular antennas into the diffusion-only model. It is also shown that for t > > 0 and with the information molecules' concentration greater than the Michaelis-Menten kinetic constant of the systems, the inclusion of surface receptors proteins and enzymes in the models

  11. Hydrodynamic chronoamperometry for probing kinetics of anaerobic microbial metabolism - case study of Faecalibacterium prausnitzii

    Science.gov (United States)

    Prévoteau, Antonin; Geirnaert, Annelies; Arends, Jan B. A.; Lannebère, Sylvain; van de Wiele, Tom; Rabaey, Korneel

    2015-07-01

    Monitoring in vitro the metabolic activity of microorganisms aids bioprocesses and enables better understanding of microbial metabolism. Redox mediators can be used for this purpose via different electrochemical techniques that are either complex or only provide non-continuous data. Hydrodynamic chronoamperometry using a rotating disc electrode (RDE) can alleviate these issues but was seldom used and is poorly characterized. The kinetics of Faecalibacterium prausnitzii A2-165, a beneficial gut microbe, were determined using a RDE with riboflavin as redox probe. This butyrate producer anaerobically ferments glucose and reduces riboflavin whose continuous monitoring on a RDE provided highly accurate kinetic measurements of its metabolism, even at low cell densities. The metabolic reaction rate increased linearly over a broad range of cell concentrations (9 × 104 to 5 × 107 cells.mL-1). Apparent Michaelis-Menten kinetics was observed with respect to riboflavin (KM = 6 μM kcat = 5.3×105 s-1, at 37 °C) and glucose (KM = 6 μM kcat = 2.4 × 105 s-1). The short temporal resolution allows continuous monitoring of fast cellular events such as kinetics inhibition with butyrate. Furthermore, we detected for the first time riboflavin reduction by another potential probiotic, Butyricicoccus pullicaecorum. The ability of the RDE for fast, accurate, simple and continuous measurements makes it an ad hoc tool for assessing bioprocesses at high resolution.

  12. Preventing Corrosion by Controlling Cathodic Reaction Kinetics

    Science.gov (United States)

    2016-03-25

    3. DATES COVERED (From - To) 09/23/15 - 04/22/16 4. TITLE AND SUBTITLE Sa. CONTRACT NUMBER Preventing Corrosion by Controlling Cathodic Reaction...Preventing corrosion by controlling cathodic reaction kinetics Progress Report for Period: 1 SEP 2015-31 MAR 2016 John Keith Department of...25 March 2016 Preventing corrosion by controlling cathodic reaction kinetics Annual Summary Report: FY16 PI: John Keith, 412-624-7016,jakeith

  13. A kinetic model and simulation of starch saccharification and simultaneous ethanol fermentation by amyloglucosidase and Zymomonas mobilis

    Energy Technology Data Exchange (ETDEWEB)

    Lee, C G [Michigan Univ., Ann Arbor, MI (United States). Dept. of Chemical Engineering; Kim, C H; Rhee, S K [Korea Inst. of Science and Technology, Taejon (Korea, Republic of). Genetic Engineering Research Inst.

    1992-07-01

    A mathematical model is described for the simultaneous saccharification and ethanol fermentation (SSF) of sago starch using amyloglycosidase (AMG) and Zymomonas mobilis. By introducing the degree of polymerization (DP) of oligosaccharides produced from sago starch treated with {alpha}-amylase, a series of Michaelis-Menten equations was obtained. After determining kinetic parameters from the results of simple experiments and from the subsite mapping theory, this model was adapted to simulate the SSF process. The results of simulation for SSF are in good agreement with experimental results. (orig.).

  14. Practical steady-state enzyme kinetics.

    Science.gov (United States)

    Lorsch, Jon R

    2014-01-01

    Enzymes are key components of most biological processes. Characterization of enzymes is therefore frequently required during the study of biological systems. Steady-state kinetics provides a simple and rapid means of assessing the substrate specificity of an enzyme. When combined with site-directed mutagenesis (see Site-Directed Mutagenesis), it can be used to probe the roles of particular amino acids in the enzyme in substrate recognition and catalysis. Effects of interaction partners and posttranslational modifications can also be assessed using steady-state kinetics. This overview explains the general principles of steady-state enzyme kinetics experiments in a practical, rather than theoretical, way. Any biochemistry textbook will have a section on the theory of Michaelis-Menten kinetics, including derivations of the relevant equations. No specific enzymatic assay is described here, although a method for monitoring product formation or substrate consumption over time (an assay) is required to perform the experiments described. © 2014 Elsevier Inc. All rights reserved.

  15. Kinetic studies of elementary chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Durant, J.L. Jr. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    This program concerning kinetic studies of elementary chemical reactions is presently focussed on understanding reactions of NH{sub x} species. To reach this goal, the author is pursuing experimental studies of reaction rate coefficients and product branching fractions as well as using electronic structure calculations to calculate transition state properties and reaction rate calculations to relate these properties to predicted kinetic behavior. The synergy existing between the experimental and theoretical studies allow one to gain a deeper insight into more complex elementary reactions.

  16. Hydrogen electrode reaction: A complete kinetic description

    International Nuclear Information System (INIS)

    Quaino, P.M.; Gennero de Chialvo, M.R.; Chialvo, A.C.

    2007-01-01

    The kinetic description of the hydrogen electrode reaction (HER) in the whole range of overpotentials (-0.2 < η (V) < 0.40) is presented. The Volmer-Heyrovsky-Tafel mechanism was solved considering simultaneously the following items: (i) the diffusional contribution of the molecular hydrogen from and towards the electrode surface, (ii) the forward and backward reaction rates of each elementary step and (iii) a Frumkin type adsorption for the reaction intermediate. In order to verify the descriptive capability of the kinetic expressions derived, an experimental study of the HER was carried out on a rotating platinum disc electrode in acid solution. From the correlation of these results the elementary kinetic parameters were evaluated and several aspects related to the kinetic mechanism were discussed. Finally, the use of these kinetic expressions to interpret results obtained on microelectrodes is also analysed

  17. Chemical kinetics and reaction dynamics

    CERN Document Server

    Houston, Paul L

    2006-01-01

    This text teaches the principles underlying modern chemical kinetics in a clear, direct fashion, using several examples to enhance basic understanding. It features solutions to selected problems, with separate sections and appendices that cover more technical applications.Each chapter is self-contained and features an introduction that identifies its basic goals, their significance, and a general plan for their achievement. This text's important aims are to demonstrate that the basic kinetic principles are essential to the solution of modern chemical problems, and to show how the underlying qu

  18. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    ... behaves as an effective catalyst towards oxidation of 3,5-ditertiarybutyl catechol (3,5-DTBC) in acetonitrile to its corresponding quinone derivative in air. The reaction follows first-order reaction kinetics with rate constant 4.28 × 10−5 min-1. The reaction follows Michaelis-Menten enzymatic kinetics with a turnover number of ...

  19. Communication: Limitations of the stochastic quasi-steady-state approximation in open biochemical reaction networks

    Science.gov (United States)

    Thomas, Philipp; Straube, Arthur V.; Grima, Ramon

    2011-11-01

    It is commonly believed that, whenever timescale separation holds, the predictions of reduced chemical master equations obtained using the stochastic quasi-steady-state approximation are in very good agreement with the predictions of the full master equations. We use the linear noise approximation to obtain a simple formula for the relative error between the predictions of the two master equations for the Michaelis-Menten reaction with substrate input. The reduced approach is predicted to overestimate the variance of the substrate concentration fluctuations by as much as 30%. The theoretical results are validated by stochastic simulations using experimental parameter values for enzymes involved in proteolysis, gluconeogenesis, and fermentation.

  20. Effects of multi-frequency power ultrasound on the enzymolysis of corn gluten meal: Kinetics and thermodynamics study.

    Science.gov (United States)

    Jin, Jian; Ma, Haile; Qu, Wenjuan; Wang, Kai; Zhou, Cunshan; He, Ronghai; Luo, Lin; Owusu, John

    2015-11-01

    The effects of multi-frequency power ultrasound (MPU) pretreatment on the kinetics and thermodynamics of corn gluten meal (CGM) were investigated in this research. The apparent constant (KM), apparent break-down rate constant (kA), reaction rate constants (k), energy of activation (Ea), enthalpy of activation (ΔH), entropy of activation (ΔS) and Gibbs free energy of activation (ΔG) were determined by means of the Michaelis-Menten equation, first-order kinetics model, Arrhenius equation and transition state theory, respectively. The results showed that MPU pretreatment can accelerate the enzymolysis of CGM under different enzymolysis conditions, viz. substrate concentration, enzyme concentration, pH, and temperature. Kinetics analysis revealed that MPU pretreatment decreased the KM value by 26.1% and increased the kA value by 7.3%, indicating ultrasound pretreatment increased the affinity between enzyme and substrate. In addition, the values of k for ultrasound pretreatment were increased by 84.8%, 41.9%, 28.9%, and 18.8% at the temperature of 293, 303, 313 and 323 K, respectively. For the thermodynamic parameters, ultrasound decreased Ea, ΔH and ΔS by 23.0%, 24.3% and 25.3%, respectively, but ultrasound had little change in ΔG value in the temperature range of 293-323 K. In conclusion, MPU pretreatment could remarkably enhance the enzymolysis of CGM, and this method can be applied to protein proteolysis industry to produce peptides. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Bilirubin glucuronidation revisited: proper assay conditions to estimate enzyme kinetics with recombinant UGT1A1.

    Science.gov (United States)

    Zhou, Jin; Tracy, Timothy S; Remmel, Rory P

    2010-11-01

    Bilirubin, an end product of heme catabolism, is primarily eliminated via glucuronic acid conjugation by UGT1A1. Impaired bilirubin conjugation, caused by inhibition of UGT1A1, can result in clinical consequences, including jaundice and kernicterus. Thus, evaluation of the ability of new drug candidates to inhibit UGT1A1-catalyzed bilirubin glucuronidation in vitro has become common practice. However, the instability of bilirubin and its glucuronides presents substantial technical challenges to conduct in vitro bilirubin glucuronidation assays. Furthermore, because bilirubin can be diglucuronidated through a sequential reaction, establishment of initial rate conditions can be problematic. To address these issues, a robust high-performance liquid chromatography assay to measure both bilirubin mono- and diglucuronide conjugates was developed, and the incubation conditions for bilirubin glucuronidation by human embryonic kidney 293-expressed UGT1A1 were carefully characterized. Our results indicated that bilirubin glucuronidation should be assessed at very low protein concentrations (0.05 mg/ml protein) and over a short incubation time (5 min) to assure initial rate conditions. Under these conditions, bilirubin total glucuronide formation exhibited a hyperbolic (Michaelis-Menten) kinetic profile with a K(m) of ∼0.2 μM. In addition, under these initial rate conditions, the relative proportions between the total monoglucuronide and the diglucuronide product were constant across the range of bilirubin concentration evaluated (0.05-2 μM), with the monoglucuronide being the predominant species (∼70%). In conclusion, establishment of appropriate incubation conditions (i.e., very low protein concentrations and short incubation times) is necessary to properly characterize the kinetics of bilirubin glucuronidation in a recombinant UGT1A1 system.

  2. An Integrated Circuit for Chip-Based Analysis of Enzyme Kinetics and Metabolite Quantification.

    Science.gov (United States)

    Cheah, Boon Chong; Macdonald, Alasdair Iain; Martin, Christopher; Streklas, Angelos J; Campbell, Gordon; Al-Rawhani, Mohammed A; Nemeth, Balazs; Grant, James P; Barrett, Michael P; Cumming, David R S

    2016-06-01

    We have created a novel chip-based diagnostic tools based upon quantification of metabolites using enzymes specific for their chemical conversion. Using this device we show for the first time that a solid-state circuit can be used to measure enzyme kinetics and calculate the Michaelis-Menten constant. Substrate concentration dependency of enzyme reaction rates is central to this aim. Ion-sensitive field effect transistors (ISFET) are excellent transducers for biosensing applications that are reliant upon enzyme assays, especially since they can be fabricated using mainstream microelectronics technology to ensure low unit cost, mass-manufacture, scaling to make many sensors and straightforward miniaturisation for use in point-of-care devices. Here, we describe an integrated ISFET array comprising 2(16) sensors. The device was fabricated with a complementary metal oxide semiconductor (CMOS) process. Unlike traditional CMOS ISFET sensors that use the Si3N4 passivation of the foundry for ion detection, the device reported here was processed with a layer of Ta2O5 that increased the detection sensitivity to 45 mV/pH unit at the sensor readout. The drift was reduced to 0.8 mV/hour with a linear pH response between pH 2-12. A high-speed instrumentation system capable of acquiring nearly 500 fps was developed to stream out the data. The device was then used to measure glucose concentration through the activity of hexokinase in the range of 0.05 mM-231 mM, encompassing glucose's physiological range in blood. Localised and temporal enzyme kinetics of hexokinase was studied in detail. These results present a roadmap towards a viable personal metabolome machine.

  3. Effect of pulsed electric field treatment on enzyme kinetics and thermostability of endogenous ascorbic acid oxidase in carrots (Daucus carota cv. Nantes).

    Science.gov (United States)

    Leong, Sze Ying; Oey, Indrawati

    2014-03-01

    The objective of this research was to study the enzyme kinetics and thermostability of endogenous ascorbic acid oxidase (AAO) in carrot purée (Daucus carota cv. Nantes) after being treated with pulsed electric field (PEF) processing. Various PEF treatments using electric field strength between 0.2 and 1.2kV/cm and pulsed electrical energy between 1 and 520kJ/kg were conducted. The enzyme kinetics and the kinetics of AAO thermal inactivation (55-70°C) were described using Michaelis-Menten model and first order reaction model, respectively. Overall, the estimated Vmax and KM values were situated in the same order of magnitude as the untreated carrot purée after being exposed to pulsed electrical energy between 1 and 400kJ/kg, but slightly changed at pulsed electrical energy above 500kJ/kg. However, AAO presented different thermostability depending on the electric field strength applied. After PEF treatment at the electric field strength between 0.2 and 0.5kV/cm, AAO became thermolabile (i.e. increase in inactivation rate (k value) at reference temperature) but the temperature dependence of k value (Ea value) for AAO inactivation in carrot purée decreased, indicating that the changes in k values were less temperature dependent. It is obvious that PEF treatment affects the temperature stability of endogenous AAO. The changes in enzyme kinetics and thermostability of AAO in carrot purée could be related to the resulting carrot purée composition, alteration in intracellular environment and the effective concentration of AAO released after being subjected to PEF treatment. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. The kinetics of denitrification in permeable sediments

    DEFF Research Database (Denmark)

    Evrard, Victor; Glud, Ronnie N.; Cook, Perran L. M.

    2013-01-01

    Permeable sediments comprise the majority of shelf sediments, yet the rates of denitrification remain highly uncertain in these environments. Computational models are increasingly being used to understand the dynamics of denitrification in permeable sediments, which are complex environments...... on sediments taken from six shallow coastal sites in Port Phillip Bay, Victoria, Australia. The results showed that denitrification commenced rapidly (within 30 min) after the onset of anoxia and the kinetics could be well described by Michaelis-Menten kinetics with half saturation constants (apparent K...... in cohesive sediments despite organic carbon contents one order of magnitude lower for the sediments studied here. The ratio of sediment O-2 consumption to V-max was in the range of 0.02-0.09, and was on average much lower than the theoretical ratio of 0.8. As a consequence, models implemented...

  5. Picolinic acid promoted oxidative decarboxylation of ...

    African Journals Online (AJOL)

    The kinetics and mechanism of picolinic acid promoted reaction of phenylsulfinylacetic acid (PSAA) with Cr(VI) was carried out in aqueous acetonitrile medium under pseudo first order conditions. The reaction follows Michaelis-Menten type of kinetics with respect to PSAA. The catalytic activity by picolinic acid can be ...

  6. A Critical View on In Vitro Analysis of P-glycoprotein (P-gp) Transport Kinetics.

    Science.gov (United States)

    Saaby, Lasse; Brodin, Birger

    2017-09-01

    Transport proteins expressed in the different barriers of the human body can have great implications on absorption, distribution, and excretion of drug compounds. Inhibition or saturation of a transporter can potentially alter these absorbtion, distribution, metabolism and elimination properties and thereby also the pharmacokinetic profile and bioavailability of drug compounds. P-glycoprotein (P-gp, ABCB1) is an efflux transporter which is present in most of the barriers of the body, including the small intestine, the blood-brain barrier, the liver, and the kidney. In all these tissues, P-gp may mediate efflux of drug compounds and may also be a potential site for drug-drug interactions. Consequently, there is a need to be able to predict the saturation and inhibition of P-gp and other transporters in vivo. For this purpose, Michaelis-Menten steady-state analysis has been applied to estimate kinetic parameters, such as K m and V max , for carrier-mediated transport, whereas half-maximal inhibitor concentration (IC 50 ) and the disassociation constant for an inhibitor/P-gp complex (K i ) have been determined to estimate P-gp inhibition. This review addresses in vitro methods commonly used to study P-gp transport kinetics and aims at providing a critical evaluation of the application of steady-state Michaelis-Menten analysis of kinetic parameters for substrate/P-gp interactions. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  7. Kinetic modeling of reactions in Foods

    NARCIS (Netherlands)

    Boekel, van M.A.J.S.

    2008-01-01

    The level of quality that food maintains as it travels down the production-to-consumption path is largely determined by the chemical, biochemical, physical, and microbiological changes that take place during its processing and storage. Kinetic Modeling of Reactions in Foods demonstrates how to

  8. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Kinetics and mechanism of oxidation of formic and oxalic acids by quinolinium fluorochromate (QFC) have been studied in dimethylsulphoxide. The main product of oxidation is carbon dioxide. The reaction is first-order with respect to QFC. Michaelis-Menten type of kinetics were observed with respect to the reductants.

  9. Microbial respiration and kinetics of extracellular enzymes activities through rhizosphere and detritusphere at agricultural site

    Science.gov (United States)

    Löppmann, Sebastian; Blagodatskaya, Evgenia; Kuzyakov, Yakov

    2014-05-01

    Rhizosphere and detritusphere are soil microsites with very high resource availability for microorganisms affecting their biomass, composition and functions. In the rhizosphere low molecular compounds occur with root exudates and low available polymeric compounds, as belowground plant senescence. In detritusphere the substrate for decomposition is mainly a polymeric material of low availability. We hypothesized that microorganisms adapted to contrasting quality and availability of substrates in the rhizosphere and detritusphere are strongly different in affinity of hydrolytic enzymes responsible for decomposition of organic compounds. According to common ecological principles easily available substrates are quickly consumed by microorganisms with enzymes of low substrate affinity (i.e. r-strategists). The slow-growing K-strategists with enzymes of high substrate affinity are better adapted for growth on substrates of low availability. Estimation of affinity of enzyme systems to the substrate is based on Michaelis-Menten kinetics, reflecting the dependency of decomposition rates on substrate amount. As enzymes-mediated reactions are substrate-dependent, we further hypothesized that the largest differences in hydrolytic activity between the rhizosphere and detritusphere occur at substrate saturation and that these differences are smoothed with increasing limitation of substrate. Affected by substrate limitation, microbial species follow a certain adaptation strategy. To achieve different depth gradients of substrate availability 12 plots on an agricultural field were established in the north-west of Göttingen, Germany: 1) 4 plots planted with maize, reflecting lower substrate availability with depth; 2) 4 unplanted plots with maize litter input (0.8 kg m-2 dry maize residues), corresponding to detritusphere; 3) 4 bare fallow plots as control. Maize litter was grubbed homogenously into the soil at the first 5 cm to ensure comparable conditions for the herbivore and

  10. Kinetic Studies on Trichoderna Viride Cellulase

    International Nuclear Information System (INIS)

    Saw Aung; Oo Aung; Aung Myint

    2002-02-01

    Studies on cellulase enzyme (EC 3.2.1.4), which catalyzes the hydrolysis of. cellulose to yield glucose, were made. Cellulase from a fungus source, Trichoderma viride was cultivated on Czapek's agar medium and enzyme production broth medium was employed for parameter tests. The microscopic examination and cellulase hydrolysis test on subcultured fungi were applied to confirm the T. viride species. A calibration curve for standard glucose was plotted by using visible spectroscopy. Dinitrosalicylic acid was used as enzyme reaction inhibitor and the colour intensity was measured in a UV-visible spectrophotometer at a λ max of 570 nm. The parameters such as optimum pH, optimum temperature, effect of substrate concentration, effect, of enzyme concentration, enzyme unit (EU), reaction order (n), maximum velocity (V max ), Michaelis-Menten constant (K m ) using various substrates, viz., carboxy methylcellulose, cotton fibre and filter paper determined. (author)

  11. Reaction kinetics of bond rotations in graphene

    KAUST Repository

    Skowron, Stephen T.; Koroteev, Victor O.; Baldoni, Matteo; Lopatin, Sergei; Zurutuza, Amaia; Chuvilin, Andrey; Besley, Elena

    2016-01-01

    The formation and healing processes of the fundamental topological defect in graphitic materials, the Stone-Wales (SW) defect, are brought into a chemical context by considering the rotation of a carbon-carbon bond as chemical reaction. We investigate the rates and mechanisms of these SW transformations in graphene at the atomic scale using transmission electron microscopy. We develop a statistical atomic kinetics formalism, using direct observations obtained under different conditions to determine key kinetic parameters of the reactions. Based on the obtained statistics we quantify thermally and irradiation induced routes, identifying a thermal process of healing with an activation energy consistent with predicted adatom catalysed mechanisms. We discover exceptionally high rates for irradiation induced SW healing, incompatible with the previously assumed mechanism of direct knock-on damage and indicating the presence of an efficient nonadiabatic coupling healing mechanism involving beam induced electronic excitations of the SW defect.

  12. Reaction kinetics of bond rotations in graphene

    KAUST Repository

    Skowron, Stephen T.

    2016-04-12

    The formation and healing processes of the fundamental topological defect in graphitic materials, the Stone-Wales (SW) defect, are brought into a chemical context by considering the rotation of a carbon-carbon bond as chemical reaction. We investigate the rates and mechanisms of these SW transformations in graphene at the atomic scale using transmission electron microscopy. We develop a statistical atomic kinetics formalism, using direct observations obtained under different conditions to determine key kinetic parameters of the reactions. Based on the obtained statistics we quantify thermally and irradiation induced routes, identifying a thermal process of healing with an activation energy consistent with predicted adatom catalysed mechanisms. We discover exceptionally high rates for irradiation induced SW healing, incompatible with the previously assumed mechanism of direct knock-on damage and indicating the presence of an efficient nonadiabatic coupling healing mechanism involving beam induced electronic excitations of the SW defect.

  13. Kinetics of catalytic reactions solutions manual

    CERN Document Server

    Vannice, M Albert

    2005-01-01

    Including countless exercises and worked examples, this advanced reference work and textbook will be extremely useful for the work of many industrial scientists. It teaches readers to design kinetic experiments involving heterogeneous catalysts, to characterize these catalysts, to acquire rate data, to find heat and mass transfer limitations in these data, to select reaction models, to derive rate expressions based on these models, and to assess the consistency of these rate equations.

  14. Kinetic modelling of the Maillard reaction between proteins and sugars

    NARCIS (Netherlands)

    Brands, C.M.J.

    2002-01-01

    Keywords: Maillard reaction, sugar isomerisation, kinetics, multiresponse modelling, brown colour formation, lysine damage, mutagenicity, casein, monosaccharides, disaccharides, aldoses, ketoses

    The aim of this thesis was to determine the kinetics of the Maillard reaction between

  15. Spectroscopy and reaction kinetics of HCO

    International Nuclear Information System (INIS)

    Guo, Yili.

    1989-01-01

    The high-resolution infrared spectrum of the C-H stretching fundamental of HCO has been studied by means of infrared flash kinetic spectroscopy. HCO was generated by flash photolysis of acetaldehyde or formaldehyde using a 308 nm (XeCl) excimer laser. The transient absorption was probed with an infrared difference frequency laser system. The high resolution spectra obtained were assigned and fitted with rotational, spin-rotational, and centrifugal distortion constants. The ν 1 band origin is 2434.48 cm/sup /minus/1/. New ground state constants have been derived from a least-squares fit combining the ν 1 data with previous microwave and FIR LMR measurements. A new set of spectroscopic constants for the (1, 0, 0) state, the equilibrium rotational constants, and the orientation of the transition dipole moment are also reported. The kinetics and product branching ratios of the HCO + NO 2 reaction have been studied using visible and infrared laser flash kinetic spectroscopy. The rate constant for the disappearance of HCO radical at 296 K is (5.7 +- 0.9) /times/ 10/sup /minus/11/ cm 3 molec/sup /minus/1/ sec/sup /minus/1/, and it is independent of the pressure of SF 6 buffer gas up to 700 torr. Less than 10% of the reaction goes through the most exothermic product channel, HNO + CO 2 . The product channel, H + CO 2 + NO, is responsible for 52% of the reaction. HONO has been observed, though not quantitatively, as a reaction product corresponding to the HONO + CO channel. 51 refs., 21 figs., 8 tabs

  16. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    The oxidation of eleven amino acids by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid results in the formation of the corresponding carbonyl compounds and ammonia. The reaction is first order with respect to TBATB. Michaelis-Menten type kinetics is observed with some of the amino acids while others ...

  17. Kinetics of elementary atom and radical reactions

    International Nuclear Information System (INIS)

    Gordon, R.J.

    1990-06-01

    During the past three years we have been working on four problems in the general area of gas phase kinetics and energy transfer of small molecules. These are: (1) measurements of the fine structure populations of ground state oxygen atoms produced in photodissociation reactions; (2) quenching of the Rydberg B ( 1 Σ + ) state of CO; (3) vibrational relaxation of highly excited molecules; and (4) kinetics of hydrogen molecules. The first two topics, which involve transitions between different electronic states of the parent molecule, are a departure from our previous research interests. In the accompanying renewal proposal we discuss plans to pursue these new topics vigorously during the coming year. The third topic is a continuation of our long interest in the energy dependence of the rates laws governing vibrational-to-translational energy transfer of molecules having large initial amounts of vibrational excitation. The final topic is a continuation of our studies of the reaction of O( 3 P) + H 2 . In this work we measured the rate constant for the reaction O( 3 P) with deuterium and also analyzed spectroscopically different sources of vibrationally excited hydrogen for possible future work. We discuss each of these four studies in the following sections

  18. Reaction kinetic analysis of reactor surveillance data

    Energy Technology Data Exchange (ETDEWEB)

    Yoshiie, T., E-mail: yoshiie@rri.kyoto-u.ac.jp [Research Reactor Institute, Kyoto University, Kumatori-cho, Sennan-gun, Osaka-fu 590-0494 (Japan); Kinomura, A. [Research Reactor Institute, Kyoto University, Kumatori-cho, Sennan-gun, Osaka-fu 590-0494 (Japan); Nagai, Y. [The Oarai Center, Institute for Materials Research, Tohoku University, Oarai, Ibaraki 311-1313 (Japan)

    2017-02-15

    In the reactor pressure vessel surveillance data of a European-type pressurized water reactor (low-Cu steel), it was found that the concentration of matrix defects was very high, and a large number of precipitates existed. In this study, defect structure evolution obtained from surveillance data was simulated by reaction kinetic analysis using 15 rate equations. The saturation of precipitation and the growth of loops were simulated, but it was not possible to explain the increase in DBTT on the basis of the defect structures. The sub-grain boundary segregation of solutes was discussed for the origin of the DBTT increase.

  19. Atypical profiles and modulations of heme-enzymes catalyzed outcomes by low amounts of diverse additives suggest diffusible radicals' obligatory involvement in such redox reactions.

    Science.gov (United States)

    Manoj, Kelath Murali; Parashar, Abhinav; Venkatachalam, Avanthika; Goyal, Sahil; Satyalipsu; Singh, Preeti Gunjan; Gade, Sudeep K; Periyasami, Kalaiselvi; Jacob, Reeba Susan; Sardar, Debosmita; Singh, Shanikant; Kumar, Rajan; Gideon, Daniel A

    2016-06-01

    Peroxidations mediated by heme-enzymes have been traditionally studied under a single-site (heme distal pocket), non-sequential (ping-pong), two-substrates binding scheme of Michaelis-Menten paradigm. We had reported unusual modulations of peroxidase and P450 reaction outcomes and explained it invoking diffusible reactive species [Manoj, 2006; Manoj et al., 2010; Andrew et al., 2011, Parashar et al., 2014 & Venkatachalam et al., 2016]. A systematic investigation of specific product formation rates was undertaken to probe the hypothesis that involvement of diffusible reactive species could explain undefined substrate specificities and maverick modulations (sponsored by additives) of heme-enzymes. When the rate of specific product formation was studied as a function of reactants' concentration or environmental conditions, we noted marked deviations from normal profiles. We report that heme-enzyme mediated peroxidations of various substrates are inhibited (or activated) by sub-equivalent concentrations of diverse redox-active additives and this is owing to multiple redox equilibriums in the milieu. At low enzyme and peroxide concentrations, the enzyme is seen to recycle via a one-electron (oxidase) cycle, which does not require the substrate to access the heme centre. Schemes are provided that explain the complex mechanistic cycle, kinetics & stoichiometry. It is not obligatory for an inhibitor or substrate to interact with the heme centre for influencing overall catalysis. Roles of diffusible reactive species explain catalytic outcomes at low enzyme and reactant concentrations. The current work highlights the scope/importance of redox enzyme reactions that could occur "out of the active site" in biological or in situ systems. Copyright © 2016 Elsevier B.V. and Société française de biochimie et biologie Moléculaire (SFBBM). All rights reserved.

  20. Kinetics of the norepinephrine analog [76Br]-meta-bromobenzylguanidine in isolated working rat heart

    International Nuclear Information System (INIS)

    Raffel, David; Loc'h, Christian; Mardon, Karine; Maziere, Bernard; Syrota, Andre

    1998-01-01

    A related set of kinetic studies of the norepinephrine analog [ 76 Br]-meta-bromobenzylguanidine (MBBG) were performed with an isolated working rat heart preparation. A series of constant infusion studies over a wide range of MBBG concentrations allowed estimation of the Michaelis-Menten constants for transport by the neuronal norepinephrine transporter (uptake 1 ) and the extraneuronal uptake system (uptake 2 ). Pharmacological blocking studies with inhibitors of uptake 1 , uptake 2 and vesicular uptake were performed to delineate the relative importance of these norepinephrine handling mechanisms on the kinetics of MBBG in the rat heart. Bolus injection studies were done to assess the ability of compartmental modeling techniques to characterize the kinetics of MBBG. These studies demonstrate that MBBG shares many of the same uptake mechanisms as norepinephrine in the rat heart. PET imaging studies with MBBG would be useful for assessing sympathetic nerve status in the living human heart

  1. Reaction kinetics of dolomite rim growth

    Science.gov (United States)

    Helpa, V.; Rybacki, E.; Abart, R.; Morales, L. F. G.; Rhede, D.; Jeřábek, P.; Dresen, G.

    2014-04-01

    Reaction rims of dolomite (CaMg[CO3]2) were produced by solid-state reactions at the contacts of oriented calcite (CaCO3) and magnesite (MgCO3) single crystals at 400 MPa pressure, 750-850 °C temperature, and 3-146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO3 interface with length ranging from about 6 to 41 µm. At the same time, a 5-71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO3. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12-80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E a (CaO) = 192 ± 54 kJ/mol and E a (MgO) = 198 ± 44 kJ/mol, respectively.

  2. Thermal and single frequency counter-current ultrasound pretreatments of sodium caseinate: enzymolysis kinetics and thermodynamics, amino acids composition, molecular weight distribution and antioxidant peptides.

    Science.gov (United States)

    Abdualrahman, Mohammed Adam Y; Ma, Haile; Zhou, Cunshan; Yagoub, Abu ElGasim A; Hu, Jiali; Yang, Xue

    2016-12-01

    Due to the disadvantages of traditional enzymolysis, pretreatments are crucial to enhance protein enzymolysis. Enzymolysis kinetics and thermodynamics, amino acids composition, molecular weight distribution, fluorescence spectroscopy and antioxidant activity of thermal (HT) and single frequency counter-current ultrasound (SCFU) pretreated sodium caseinate (NaCas) were studied. Enzymolysis of untreated NaCas (control) improved significantly (P < 0.05) by SFCU and followed by HT. Values of the Michaelis-Menten constant (K M ) of SFCU and HT were 0.0212 and 0.0250, respectively. HT and SFCU increased (P < 0.05) the reaction rate constant (k) by 38.64 and 90.91%, respectively at 298 K. k values decreased with increasing temperature. The initial activation energy (46.39 kJ mol -1 ) reduced (P < 0.05) by HT (39.66 kJ mol -1 ) and further by SFCU (33.42 kJ mol -1 ). SFCU-pretreated NaCas hydrolysates had the highest contents of hydrophobic, aromatic, positively and negatively charged amino acids. Medium-sized peptides (5000-1000 Da) are higher in SFCU (78.11%) than HT and the control. SFCU induced molecular unfolding of NaCas proteins. Accordingly, SFCU-pretreated NaCas hydrolysate exhibited the highest scavenging activity on DPPH and hydroxyl radicals, reducing power, and iron chelating ability. SFCU pretreatment would be a useful tool for production of bioactive peptides from NaCas hydrolysate. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  3. Enzyme activity and kinetics in substrate-amended river sediments

    Energy Technology Data Exchange (ETDEWEB)

    Duddridge, J E; Wainwright, M

    1982-01-01

    In determining the effects of heavy metals in microbial activity and litter degradation in river sediments, one approach is to determine the effects of these pollutants on sediment enzyme activity and synthesis. Methods to assay amylase, cellulase and urease activity in diverse river sediments are reported. Enzyme activity was low in non-amended sediments, but increased markedly when the appropriate substrate was added, paralleling both athropogenic and natural amendment. Linear relationships between enzyme activity, length of incubation, sample size and substrate concentration were established. Sediment enzyme activity generally obeyed Michaelis-Menton kinetics, but of the three enzymes, urease gave least significant correlation coefficients when the data for substrate concentration versus activity was applied to the Eadie-Hofstee transformation of the Michaelis-Menten equation. K/sub m/ and V/sub max/ for amylase, cellulase and urease in sediments are reported. (JMT)

  4. Kinetic aspects of the Maillard reaction: a critical review

    NARCIS (Netherlands)

    Boekel, van M.A.J.S.

    2001-01-01

    The literature concerning the kinetics of the Maillard reaction was critically discussed according to the initial, intermediate and advanced stages, as this is the way the Maillard reaction is traditionally analysed. For each stage, a division is made between simple kinetics and complex kinetics.

  5. Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks

    Science.gov (United States)

    Cloonan, Carrie A.; Nichol, Carolyn A.; Hutchinson, John S.

    2011-01-01

    Chemical reaction kinetics and equilibrium are essential core concepts of chemistry but are challenging topics for many students, both at the high school and undergraduate university level. Visualization at the molecular level is valuable to aid understanding of reaction kinetics and equilibrium. This activity provides a discovery-based method to…

  6. NUMERICAL SOLUTION OF STEADY STATE DISPERSION FLOW MODEL FOR LACTOSE-LACTASE HYDROLYSIS WITH DIFFERENT KINETICS IN FIXED BED

    Directory of Open Access Journals (Sweden)

    OLAOSEBIKAN ABIDOYE OLAFADEHAN

    2010-06-01

    Full Text Available A detailed computational procedure for evaluating lactose hydrolysis with immobilized enzyme in a packed bed tubular reactor under dispersion flow conditions is presented. The dispersion flow model for lactose hydrolysis using different kinetics, taking cognizance of external mass transfer resistances, was solved by the method of orthogonal collocation. The reliability of model simulations was tested using experimental data from a laboratory packed bed column, where the -galactosidase of Kluyveromyces fragilis was immobilized on spherical chitosan beads. Comparison of the simulated results with experimental exit conversion shows that the dispersion flow model and using Michaelis-Menten kinetics with competitive product (galactose inhibition are appropriate to interpret the experimental results and simulate the process of lactose hydrolysis in a fixed bed.

  7. Nutrient Removal from Wastewater using Microalgae: A Kinetic Evaluation and Lipid Analysis.

    Science.gov (United States)

    2017-09-15

    The objective of this study was to examine the performance of mixed microalgal bioreactors in treating three differenttypes of wastewaters - kitchen wastewater (KWW), palm oil mill effluent (POME), and pharmaceutical wastewater (PWW) in semi-continuous mode and to analyze the lipid content in the harvested algal biomass. The reactors were monitored for total nitrogen and phosphate removal at eight solid retention times (SRTs) - 2, 4, 6, 8, 10, 12, 14, and 16 days. The nutrient uptake kinetic parameters were quantified using linearized Michaelis-Menten and Monod models at steady-state conditions. The nutrient removal efficiency and lipid production were found to be higher in KWW when compared with the other wastewaters. Saturated fatty acids (C16:0, C18:0, and C18:1) accounted for more than 60% of the algal fatty acids for all the wastewaters. The lipid is, therefore, considered suitable for synthesizing biodiesel.

  8. Extraction of Crude Chitinase from Higher Plants and their Chitin-Hydrolysis Activities; Kotosyokubutu yurai kichinaze no chusyutu to kichin bunkai kassei

    Energy Technology Data Exchange (ETDEWEB)

    Kondo, K.; Harada, K.; Shibata, M.; Maeda, R. [Doshisha Univ., Kyoto (Japan). Faculty of Engineering

    1997-07-10

    To prepare a purified chitinase from higher plants, firstly, crude enzymes were extracted from six higher plants, namely, radish seeds, sunflower seeds, watermelon seeds, bamboo leaves, orange skin, and persimmon skin. Using these crude enzymes, pH dependencies of hydrolysis reaction of colloidal chitin are investigated. For radish seeds and bamboo leaves, which have relatively high activities, the kinetics of enzymatic reaction are studies. It is clear that these reactions obey Michaelis-Menten kinetics. 7 refs., 3 figs., 2 tabs.

  9. Kinetics of gaseous uranium hexafluoride reaction with hydrogen chloride

    International Nuclear Information System (INIS)

    Ezubchenko, A.N.; Ilyukhin, A.I.; Merzlyakov, A.V.

    1993-01-01

    Kinetics of decrease of concentration of gaseous uranium hexafluoride in reaction with hydrogen chloride at temperatures close to room ones, was investigated by the method of IR spectroscopy. It was established that the process represented the first order reaction by both UF 6 and HCl. Activation energy of the reaction was determined: 7.6 ± 0.7 kcal/mol. Specific feature of reaction kinetics was noted: inversely proportional dependence of effective constant on UF 6 initial pressure. 5 refs., 3 figs

  10. 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.

  11. 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 ...

  12. Photocatalytic Water-Splitting Reaction from Catalytic and Kinetic Perspectives

    KAUST Repository

    Hisatomi, Takashi

    2014-10-16

    Abstract: Some particulate semiconductors loaded with nanoparticulate catalysts exhibit photocatalytic activity for the water-splitting reaction. The photocatalysis is distinct from the thermal catalysis because photocatalysis involves photophysical processes in particulate semiconductors. This review article presents a brief introduction to photocatalysis, followed by kinetic aspects of the photocatalytic water-splitting reaction.Graphical Abstract: [Figure not available: see fulltext.

  13. Kinetics of elementary atom and radical reactions: Progress report

    International Nuclear Information System (INIS)

    Gordon, R.J.

    1986-01-01

    Our research program is concerned with the kinetics of elementary gas phase reactions and energy transfer involving polyatomic molecules. We report here on three ongoing projects: The reaction of oxygen atoms with hydrogen molecules, the electronic relaxation of NH radicals, and the vibrational relaxation of highly excited SF 6 molecules. 10 refs., 5 figs

  14. Deuterium secondary isotope kinetic effects in imine formation reactions

    International Nuclear Information System (INIS)

    Amaral, L. do; Rossi, M.H.

    1986-01-01

    The kinetic α-deuterium isotope effects, K D /K H , for reaction mechanisms is studied. The reaction of pH function to m-bromobenzaldehyde, semicarbazide nucleophile, methoxy-amine and hydroxylamine are analysed. (M.J.C.) [pt

  15. Unravelling the Maillard reaction network by multiresponse kinetic modelling

    NARCIS (Netherlands)

    Martins, S.I.F.S.

    2003-01-01

    The Maillard reaction is an important reaction in food industry. It is responsible for the formation of colour and aroma, as well as toxic compounds as the recent discovered acrylamide. The knowledge of kinetic parameters, such as rate constants and activation energy, is necessary to predict its

  16. Discussion of the Investigation Method on the Reaction Kinetics of Metallurgical Reaction Engineering

    Science.gov (United States)

    Du, Ruiling; Wu, Keng; Zhang, Jiazhi; Zhao, Yong

    Reaction kinetics of metallurgical physical chemistry which was successfully applied in metallurgy (as ferrous metallurgy, non-ferrous metallurgy) became an important theoretical foundation for subject system of traditional metallurgy. Not only the research methods were very perfect, but also the independent structures and systems of it had been formed. One of the important tasks of metallurgical reaction engineering was the simulation of metallurgical process. And then, the mechanism of reaction process and the conversion time points of different control links should be obtained accurately. Therefore, the research methods and results of reaction kinetics in metallurgical physical chemistry were not very suitable for metallurgical reaction engineering. In order to provide the definite conditions of transmission, reaction kinetics parameters and the conversion time points of different control links for solving the transmission and reaction equations in metallurgical reaction engineering, a new method for researching kinetics mechanisms in metallurgical reaction engineering was proposed, which was named stepwise attempt method. Then the comparison of results between the two methods and the further development of stepwise attempt method were discussed in this paper. As a new research method for reaction kinetics in metallurgical reaction engineering, stepwise attempt method could not only satisfy the development of metallurgical reaction engineering, but also provide necessary guarantees for establishing its independent subject system.

  17. Kinetics of hydrogen isotope exchange reactions

    International Nuclear Information System (INIS)

    Gold, V.; McAdam, M.E.

    1975-01-01

    Under the influence of tritium β-radiation, 1,4-dioxan undergoes hydrogen exchange with the solvent water. The inhibition of the reaction by known electron scavengers (Ag + , Cu 2+ , Ni 2+ , Co 2+ , Zn 2+ , H 3 + O) and also by species with high reactivity towards hydroxyl radicals but negligible reactivity towards solvated electrons (N 3 - , Br - , SCN - ) has been examined in detail. γ-irradiation similarly induces hydrogen exchange. The action of scavengers is interpreted as requiring the involvement of two separately scavengeable primary radiolysis products in the sequence of reactions leading to exchange. The presence of electron scavengers, even at high concentration, does not totally inhibit the exchange, and a secondary exchange route, involving a low vacancy state of inhibitor cations, is considered responsible for the 'unscavengeable' portion of the reaction, by providing an alternative exchange route. Analogies are drawn between the exchange reaction and other radiation-induced reactions that are thought to involve spur processes. Some implication of radiation-chemical studies in water-alcohol mixtures are indicated. (author)

  18. Kinetics of transuranium element oxidation-reduction reactions in solution

    International Nuclear Information System (INIS)

    Gourisse, D.

    1966-09-01

    A review of the kinetics of U, Np, Pu, Am oxidation-reduction reactions is proposed. The relations between the different activation thermodynamic functions (compensatory effect, formal entropy of the activated complex, magnitude of reactions velocities) are considered. The effects of acidity, ionic strength deuterium and mixed solvents polarity on reactions rates are described. The effect of different anions on reactions rates are explained by variations of the reaction standard free energy and variations of the activation free energy (coulombic interactions) resulting from the complexation of dissolved species by these anions. (author) [fr

  19. Reaction wheels for kinetic energy storage

    Science.gov (United States)

    Studer, P. A.

    1984-11-01

    In contrast to all existing reaction wheel implementations, an order of magnitude increase in speed can be obtained efficiently if power to the actuators can be recovered. This allows a combined attitude control-energy storage system to be developed with structure mounted reaction wheels. The feasibility of combining reaction wheels with energy storage wwheels is demonstrated. The power required for control torques is a function of wheel speed but this energy is not dissipated; it is stored in the wheel. The I(2)R loss resulting from a given torque is shown to be constant, independent of the design speed of the motor. What remains, in order to efficiently use high speed wheels (essential for energy storage) for control purposes, is to reduce rotational losses to acceptable levels. Progress was made in permanent magnet motor design for high speed operation. Variable field motors offer more control flexibility and efficiency over a broader speed range.

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

    Science.gov (United States)

    Silvestri, Michael G.; Dills, Charles E.

    1989-01-01

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

  1. Environmentally relevant organophosphate triesters in herring gulls: In vitro biotransformation and kinetics and diester metabolite formation using a hepatic microsomal assay

    International Nuclear Information System (INIS)

    Greaves, Alana K.; Su, Guanyong; Letcher, Robert J.

    2016-01-01

    The in vitro biotransformation and kinetics of six organophosphate triester (OPE) flame retardants were investigated in herring gulls (Larus argentatus) from the Great Lakes using a hepatic microsomal metabolism assay. Administration of each individual OPE (tri-n-butyl phosphate (TNBP), tris(2-butoxyethyl) phosphate (TBOEP), triphenyl phosphate (TPHP), triethyl phosphate (TEP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and tris(2-chloroisopropyl) phosphate (TCIPP)) to the in vitro assay (concentration range 0.01 to 10 μM) resulted in rapid depletion with the exception of TEP. Following the Michaelis-Menten enzyme kinetics model, a preliminary 2-minute incubation period was used to estimate the V max (± SE) values (i.e., the maximal rate of reaction for a saturated enzyme system), which ranged from 5.0 ± 0.4 (TPHP) to 29 ± 18 pmol/min/mg protein (TBOEP), as well as the K M (± SE) values (i.e., the OPE concentration corresponding to one half of the V max ), which ranged from 9.8 ± 1 (TPHP) to 189 ± 135 nM (TBOEP). Biotransformation assays over a 100-minute incubation period revealed that TNBP was metabolized most rapidly (with a depletion rate of 73 ± 4 pmol/min/mg protein), followed by TBOEP (53 ± 8 pmol/min/mg), TCIPP (27 ± 1 pmol/min/mg), TPHP (22 ± 2 pmol/min/mg) and TDCIPP (8 ± 1 pmol/min/mg). In vitro biotransformation of OP triesters was clearly structure-dependent where non-halogenated alkyl OP triesters were metabolized more rapidly than halogenated alkyl triesters. Halogenated OP triesters were transformed to their respective diesters more efficiently relative to non-halogenated OP triesters. To our knowledge, this is the first study to investigate OP triester metabolism and OP diester formation in an avian or wildlife model system, which is important to understand the fate and biological activity of OPEs in an exposed organism. - Highlights: • The metabolism and kinetics of 6 OPEs were examined in herring gull liver microsomes. • The

  2. Environmentally relevant organophosphate triesters in herring gulls: In vitro biotransformation and kinetics and diester metabolite formation using a hepatic microsomal assay

    Energy Technology Data Exchange (ETDEWEB)

    Greaves, Alana K. [Wildlife and Landscape Directorate, Science and Technology Branch, Environment and Climate Change Canada, National Wildlife Research Centre, Carleton University, Ottawa, ON K1A 0H3 (Canada); Department of Chemistry, Carleton University, Ottawa, ON K1S 5B6 (Canada); Su, Guanyong, E-mail: guanyong.su85@gmail.com [Wildlife and Landscape Directorate, Science and Technology Branch, Environment and Climate Change Canada, National Wildlife Research Centre, Carleton University, Ottawa, ON K1A 0H3 (Canada); Department of Chemistry, Carleton University, Ottawa, ON K1S 5B6 (Canada); Letcher, Robert J., E-mail: robert.letcher@canada.ca [Wildlife and Landscape Directorate, Science and Technology Branch, Environment and Climate Change Canada, National Wildlife Research Centre, Carleton University, Ottawa, ON K1A 0H3 (Canada); Department of Chemistry, Carleton University, Ottawa, ON K1S 5B6 (Canada)

    2016-10-01

    The in vitro biotransformation and kinetics of six organophosphate triester (OPE) flame retardants were investigated in herring gulls (Larus argentatus) from the Great Lakes using a hepatic microsomal metabolism assay. Administration of each individual OPE (tri-n-butyl phosphate (TNBP), tris(2-butoxyethyl) phosphate (TBOEP), triphenyl phosphate (TPHP), triethyl phosphate (TEP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) and tris(2-chloroisopropyl) phosphate (TCIPP)) to the in vitro assay (concentration range 0.01 to 10 μM) resulted in rapid depletion with the exception of TEP. Following the Michaelis-Menten enzyme kinetics model, a preliminary 2-minute incubation period was used to estimate the V{sub max} (± SE) values (i.e., the maximal rate of reaction for a saturated enzyme system), which ranged from 5.0 ± 0.4 (TPHP) to 29 ± 18 pmol/min/mg protein (TBOEP), as well as the K{sub M} (± SE) values (i.e., the OPE concentration corresponding to one half of the V{sub max}), which ranged from 9.8 ± 1 (TPHP) to 189 ± 135 nM (TBOEP). Biotransformation assays over a 100-minute incubation period revealed that TNBP was metabolized most rapidly (with a depletion rate of 73 ± 4 pmol/min/mg protein), followed by TBOEP (53 ± 8 pmol/min/mg), TCIPP (27 ± 1 pmol/min/mg), TPHP (22 ± 2 pmol/min/mg) and TDCIPP (8 ± 1 pmol/min/mg). In vitro biotransformation of OP triesters was clearly structure-dependent where non-halogenated alkyl OP triesters were metabolized more rapidly than halogenated alkyl triesters. Halogenated OP triesters were transformed to their respective diesters more efficiently relative to non-halogenated OP triesters. To our knowledge, this is the first study to investigate OP triester metabolism and OP diester formation in an avian or wildlife model system, which is important to understand the fate and biological activity of OPEs in an exposed organism. - Highlights: • The metabolism and kinetics of 6 OPEs were examined in herring gull liver

  3. Kinetics of chemical reactions initiated by hot atoms

    International Nuclear Information System (INIS)

    Firsova, L.P.

    1977-01-01

    Modern ideas about kinetics of chemical reactions of hot atoms are generalized. The main points of the phenomenological theories (''kinetic theory'' of Wolfgang-Estrup hot reactions and the theory of ''reactions integral probability'' of Porter) are given. Physico-chemical models of elastic and non-elastic collisions are considered which are used in solving Boltzmann integro-differential equations and stochastic equations in the Porter theory. The principal formulas are given describing probabilities or yields of chemical reactions, initiated with hot atoms, depending on the distribution functions of hot particles with respect to energy. Briefly described are the techniques and the results of applying the phenomenological theories for interpretation of the experimental data obtained during nuclear reactions with hot atoms, photochemical investigations, etc. 96 references are given

  4. Comparison of dopamine kinetics in the larval Drosophila ventral nerve cord and protocerebrum with improved optogenetic stimulation.

    Science.gov (United States)

    Privman, Eve; Venton, B Jill

    2015-11-01

    Dopamine release and uptake have been studied in the Drosophila larval ventral nerve cord (VNC) using optogenetics to stimulate endogenous release. However, other areas of the central nervous system remain uncharacterized. Here, we compare dopamine release in the VNC and protocerebrum of larval Drosophila. Stimulations were performed with CsChrimson, a new, improved, red light-activated channelrhodopsin. In both regions, dopamine release was observed after only a single, 4 ms duration light pulse. Michaelis-Menten modeling was used to understand release and uptake parameters for dopamine. The amount of dopamine released ([DA]p ) on the first stimulation pulse is higher than the average [DA]p released from subsequent pulses. The initial and average amount of dopamine released per stimulation pulse is smaller in the protocerebrum than in the VNC. The average Vmax of 0.08 μM/s in the protocerebrum was significantly higher than the Vmax of 0.05 μM/s in the VNC. The average Km of 0.11 μM in the protocerebrum was not significantly different from the Km of 0.10 μM in the VNC. When the competitive dopamine transporter (DAT) inhibitor nisoxetine was applied, the Km increased significantly in both regions while Vmax stayed the same. This work demonstrates regional differences in dopamine release and uptake kinetics, indicating important variation in the amount of dopamine available for neurotransmission and neuromodulation. We use a new optogenetic tool, red light activated CsChrimson, to stimulate the release of dopamine in the ventral nerve cord and medial protocerebrum of the larval Drosophila central nervous system. We monitored extracellular dopamine by fast scan cyclic voltammetry and used Michaelis-Menten modeling to probe the regulation of extracellular dopamine, discovering important similarities and differences in these two regions. © 2015 International Society for Neurochemistry.

  5. Kinetic concepts of thermally stimulated reactions in solids

    Science.gov (United States)

    Vyazovkin, Sergey

    Historical analysis suggests that the basic kinetic concepts of reactions in solids were inherited from homogeneous kinetics. These concepts rest upon the assumption of a single-step reaction that disagrees with the multiple-step nature of solid-state processes. The inadequate concepts inspire such unjustified anticipations of kinetic analysis as evaluating constant activation energy and/or deriving a single-step reaction mechanism for the overall process. A more adequate concept is that of the effective activation energy, which may vary with temperature and extent of conversion. The adequacy of this concept is illustrated by literature data as well as by experimental data on the thermal dehydration of calcium oxalate monohydrate and thermal decomposition of calcium carbonate, ammonium nitrate and 1,3,5,7- tetranitro-1,3,5,7-tetrazocine.

  6. Kinetic investigation of heterogeneous catalytic reactions by means of the kinetic isotope method

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, F; Dermietzel, J [Akademie der Wissenschaften der DDR, Leipzig. Zentralinstitut fuer Isotopen- und Strahlenforschung

    1978-09-01

    The application of the kinetic isotope method to heterogeneous catalytic processes is possible for surface compounds by using the steady-state relation. However, the characterization of intermediate products becomes ambiguous if sorption rates are of the same order of magnitude as surface reactions rates. The isotopic exchange reaction renders possible the estimation of sorption rates.

  7. KINETIKA FERMENTASI SELULOSA MURNI OLEH Trichoderma reesi QM 9414 MENJADI GLUKOSA DAN PENERAPANNYA PADA JERAMI PADI BEBAS LIGNIN [Kinetics of Pure Cellulose Fermentation by Trichoderma Reesei QM 9414 to Glucose and Its Application of on Lignin Free Rice Straw

    Directory of Open Access Journals (Sweden)

    M Iyan Sofyan

    2004-12-01

    Full Text Available The objectives of this research were: 1 to determine aeration rate and substrate concentration of pure cellulose to produce maximum glucose by Trichoderma reesei QM 9414 at 30 oC, and agitation 150 rpm; 2 to study the kinetics of pure cellulose fermentation by Trichoderma reesei QM 9414 to glucose and its implication upon fermentation of the lignin free rice straw. The experiment was arranged in factorial randomized complete design in three times replication. Treatments consisted of three levels of aeration (1,00 vvm; 1,5 vvm; 2,0 vvm and three levels of substrate concentration (0,75 ; 1,00 ; 1,25 % w/v. The results showed that at the exponential phase the average specific growth of Trichoderma reesei QM 9414 was 0,05374 hour-1, the maximum glucose product concentration of pure cellulose was 0.1644 gL-1,and the oxygen transfer was 0,0328 mg L-1 hour-1. According to t-test, the kinetics of pure cellulose fermentation model just the same as the lignin free rice straw fermentation.The enzymes produced by Trichoderma reesei QM 9414 in pure cellulose fermentation media followed the Michaelis-Menten model. The enzyme kinetic parameters were the maximum growth rate was 37x10-3 hour-1 and Michaelis-Menten constant was ½ maximum μ =17,5x10-3 hour-1. The volumetric oxygen transfer (KLa using rice straw was 0,0337 mg.hour-1. The value of KLa could be used for conversion from bioreactor at laboratory scale to commercial scale design.

  8. Formation kinetics of gemfibrozil chlorination reaction products: analysis and application.

    Science.gov (United States)

    Krkosek, Wendy H; Peldszus, Sigrid; Huck, Peter M; Gagnon, Graham A

    2014-07-01

    Aqueous chlorination kinetics of the lipid regulator gemfibrozil and the formation of reaction products were investigated in deionized water over the pH range 3 to 9, and in two wastewater matrices. Chlorine oxidation of gemfibrozil was found to be highly dependent on pH. No statistically significant degradation of gemfibrozil was observed at pH values greater than 7. Gemfibrozil oxidation between pH 4 and 7 was best represented by first order kinetics. At pH 3, formation of three reaction products was observed. 4'-C1Gem was the only reaction product formed from pH 4-7 and was modeled with zero order kinetics. Chlorine oxidation of gemfibrozil in two wastewater matrices followed second order kinetics. 4'-C1Gem was only formed in wastewater with pH below 7. Deionized water rate kinetic models were applied to two wastewater effluents with gemfibrozil concentrations reported in literature in order to calculate potential mass loading rates of 4'C1Gem to the receiving water.

  9. Ametryn degradation by aqueous chlorine: Kinetics and reaction influences

    International Nuclear Information System (INIS)

    Xu Bin; Gao Naiyun; Cheng Hefa; Hu Chenyan; Xia Shengji; Sun Xiaofeng; Wang Xuejiao; Yang Shaogui

    2009-01-01

    The chemical oxidation of the herbicide ametryn was investigated by aqueous chlorination between pH 4 and 10 at a temperature of 25 deg. C. Ametryn was found to react very rapidly with aqueous chlorine. The reaction kinetics can be well described by a second-order kinetic model. The apparent second-order rate constants are greater than 5 x 10 2 M -1 s -1 under acidic and neutral conditions. The reaction proceeds much more slowly under alkaline conditions. The predominant reactions were found to be the reactions of HOCl with neutral ametryn and the charged ametryn, with rate constants equal to 7.22 x 10 2 and 1.58 x 10 3 M -1 s -1 , respectively. The ametryn degradation rate increases with addition of bromide and decreases with addition of ammonia during the chlorination process. Based on elementary chemical reactions, a kinetic model of ametryn degradation by chlorination in the presence of bromide or ammonia ion was also developed. By employing this model, we estimate that the rate constants for the reactions of HOBr with neutral ametryn and charged ametryn were 9.07 x 10 3 and 3.54 x 10 6 M -1 s -1 , respectively. These values are 10- to 10 3 -fold higher than those of HOCl, suggesting that the presence of bromine species during chlorination could significantly accelerate ametryn degradation.

  10. Internal Diffusion-Controlled Enzyme Reaction: The Acetylcholinesterase Kinetics.

    Science.gov (United States)

    Lee, Sangyun; Kim, Ji-Hyun; Lee, Sangyoub

    2012-02-14

    Acetylcholinesterase is an enzyme with a very high turnover rate; it quenches the neurotransmitter, acetylcholine, at the synapse. We have investigated the kinetics of the enzyme reaction by calculating the diffusion rate of the substrate molecule along an active site channel inside the enzyme from atomic-level molecular dynamics simulations. In contrast to the previous works, we have found that the internal substrate diffusion is the determinant of the acetylcholinesterase kinetics in the low substrate concentration limit. Our estimate of the overall bimolecular reaction rate constant for the enzyme is in good agreement with the experimental data. In addition, the present calculation provides a reasonable explanation for the effects of the ionic strength of solution and the mutation of surface residues of the enzyme. The study suggests that internal diffusion of the substrate could be a key factor in understanding the kinetics of enzymes of similar characteristics.

  11. Diagnostic Appraisal of Grade 12 Students' Understanding of Reaction Kinetics

    Science.gov (United States)

    Yan, Yaw Kai; Subramaniam, R.

    2016-01-01

    The study explored grade 12 students' understanding of reaction kinetics, a topic which has not been extensively explored in the chemistry education literature at this level. A 3-tier diagnostic instrument with 11 questions was developed--this format is of very recent origin and has been the subject of only a handful of studies. The findings…

  12. Penicillin Hydrolysis: A Kinetic Study of a Multistep, Multiproduct Reaction.

    Science.gov (United States)

    McCarrick, Thomas A.; McLafferty, Fred W.

    1984-01-01

    Background, procedures used, and typical results are provided for an experiment in which students carry out the necessary measurements on the acid-catalysis of penicillin in two hours. By applying kinetic theory to the data obtained, the reaction pathways for the hydrolysis of potassium benzyl penicillin are elucidated. (JN)

  13. Energetics and kinetics of ferrocyanide and nitrate/nitrite reactions

    International Nuclear Information System (INIS)

    Scheele, R.D.; Burger, L.L.; Sell, R.L.

    1994-01-01

    During the 1950's, radiocesium scavenging at the Hanford site resulted in radioactive waste sludges containing ferrocyanide, nitrate, and nitrite. These waters are a concern since certain mixtures of ferrocyanide and nitrate and/or nitrite are known to explode when heated. The authors have used differential scanning calorimetry, thermogravimetric analysis, isothermal calorimetry and gravimetry, and accelerating rate calorimetry to measure the thermal behavior, the reaction enthalpies, and selected kinetic parameters for reactions between sodium nickel ferrocyanide, the suspected ferrocyanide form in Hanford wastes, and nitrate and/or nitrite. These studies indicate that the oxidation proceeds via multiple steps, the initial reaction begins near 200 degrees C, the initial step has a high activation energy (>200 kJ/mole-K), succeeding reaction steps have activation energies ranging from 90 to 160 kJ/mole-K, and that the oxidation yields about 50% of the theoretical heat of reaction for the most energetic reaction

  14. Effects of reaction-kinetic parameters on modeling reaction pathways in GaN MOVPE growth

    Science.gov (United States)

    Zhang, Hong; Zuo, Ran; Zhang, Guoyi

    2017-11-01

    In the modeling of the reaction-transport process in GaN MOVPE growth, the selections of kinetic parameters (activation energy Ea and pre-exponential factor A) for gas reactions are quite uncertain, which cause uncertainties in both gas reaction path and growth rate. In this study, numerical modeling of the reaction-transport process for GaN MOVPE growth in a vertical rotating disk reactor is conducted with varying kinetic parameters for main reaction paths. By comparisons of the molar concentrations of major Ga-containing species and the growth rates, the effects of kinetic parameters on gas reaction paths are determined. The results show that, depending on the values of the kinetic parameters, the gas reaction path may be dominated either by adduct/amide formation path, or by TMG pyrolysis path, or by both. Although the reaction path varies with different kinetic parameters, the predicted growth rates change only slightly because the total transport rate of Ga-containing species to the substrate changes slightly with reaction paths. This explains why previous authors using different chemical models predicted growth rates close to the experiment values. By varying the pre-exponential factor for the amide trimerization, it is found that the more trimers are formed, the lower the growth rates are than the experimental value, which indicates that trimers are poor growth precursors, because of thermal diffusion effect caused by high temperature gradient. The effective order for the contribution of major species to growth rate is found as: pyrolysis species > amides > trimers. The study also shows that radical reactions have little effect on gas reaction path because of the generation and depletion of H radicals in the chain reactions when NH2 is considered as the end species.

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

    NARCIS (Netherlands)

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

    2015-01-01

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

  16. 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.

  17. Reaction kinetics for preparation of silica film with Stoeber method

    International Nuclear Information System (INIS)

    Shang Mengying; Jiang Xiaodong; Liu Miao; Luo Xuan; Tang Yongjian; Cao Linhong

    2013-01-01

    A new formula was proposed to investigate the relationship between reaction time and tetraethylorthosilicate (TEOS) conversion rate for preparation of silica sol with Stöber method, by studying the reaction kinetics of TEOS hydrolytic process. An appropriate conversion rate was then determined and used to calculate the theoretical optimal reaction time. Meanwhile, silica sols were prepared by sol-gel process using TEOS as precursor and ammonia as catalyst. It was found that the reaction time decreases with an increasing amount of ammonia and water. The values of experimental optimal reaction time were obtained, and agree with the theoretical results (the errors are within 5%), which shows good applicability of our formula. (authors)

  18. Non-equilibrium reaction rates in chemical kinetic equations

    Science.gov (United States)

    Gorbachev, Yuriy

    2018-05-01

    Within the recently proposed asymptotic method for solving the Boltzmann equation for chemically reacting gas mixture, the chemical kinetic equations has been derived. Corresponding one-temperature non-equilibrium reaction rates are expressed in terms of specific heat capacities of the species participate in the chemical reactions, bracket integrals connected with the internal energy transfer in inelastic non-reactive collisions and energy transfer coefficients. Reactions of dissociation/recombination of homonuclear and heteronuclear diatomic molecules are considered. It is shown that all reaction rates are the complex functions of the species densities, similarly to the unimolecular reaction rates. For determining the rate coefficients it is recommended to tabulate corresponding bracket integrals, additionally to the equilibrium rate constants. Correlation of the obtained results with the irreversible thermodynamics is established.

  19. Reaction kinetics of cellulose hydrolysis in subcritical and supercritical water

    Science.gov (United States)

    Olanrewaju, Kazeem Bode

    The uncertainties in the continuous supply of fossil fuels from the crisis-ridden oil-rich region of the world is fast shifting focus on the need to utilize cellulosic biomass and develop more efficient technologies for its conversion to fuels and chemicals. One such technology is the rapid degradation of cellulose in supercritical water without the need for an enzyme or inorganic catalyst such as acid. This project focused on the study of reaction kinetics of cellulose hydrolysis in subcritical and supercritical water. Cellulose reactions at hydrothermal conditions can proceed via the homogeneous route involving dissolution and hydrolysis or the heterogeneous path of surface hydrolysis. The work is divided into three main parts. First, the detailed kinetic analysis of cellulose reactions in micro- and tubular reactors was conducted. Reaction kinetics models were applied, and kinetics parameters at both subcritical and supercritical conditions were evaluated. The second major task was the evaluation of yields of water soluble hydrolysates obtained from the hydrolysis of cellulose and starch in hydrothermal reactors. Lastly, changes in molecular weight distribution due to hydrothermolytic degradation of cellulose were investigated. These changes were also simulated based on different modes of scission, and the pattern generated from simulation was compared with the distribution pattern from experiments. For a better understanding of the reaction kinetics of cellulose in subcritical and supercritical water, a series of reactions was conducted in the microreactor. Hydrolysis of cellulose was performed at subcritical temperatures ranging from 270 to 340 °C (tau = 0.40--0.88 s). For the dissolution of cellulose, the reaction was conducted at supercritical temperatures ranging from 375 to 395 °C (tau = 0.27--0.44 s). The operating pressure for the reactions at both subcritical and supercritical conditions was 5000 psig. The results show that the rate-limiting step in

  20. Collective behaviours: from biochemical kinetics to electronic circuits

    Science.gov (United States)

    Agliari, Elena; Barra, Adriano; Burioni, Raffaella; di Biasio, Aldo; Uguzzoni, Guido

    2013-12-01

    In this work we aim to highlight a close analogy between cooperative behaviors in chemical kinetics and cybernetics; this is realized by using a common language for their description, that is mean-field statistical mechanics. First, we perform a one-to-one mapping between paradigmatic behaviors in chemical kinetics (i.e., non-cooperative, cooperative, ultra-sensitive, anti-cooperative) and in mean-field statistical mechanics (i.e., paramagnetic, high and low temperature ferromagnetic, anti-ferromagnetic). Interestingly, the statistical mechanics approach allows a unified, broad theory for all scenarios and, in particular, Michaelis-Menten, Hill and Adair equations are consistently recovered. This framework is then tested against experimental biological data with an overall excellent agreement. One step forward, we consistently read the whole mapping from a cybernetic perspective, highlighting deep structural analogies between the above-mentioned kinetics and fundamental bricks in electronics (i.e. operational amplifiers, flashes, flip-flops), so to build a clear bridge linking biochemical kinetics and cybernetics.

  1. Kinetic aspects of the embedded clusters: Reaction - Rate Theory

    International Nuclear Information System (INIS)

    Despa, F.; Apostol, M.

    1995-07-01

    The main stages of the cluster growth process are reviewed using Reaction - Rate Theory. The precipitation stage is shown as a relaxation of the solute towards a cluster state characterized by a higher stability. The kinetic of the late stage of phase separation, the coarsening process, is analyzed by an off-centre diffusion mechanism. The theoretical results are compared to the experimental ones. (author). 37 refs, 6 figs

  2. Isothermal reaction calorimetry as a tool for kinetic analysis

    International Nuclear Information System (INIS)

    Zogg, Andreas; Stoessel, Francis; Fischer, Ulrich; Hungerbuehler, Konrad

    2004-01-01

    Reaction calorimetry has found widespread application for thermal and kinetic analysis of chemical reactions in the context of thermal process safety as well as process development. This paper reviews the most important reaction calorimetric principles (heat-flow, heat-balance, power-compensation, and Peltier principle) and their applications in commercial or scientific devices. The discussion focuses on the different dynamic behavior of the main calorimetric principles during an isothermal reaction measurement. Examples of available reaction calorimeters are further compared considering their detection limit, time constant as well as temperature range. In a second part, different evaluation methods for the isothermally measured calorimetric data are reviewed and discussed. The methods will be compared, focusing especially on the fact that reaction calorimetric data always contains additional informations not directly related to the actual chemical reaction such as heat of mixing, heat of phase-transfer/change processes or simple measurement errors. Depending on the evaluation method applied such disturbances have a significant influence on the calculated reaction enthalpies or rate constants

  3. Bayesian experts in exploring reaction kinetics of transcription circuits.

    Science.gov (United States)

    Yoshida, Ryo; Saito, Masaya M; Nagao, Hiromichi; Higuchi, Tomoyuki

    2010-09-15

    Biochemical reactions in cells are made of several types of biological circuits. In current systems biology, making differential equation (DE) models simulatable in silico has been an appealing, general approach to uncover a complex world of biochemical reaction dynamics. Despite of a need for simulation-aided studies, our research field has yet provided no clear answers: how to specify kinetic values in models that are difficult to measure from experimental/theoretical analyses on biochemical kinetics. We present a novel non-parametric Bayesian approach to this problem. The key idea lies in the development of a Dirichlet process (DP) prior distribution, called Bayesian experts, which reflects substantive knowledge on reaction mechanisms inherent in given models and experimentally observable kinetic evidences to the subsequent parameter search. The DP prior identifies significant local regions of unknown parameter space before proceeding to the posterior analyses. This article reports that a Bayesian expert-inducing stochastic search can effectively explore unknown parameters of in silico transcription circuits such that solutions of DEs reproduce transcriptomic time course profiles. A sample source code is available at the URL http://daweb.ism.ac.jp/~yoshidar/lisdas/.

  4. Reaction kinetics of resveratrol with thiyl and alkoxyl radicals

    International Nuclear Information System (INIS)

    Dzeba, I.; Mihaljevic, B.

    2011-01-01

    Complete text of publication follows. Plant derived resveratrol (trans-3,5,4'-trihydroxystilbene) possesses a broad spectrum of biological activities, one of them are very well known its antioxidative properties. Our work aims to provide kinetic data with regard to the reactivity of resveratrol with uninvestigated short-lived bioradicals, identified as mediators in oxidative lipid degradation processes. Radicals of our interest are alkoxyl radicals, well known propagators of the chain free radical reactions in lipids, and thiyl radicals which protect lipids from their degradation pathway, but at the same time cause the isomerization of the double bonds. In order to investigate these reactions of resveratrol laser flash photolysis was used. On the basis of competitive kinetics the rate constants were determined under pseudo-first order conditions in acetonitrile solutions at room temperature. Thiyl radicals were generated indirectly in solution containing 1-octadecanthiol and photosensitive benzophenone in acetonitrile using the light pulses at 347 nm from ruby laser. Tert-butoxyl radicals were generated directly by peroxide bond cleavage from di-tert-butyl peroxide in acetonitrile by light pulses of Nd:YAG at 355 nm, and ruby at 347 nm. Obtained rate constants for the reactions of resveratrol and radicals generated by laser flash photolysis will be summarized and compared with rare literature data for the rate constants of investigated reactions of resveratrol and other radicals generated by pulse radiolysis.

  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. Determination of kinetic parameters of heterogeneous isotopic exchange reaction

    International Nuclear Information System (INIS)

    Huang, Ting-Chia; Tsai, Fuan-Nan

    1977-01-01

    A mathematical model has been proposed for a heterogeneous isotopic exchange reaction which involves film diffusion, surface chemical reaction and intraparticle diffusion. The exchange equation to predict the exchange fraction as a function of time for the spherical particles immersed in a solution of finite volume has been derived. The relations between the exchange fraction and dimensionless time are plotted with xi(=ak sub(f)/KD sub(e)), xi 1 (=K 1 a 2 /D sub(e)) and final fractional uptake as parameters. From the values of the kinetic parameters xi and xi 1 , the relative importance of each limiting step is discussed. Experimental results of the isotopic exchange reaction of calcium ion in both system CaCO 3 (s)/Ca 2+ (aq) and system calcium type resin Dowex 50W-X8/Ca 2+ (aq) are coincident with the theoretical equation proposed in this study. (auth.)

  7. Kinetics of liquid lithium reaction with oxygen-nitrogen mixtures

    International Nuclear Information System (INIS)

    Gil, T.K.; Kazimi, M.S.

    1986-01-01

    A series of experiments have been conducted in order to characterize the kinetics of lithium chemical reaction with a mixture of oxygen and nitrogen. Three mixed gas compositions were used; 80% N 2 and 20% O 2 , 90% N 2 and 10% O 2 , and 95% N 2 and 5% O 2 . The reaction rate was obtained as a function of lithium temperature and the oxygen fraction. Liquid lithium temperature varied from 400 to 1100 0 C. By varying the composition, the degree of inhibition of the lithium-nitrogen reaction rate due to the presence of oxygen was observed. The results indicate that the lithium-nitrogen reaction rate depended on both the fraction of oxygen present and lithium temperature. The lithium nitride layer formed from the reaction also had a significant inhibition effect on the lithium-nitrogen reaction rate while the lithium-oxygen reaction rate was not as greatly hindered. LITFIRE, a computer code which simulates temperature and pressure history in a containment building following lithium spills, was modified by including (1) an improved model for the lithium-nitrogen reaction rate and (2) a model for the lithium-CO 2 reaction. LITFIRE was used to simulate HEDL's LC-2 and LA-5 experiments, and the predicted temperatures and pressures were in a reasonable agreement. Furthermore, LITFIRE was applied to a prototypical fusion reactor containment in order to simulate the consequences of a lithium spill accident. The result indicated that if nitrogen was used as containment building gas during the accident, the consequences of the accident would be less severe than those with air. The pressure rise in the building was found to be reduced by 50% and the maximum temperature of the combustion zone was limited to 900 0 C instead of 1200 0 C in the case of air

  8. Thermodynamic criteria for estimating the kinetic parameters of catalytic reactions

    Science.gov (United States)

    Mitrichev, I. I.; Zhensa, A. V.; Kol'tsova, E. M.

    2017-01-01

    Kinetic parameters are estimated using two criteria in addition to the traditional criterion that considers the consistency between experimental and modeled conversion data: thermodynamic consistency and the consistency with entropy production (i.e., the absolute rate of the change in entropy due to exchange with the environment is consistent with the rate of entropy production in the steady state). A special procedure is developed and executed on a computer to achieve the thermodynamic consistency of a set of kinetic parameters with respect to both the standard entropy of a reaction and the standard enthalpy of a reaction. A problem of multi-criterion optimization, reduced to a single-criterion problem by summing weighted values of the three criteria listed above, is solved. Using the reaction of NO reduction with CO on a platinum catalyst as an example, it is shown that the set of parameters proposed by D.B. Mantri and P. Aghalayam gives much worse agreement with experimental values than the set obtained on the basis of three criteria: the sum of the squares of deviations for conversion, the thermodynamic consistency, and the consistency with entropy production.

  9. Kinetics of the gas-phase tritium oxidation reaction

    International Nuclear Information System (INIS)

    Failor, R.A.

    1989-01-01

    Homogeneous gas-phase kinetics of tritium oxidation (2T 2 + O 2 →2T 2 O) have been studied with a model that accounts explicitly for radiolysis of the major species and the kinetics of the subsequent reactions of ionic, excited-state, and neutral species. Results from model calculations are given for 10 -4 -1.0 mol% T 2 in O 2 (298 K, 1 atm). As the reaction evolves three different mechanisms control T 2 O production, each with a different overall rate expression and a different order with respect to the T 2 concentration. The effects of self-radiolysis of pure T 2 on the tritium oxidation reaction were calculated. Tritium atoms, the primary product of T 2 self-radiolysis, altered the oxidation mechanism only during the first few seconds following the initiation of the T 2 -O 2 reaction. Ozone, an important intermediate in T 2 oxidation, was monitored in-situ by U.V. absorption spectroscopy for 0.01-1.0 mol% T 2 an 1 atm O 2 . The shape of the experimental ozone time profile agreed with the model predictions. As predicted, the measured initial rate of ozone production varied linearly with initial T 2 concentration ([T 2 ] 0.6 o ), but at an initial rate one-third the predicted value. The steady-state ozone concentration ([O 3 ]ss) was predicted to be dependent on [T 2 ] 0.3 o , but the measured value was [T 2 ] 0.6 o , resulting in four times higher [O 3 ]ss than predicted for a 1.0% T 2 -O 2 mixture. Adding H 2 to the T 2 -O 2 mixture, to provide insight into the differences between the radiolytic and chemical behavior of the tritium, produced a greater decrease in [O 3 ]ss than predicted. Adjusting the reaction cell surface-to-volume ratio showed implications of minor surface removal of ozone

  10. 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.

  11. Tunneling and reflection in unimolecular reaction kinetic energy release distributions

    Science.gov (United States)

    Hansen, K.

    2018-02-01

    The kinetic energy release distributions in unimolecular reactions is calculated with detailed balance theory, taking into account the tunneling and the reflection coefficient in three different types of transition states; (i) a saddle point corresponding to a standard RRKM-type theory, (ii) an attachment Langevin cross section, and (iii) an absorbing sphere potential at short range, without long range interactions. Corrections are significant in the one dimensional saddle point states. Very light and lightly bound absorbing systems will show measurable effects in decays from the absorbing sphere, whereas the Langevin cross section is essentially unchanged.

  12. KINETIC MODELS STUDY OF HYDRODESULPHURIZATION VACUUM DISTILLATE REACTION

    Directory of Open Access Journals (Sweden)

    AbdulMunem A. Karim

    2013-05-01

    Full Text Available    This study deals with  kinetics of hydrodesulphurization (HDS reaction of vacuum gas oil (611-833 K which was distillated from Kirkuk crude oil and which was obtained by blending the fractions, light vacuum gas oil (611 - 650 K, medium vacuum gas oil (650-690 K, heavy vacuum gas oil (690-727 K and very heavy vacuum gas oil (727-833 K.   The vacuum gas oil was hydrotreated on a commercial cobalt-molybdenum alumina catalyst presulfied at specified conditions in a laboratory trickle bed reactor. The reaction temperature range (583-643 K,liquid hourly space velocity range (1.5-3.75 h-1 and hydrogen pressure was kept constant at 3.5 MPa with hydrogen to oil ratio about 250 lt/lt.           The conversion results for desulphurization reaction appeared to obey the second order reaction. According to this model, the rate constants for desulphurization reaction were determined. Finally, the apparent activation energy (Ea, enthalpy of activation ( H* and entropy ( S* were calculated based on the values of rate constant (k2 and were equal 80.3792 KJ/mole, 75.2974 KJ/mole and 197.493 J/mole, respectively.

  13. Some Investigations on Protease Enzyme Production Kinetics Using Bacillus licheniformis BBRC 100053 and Effects of Inhibitors on Protease Activity

    Directory of Open Access Journals (Sweden)

    Zahra Ghobadi Nejad

    2014-01-01

    Full Text Available Due to great commercial application of protease, it is necessary to study kinetic characterization of this enzyme in order to improve design of enzymatic reactors. In this study, mathematical modeling of protease enzyme production kinetics which is derived from Bacillus licheniformis BBRC 100053 was studied (at 37°C, pH 10 after 73 h in stationary phase, and 150 rpm. The aim of the present paper was to determine the best kinetic model and kinetic parameters for production of protease and calculating Ki (inhibition constant of different inhibitors to find the most effective one. The kinetic parameters Km (Michaelis-Menten constant and Vm (maximum rate were calculated 0.626 mM and 0.0523 mM/min. According to the experimental results, using DFP (diisopropyl fluorophosphate and PMSF (phenylmethanesulfonyl fluoride as inhibitors almost 50% of the enzyme activity could be inhibited when their concentrations were 0.525 and 0.541 mM, respectively. Ki for DFP and PMSF were 0.46 and 0.56 mM, respectively. Kinetic analysis showed that the Lineweaver-Burk model was the best fitting model for protease production kinetics DFP was more effective than PMSF and both of them should be covered in the group of noncompetitive inhibitors.

  14. A physiologically based kinetic model for bacterial sulfide oxidation.

    Science.gov (United States)

    Klok, Johannes B M; de Graaff, Marco; van den Bosch, Pim L F; Boelee, Nadine C; Keesman, Karel J; Janssen, Albert J H

    2013-02-01

    In the biotechnological process for hydrogen sulfide removal from gas streams, a variety of oxidation products can be formed. Under natron-alkaline conditions, sulfide is oxidized by haloalkaliphilic sulfide oxidizing bacteria via flavocytochrome c oxidoreductase. From previous studies, it was concluded that the oxidation-reduction state of cytochrome c is a direct measure for the bacterial end-product formation. Given this physiological feature, incorporation of the oxidation state of cytochrome c in a mathematical model for the bacterial oxidation kinetics will yield a physiologically based model structure. This paper presents a physiologically based model, describing the dynamic formation of the various end-products in the biodesulfurization process. It consists of three elements: 1) Michaelis-Menten kinetics combined with 2) a cytochrome c driven mechanism describing 3) the rate determining enzymes of the respiratory system of haloalkaliphilic sulfide oxidizing bacteria. The proposed model is successfully validated against independent data obtained from biological respiration tests and bench scale gas-lift reactor experiments. The results demonstrate that the model is a powerful tool to describe product formation for haloalkaliphilic biomass under dynamic conditions. The model predicts a maximum S⁰ formation of about 98 mol%. A future challenge is the optimization of this bioprocess by improving the dissolved oxygen control strategy and reactor design. Copyright © 2012 Elsevier Ltd. All rights reserved.

  15. A study of butyl acetate synthesis. 4-reaction kinetics

    Directory of Open Access Journals (Sweden)

    Álvaro Orjuela Londoño

    2006-05-01

    Full Text Available This work was aimed at studying liquid-phase acetic acid and butyl alcohol esterification reaction (P atm =0.76 Bar,using an ion exchange resin (Lewatit K-2431 as catalyst. The effect of the absence of internal and external mass transport on catalyst particles was established in the research conditions used here. A set of assays to determine the effect of catalyst load (0.5%, 1%, 2% w/w temperature (73°C, 80°C, 87°C and molar ratio (1:2, 1:1, 2:1 acid/alcohol on reaction rate was carried out and both LHHW and pseudo-homogeneous kinetic expressions were obtained, these being in good agreement with the experimental data.

  16. Kinetics of the reactions of hydrated electrons with metal complexes

    International Nuclear Information System (INIS)

    Korsse, J.

    1983-01-01

    The reactivity of the hydrated electron towards metal complexes is considered. Experiments are described involving metal EDTA and similar complexes. The metal ions studied are mainly Ni 2+ , Co 2+ and Cu 2+ . Rates of the reactions of the complexes with e - (aq) were measured using the pulse radiolysis technique. It is shown that the reactions of e - (aq) with the copper complexes display unusually small kinetic salt effects. The results suggest long-range electron transfer by tunneling. A tunneling model is presented and the experimental results are discussed in terms of this model. Results of approximate molecular orbital calculations of some redox potentials are given, for EDTA chelates as well as for series of hexacyano and hexaquo complexes. Finally, equilibrium constants for the formation of ternary complexes are reported. (Auth./G.J.P.)

  17. Bayesian inference of chemical kinetic models from proposed reactions

    KAUST Repository

    Galagali, Nikhil

    2015-02-01

    © 2014 Elsevier Ltd. Bayesian inference provides a natural framework for combining experimental data with prior knowledge to develop chemical kinetic models and quantify the associated uncertainties, not only in parameter values but also in model structure. Most existing applications of Bayesian model selection methods to chemical kinetics have been limited to comparisons among a small set of models, however. The significant computational cost of evaluating posterior model probabilities renders traditional Bayesian methods infeasible when the model space becomes large. We present a new framework for tractable Bayesian model inference and uncertainty quantification using a large number of systematically generated model hypotheses. The approach involves imposing point-mass mixture priors over rate constants and exploring the resulting posterior distribution using an adaptive Markov chain Monte Carlo method. The posterior samples are used to identify plausible models, to quantify rate constant uncertainties, and to extract key diagnostic information about model structure-such as the reactions and operating pathways most strongly supported by the data. We provide numerical demonstrations of the proposed framework by inferring kinetic models for catalytic steam and dry reforming of methane using available experimental data.

  18. The Nanoconfined Free Radical Polymerization: Reaction Kinetics and Thermodynamics

    Science.gov (United States)

    Zhao, Haoyu; Simon, Sindee

    The reaction kinetics and thermodynamics of nanoconfined free radical polymerizations are investigated for methyl methacrylate (MMA) and ethyl methacrylate (EMA) monomers using differential scanning calorimetry. Controlled pore glass is used as the confinement medium with pore diameters as small as 7.5 nm; the influence of both hydrophobic (silanized such that trimethylsilyl groups cover the surface) and hydrophilic (native silanol) surfaces is investigated. Propagation rates increase when monomers are reacted in the hydrophilic pores presumably due to the specific interactions between the carbonyl and silanol groups; however, the more flexible EMA monomer shows weaker effects. On the other hand, initial rates of polymerization in hydrophobic pores are unchanged from the bulk. In both pores, the onset of autoacceleration occurs earlier due to the reduced diffusivity of confined chains, which may be compensated at high temperatures. In addition to changes in kinetics, the reaction thermodynamics can be affected under nanoconfinement. Specifically, the ceiling temperature (Tc) is shifted to lower temperatures in nanopores, with pore surface chemistry showing no significant effects; the equilibrium conversion is also reduced at high temperatures below Tc. These observations are attributed to a larger negative change in entropy on propagation for the confined system, with the MMA system again showing greater effects. Funding from ACS PRF is gratefully acknowledged.

  19. Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

    Science.gov (United States)

    Liechty, Derek S.; Lewis, Mark J.

    2010-01-01

    Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

  20. Spectator Ions ARE Important! A Kinetic Study of the Copper-Aluminum Displacement Reaction

    Science.gov (United States)

    Sobel, Sabrina G.; Cohen, Skyler

    2010-01-01

    Surprisingly, spectator ions are responsible for unexpected kinetics in the biphasic copper(II)-aluminum displacement reaction, with the rate of reaction dependent on the identity of the otherwise ignored spectator ions. Application of a published kinetic analysis developed for a reaction between a rotating Al disk and a Cu(II) ion solution to the…

  1. Kinetics of reactions of aquacobalamin with aspartic and glutamic acids and their amides in water solutions

    Science.gov (United States)

    Bui, T. T. T.; Sal'nikov, D. S.; Dereven'kov, I. A.; Makarov, S. V.

    2017-04-01

    The kinetics of aquacobalamin reaction with aspartic and glutamic acids, and with their amides in water solutions, is studied via spectrophotometry. The kinetic and activation parameters of the process are determined. It is shown that the reaction product is cobalamin-amino acid complex. The data are compared to results on the reaction between aquacobalamin and primary amines.

  2. Stepwise kinetic equilibrium models of quantitative polymerase chain reaction

    Directory of Open Access Journals (Sweden)

    Cobbs Gary

    2012-08-01

    Full Text Available Abstract Background Numerous models for use in interpreting quantitative PCR (qPCR data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most potential for accurate interpretation of qPCR data. Even so, they have not been thoroughly investigated and are rarely used for interpretation of qPCR data. New results for kinetic modeling of qPCR are presented. Results Two models are presented in which the efficiency of amplification is based on equilibrium solutions for the annealing phase of the qPCR process. Model 1 assumes annealing of complementary targets strands and annealing of target and primers are both reversible reactions and reach a dynamic equilibrium. Model 2 assumes all annealing reactions are nonreversible and equilibrium is static. Both models include the effect of primer concentration during the annealing phase. Analytic formulae are given for the equilibrium values of all single and double stranded molecules at the end of the annealing step. The equilibrium values are then used in a stepwise method to describe the whole qPCR process. Rate constants of kinetic models are the same for solutions that are identical except for possibly having different initial target concentrations. Analysis of qPCR curves from such solutions are thus analyzed by simultaneous non-linear curve fitting with the same rate constant values applying to all curves and each curve having a unique value for initial target concentration. The models were fit to two data sets for which the true initial target concentrations are known. Both models give better fit to observed qPCR data than other kinetic models present in the

  3. Stepwise kinetic equilibrium models of quantitative polymerase chain reaction.

    Science.gov (United States)

    Cobbs, Gary

    2012-08-16

    Numerous models for use in interpreting quantitative PCR (qPCR) data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most potential for accurate interpretation of qPCR data. Even so, they have not been thoroughly investigated and are rarely used for interpretation of qPCR data. New results for kinetic modeling of qPCR are presented. Two models are presented in which the efficiency of amplification is based on equilibrium solutions for the annealing phase of the qPCR process. Model 1 assumes annealing of complementary targets strands and annealing of target and primers are both reversible reactions and reach a dynamic equilibrium. Model 2 assumes all annealing reactions are nonreversible and equilibrium is static. Both models include the effect of primer concentration during the annealing phase. Analytic formulae are given for the equilibrium values of all single and double stranded molecules at the end of the annealing step. The equilibrium values are then used in a stepwise method to describe the whole qPCR process. Rate constants of kinetic models are the same for solutions that are identical except for possibly having different initial target concentrations. Analysis of qPCR curves from such solutions are thus analyzed by simultaneous non-linear curve fitting with the same rate constant values applying to all curves and each curve having a unique value for initial target concentration. The models were fit to two data sets for which the true initial target concentrations are known. Both models give better fit to observed qPCR data than other kinetic models present in the literature. They also give better estimates of

  4. A simple theory of motor protein kinetics and energetics. II.

    Science.gov (United States)

    Qian, H

    2000-01-10

    A three-state stochastic model of motor protein [Qian, Biophys. Chem. 67 (1997) pp. 263-267] is further developed to illustrate the relationship between the external load on an individual motor protein in aqueous solution with various ATP concentrations and its steady-state velocity. A wide variety of dynamic motor behavior are obtained from this simple model. For the particular case of free-load translocation being the most unfavorable step within the hydrolysis cycle, the load-velocity curve is quasi-linear, V/Vmax = (cF/Fmax-c)/(1-c), in contrast to the hyperbolic relationship proposed by A.V. Hill for macroscopic muscle. Significant deviation from the linearity is expected when the velocity is less than 10% of its maximal (free-load) value--a situation under which the processivity of motor diminishes and experimental observations are less certain. We then investigate the dependence of load-velocity curve on ATP (ADP) concentration. It is shown that the free load Vmax exhibits a Michaelis-Menten like behavior, and the isometric Fmax increases linearly with ln([ATP]/[ADP]). However, the quasi-linear region is independent of the ATP concentration, yielding an apparently ATP-independent maximal force below the true isometric force. Finally, the heat production as a function of ATP concentration and external load are calculated. In simple terms and solved with elementary algebra, the present model provides an integrated picture of biochemical kinetics and mechanical energetics of motor proteins.

  5. Kinetic and reaction pathways of methanol oxidation on platinum

    International Nuclear Information System (INIS)

    McCabe, R.W.; McCready, D.F.

    1986-01-01

    Methanol oxidation kinetics were measured on Pt wires in a flow reactor at pressures between 30 and 130 Pa. The kinetics were measured as a function of oxygen-to-methanol equivalence ratio phi and wire temperature. In methanol-lean feeds (phi 2 CO, CO 2 , and H 2 O were the only products; in methanol-rich feeds (phi > 1), CO, H 2 , H 2 CO, CO 2 , and H 2 O were observed. Experiments with 18 O 2 showed that the principal methanol oxidation pathway does not involve C-O bond dissociation. However, the 18 O 2 experiments, together with other features of the methanol oxidation data, also provided evidence for a minor oxidation pathway (accounting for less than 1% of the product CO 2 ) which proceeds through a carbon intermediate. A mathematical model is presented which describes the principal CH 3 OH oxidation pathway as a series reaction involving adsorbed H 2 CO and CO intermediates. Consistent with experimental results, the model predicts that inhibition by adsorbed CO should be weaker for CH 3 OH and H 2 CO oxidation than for CO oxidation. 34 references, 10 figures, 2 tables

  6. The reaction kinetics of lithium salt with water vapor

    International Nuclear Information System (INIS)

    Balooch, M.; Dinh, L.N.; Calef, D.F.

    2002-01-01

    The interaction of lithium salt (LiH and/or LiD) with water vapor in the partial pressure range of 10 -5 -2657 Pa has been investigated. The reaction probability of water with LiH cleaved in an ultra high vacuum environment was obtained using the modulated molecular beam technique. This probability was 0.11 and independent of LiH surface temperature, suggesting a negligible activation energy for the reaction in agreement with quantum chemical calculations. The value gradually reduced, however, to 0.007 as the surface concentration of oxygen containing product approached full coverage. As the film grew beyond a monolayer, the phase lag of hydrogen product increased from 0 deg. C to 20 deg. C and the reaction probability reduced further until it approached our detection limit (∼10 -4 ). This phase lag was attributed to a diffusion-limited process in this regime. For micrometer thick hydroxide films grown in high moisture concentration environment on LiD and LiH, the reaction probability reduced to ∼4x10 -7 and was independent of exposure time. In this regime of thick hydroxide films (LiOH and/or LiOD), microcracks generated in the films to release stress provided easier pathways for moisture to reach the interface. A modified microscope, capable of both atomic force microscopy and nanoindentation, was also employed to investigate the surface morphology of hydroxide monohydrate (LiOH · H 2 O and/or LiOD · H 2 O) grown on hydroxide at high water vapor partial pressures and the kinetics of this growth

  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 of uptake of phosphates and nitrates by marine multicellular algae Gelidium latifolium (Grev.) Born. et Thur].

    Science.gov (United States)

    Silkin, V A; Chubchikova, I N

    2007-01-01

    We studied nonstationary kinetics of the uptake of phosphates and nitrates by the red marine algae Gelidium latifolium (Grev.) Born et Thur. and calculated constants of the Michaelis-Menten equation for these elements. In the area of 0-3 microM, the kinetics of phosphate consumption had the following coefficients: maximum rate of uptake 0.8 micromol/(g x h), constant of half-saturation 1.745 microM. For nitrate nitrogen at 0-30 microM, an adaptive strategy of uptake kinetics was noted with change of the equation parameters with time: after 1 h, the maximum rate of uptake was 5.1 micromol/(g x h) and constant of half-saturation 19 gM, while within 2 h, the maximum rate of uptake significantly increased. This could be related to the synthesis of nitrate reductase. Coupled with the uptake of nitrates, nonstationary kinetics of the release of nitrates in the surrounding medium had a one-peak pattern: the maximum concentration of nitrites in the medium and the time of its achievement increased with the initial concentration of nitrates. The maximum concentration of nitrites was 6 to 14% of the initial concentration in the medium.

  9. Iteration scheme for implicit calculations of kinetic and equilibrium chemical reactions in fluid dynamics

    International Nuclear Information System (INIS)

    Ramshaw, J.D.; Chang, C.H.

    1995-01-01

    An iteration scheme for the implicit treatment of equilibrium chemical reactions in partial equilibrium flow has previously been described. Here we generalize this scheme to kinetic reactions as well as equilibrium reactions. This extends the applicability of the scheme to problems with kinetic reactions that are fast in regions of the flow field but slow in others. The resulting scheme thereby provides a single unified framework for the implicit treatment of an arbitrary number of coupled equilibrium and kinetic reactions in chemically reacting fluid flow. 10 refs., 2 figs

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

    Science.gov (United States)

    Yang, Mino

    2007-06-07

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

  11. Kinetics of the Reaction of CO2 with Aqueous Potassium Salt of Taurine and Glycine

    NARCIS (Netherlands)

    Kumar, P.S.; Hogendoorn, J.A.; Versteeg, G.F.; Feron, P.H.M.

    2003-01-01

    The kinetics of the reaction between CO2 and aqueous potassium salts of taurine and glycine was measured at 295 K in a stirred-cell reactor with a flat gas–liquid interface. For aqueous potassium taurate solutions, the temperature effect on the reaction kinetics was measured at 285 and 305 K. Unlike

  12. Kinetics of the reaction of CO2 with aqueous potassium salt of taurine and glycine

    NARCIS (Netherlands)

    Kumar Paramasivam Senthil, P.S.; Hogendoorn, Kees; Versteeg, Geert; Feron, P.H.M.

    2003-01-01

    The kinetics of the reaction between CO2 and aqueous potassium salts of taurine and glycine was measured at 295 K in a stirred-cell reactor with a flat gas-liquid interface. For aqueous potassium taurate solutions, the temperature effect on the reaction kinetics was measured at 285 and 305 K. Unlike

  13. Optimizing electrode-attached redox-peptide systems for kinetic characterization of protease action on immobilized substrates. Observation of dissimilar behavior of trypsin and thrombin enzymes.

    Science.gov (United States)

    Anne, Agnès; Chovin, Arnaud; Demaille, Christophe

    2012-06-12

    In this work, we experimentally address the issue of optimizing gold electrode attached ferrocene (Fc)-peptide systems for kinetic measurements of protease action. Considering human α-thrombin and bovine trypsin as proteases of interest, we show that the recurring problem of incomplete cleavage of the peptide layer by these enzymes can be solved by using ultraflat template-stripped gold, instead of polished polycrystalline gold, as the Fc-peptide bearing electrode material. We describe how these fragile surfaces can be mounted in a rotating disk configuration so that enzyme mass transfer no longer limits the overall measured cleavage kinetics. Finally, we demonstrate that, once the system has been optimized, in situ real-time cyclic voltammetry monitoring of the protease action can yield high-quality kinetic data, showing no sign of interfering effects. The cleavage progress curves then closely match the Langmuirian variation expected for a kinetically controlled surface process. Global fit of the progress curves yield accurate values of the peptide cleavage rate for both trypsin and thrombin. It is shown that, whereas trypsin action on the surface-attached peptide closely follows Michaelis-Menten kinetics, thrombin displays a specific and unexpected behavior characterized by a nearly enzyme-concentration-independent cleavage rate in the subnanomolar enzyme concentration range. The reason for this behavior has still to be clarified, but its occurrence may limit the sensitivity of thrombin sensors based on Fc-peptide layers.

  14. Stoichiometry and kinetics of single and mixed substrate uptake in Aspergillus niger.

    Science.gov (United States)

    Lameiras, Francisca; Ras, Cor; Ten Pierick, Angela; Heijnen, Joseph J; van Gulik, Walter M

    2018-02-01

    In its natural environment, the filamentous fungus Aspergillus niger grows on decaying fruits and plant material, thereby enzymatically degrading the lignocellulosic constituents (lignin, cellulose, hemicellulose, and pectin) into a mixture of mono- and oligosaccharides. To investigate the kinetics and stoichiometry of growth of this fungus on lignocellulosic sugars, we carried out batch cultivations on six representative monosaccharides (glucose, xylose, mannose, rhamnose, arabinose, and galacturonic acid) and a mixture of these. Growth on these substrates was characterized in terms of biomass yields, oxygen/biomass ratios, and specific conversion rates. Interestingly, in combination, some of the carbon sources were consumed simultaneously and some sequentially. With a previously developed protocol, a sequential chemostat cultivation experiment was performed on a feed mixture of the six substrates. We found that the uptake of glucose, xylose, and mannose could be described with a Michaelis-Menten-type kinetics; however, these carbon sources seem to be competing for the same transport systems, while the uptake of arabinose, galacturonic acid, and rhamnose appeared to be repressed by the presence of other substrates.

  15. Continuous ammonium enrichment of a woodland stream: uptake kinetics, leaf decomposition, and nitrification

    Energy Technology Data Exchange (ETDEWEB)

    Newbold, J D; Elwood, J W; Schulze, M S; Stark, R W; Barmeier, J C

    1983-01-01

    In order to test for nitrogen limitation and examine ammonium uptake by stream sediments, ammonium hydroxide was added continuously at concentrations averaging 100 /sup +/gl/sup -1/ for 70 days to a second-order reach of Walker Branch, an undisturbed woodland stream in Tennessee. Ammonium uptake during the first 4 h of addition corresponded to adsorption kinetics rather than to first-order uptake or to Michaelis-Menten kinetics. However, the calculated adsorption partition coefficient was two to four orders of magnitude greater than values reported for physical adsorption of ammonium, suggesting that the uptake was largely biotic. Mass balance indicated that the uptake of ammonium from the water could be accounted for by increased nitrogen content in benthic organic detritus. Nitrification, inferred from longitudinal gradients in NO/sub 3/, began soon after enrichment and increased dramatically near the end of the experiment. Both ammonium and nitrate concentrations dropped quickly to near background levels when input ceased, indicating little desorption or nitrification of excess nitrogen stored in the reach. There was no evidence of nitrogen limitation as measured by weight loss, oxygen consumption, phosphorus content, and macroinvertebrate density of red oak leaf packs, or by chlorophyll content and aufwuchs biomass on plexiglass slides. A continuous phosphorus enrichment 1 year earlier had demonstrated phosphorus limitation in Walker Branch. 38 references, 6 figures, 3 tables.

  16. The reaction kinetics of amino radicals with sulfur dioxide

    DEFF Research Database (Denmark)

    Gao, Yide; Glarborg, Peter; Marshall, Paul

    2015-01-01

    Application of the laser photolysis-laser-induced fluorescence method to the reaction NH2+SO2 in argon bath gas yields pressure-dependent, third-order kinetics which may be summarized as k = (1.49 ± 0.15) × 10-31 (T/298 K)-0.83cm6 molecule-2 s-1 over 292-555K, where the uncertainty is the 95......% confidence interval and includes possible systematic errors. The quenching of vibrationally excited NH2 is consistent with a high-pressure limit for NH2+SO2 of (1.62 ± 0.25) × 10-11cm3 molecule-1 s-1 over the temperature range 295-505K, where again the 95% confidence interval is shown. Ab initio analysis...... yields a H2N-SO2 dissociation enthalpy of 73.5 kJ mol-1, and comparison with RRKM theory and the exponential down model for energy transfer yields down = 350 cm-1 for Ar at room temperature....

  17. Mechanistic rationalization of unusual sigmoidal kinetic profiles in the Machetti-De Sarlo cycloaddition reaction.

    Science.gov (United States)

    Mower, Matthew P; Blackmond, Donna G

    2015-02-18

    Unusual sigmoidal kinetic profiles in the Machetti-De Sarlo base-catalyzed 1,3-dipolar cycloaddition of acrylamide to N-methylnitroacetamide are rationalized by detailed in situ kinetic analysis. A dual role is uncovered in which a substrate acts as a precursor to catalyze its own reaction. Such kinetic studies provide a general protocol for distinguishing among different mechanistic origins of induction periods in complex organic reactions.

  18. Enzyme-catalyzed and binding reaction kinetics determined by titration calorimetry.

    Science.gov (United States)

    Hansen, Lee D; Transtrum, Mark K; Quinn, Colette; Demarse, Neil

    2016-05-01

    Isothermal calorimetry allows monitoring of reaction rates via direct measurement of the rate of heat produced by the reaction. Calorimetry is one of very few techniques that can be used to measure rates without taking a derivative of the primary data. Because heat is a universal indicator of chemical reactions, calorimetry can be used to measure kinetics in opaque solutions, suspensions, and multiple phase systems and does not require chemical labeling. The only significant limitation of calorimetry for kinetic measurements is that the time constant of the reaction must be greater than the time constant of the calorimeter which can range from a few seconds to a few minutes. Calorimetry has the unique ability to provide both kinetic and thermodynamic data. This article describes the calorimetric methodology for determining reaction kinetics and reviews examples from recent literature that demonstrate applications of titration calorimetry to determine kinetics of enzyme-catalyzed and ligand binding reactions. A complete model for the temperature dependence of enzyme activity is presented. A previous method commonly used for blank corrections in determinations of equilibrium constants and enthalpy changes for binding reactions is shown to be subject to significant systematic error. Methods for determination of the kinetics of enzyme-catalyzed reactions and for simultaneous determination of thermodynamics and kinetics of ligand binding reactions are reviewed. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Study on biofiltration capacity and kinetics of nutrient uptake by Gracilaria cervicornis (Turner J. Agardh (Rhodophyta, Gracilariaceae

    Directory of Open Access Journals (Sweden)

    Marcella A. A. Carneiro

    2011-04-01

    Full Text Available The absorption efficiency and kinetic parameters (Vmax, Ks and Vmax:Ks of the seaweed Gracilaria cervicornis for the nutrients NH4+, NO3- and PO4(3- were evaluated. Absorption efficiency was measured by monitoring nutrient concentrations for 5 h in culture media with initial concentrations of 5, 10, 20 and 30µM. Kinetic parameters were determined by using the Michaelis-Menten formula. Absorption efficiencies for this algae were greater in treatments with lower concentrations, as evidenced by a reduction of 85.3, 97.5 and 81.2% for NH4+, NO3- and PO4(3-, respectively. Kinetic parameters show that G. cervicornis exhibits greater ability to take up high concentrations of NH4+ (Vmax=158.5µM g dw-1 h-1 and low concentrations of PO4(3- (Ks=5µM and Vmax:Ks=10.3. These results suggest that this algal species has good absorption capacity for the nutrients tested and may be a promising candidate as a bioremediator of eutrophized environments.

  20. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

    International Nuclear Information System (INIS)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Brooks, Scott C; Pace, Molly; Kim, Young Jin; Jardine, Philip M.; Watson, David B.

    2007-01-01

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M. partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M. species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M-NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions

  1. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions.

    Science.gov (United States)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C; Brooks, Scott C; Pace, Molly N; Kim, Young-Jin; Jardine, Philip M; Watson, David B

    2007-06-16

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  2. Evaluating the effect of potassium on cellulose pyrolysis reaction kinetics

    International Nuclear Information System (INIS)

    Trendewicz, Anna; Evans, Robert; Dutta, Abhijit; Sykes, Robert; Carpenter, Daniel; Braun, Robert

    2015-01-01

    This paper proposes modifications to an existing cellulose pyrolysis mechanism in order to include the effect of potassium on product yields and composition. The changes in activation energies and pre-exponential factors due to potassium were evaluated based on the experimental data collected from pyrolysis of cellulose samples treated with different levels of potassium (0–1% mass fraction). The experiments were performed in a pyrolysis reactor coupled to a molecular beam mass spectrometer (MBMS). Principal component analysis (PCA) performed on the collected data revealed that cellulose pyrolysis products could be divided into two groups: anhydrosugars and other fragmentation products (hydroxyacetaldehyde, 5-hydroxymethylfurfural, acetyl compounds). Multivariate curve resolution (MCR) was used to extract the time resolved concentration score profiles of principal components. Kinetic tests revealed that potassium apparently inhibits the formation of anhydrosugars and catalyzes char formation. Therefore, the oil yield predicted at 500 ° C decreased from 87.9% from cellulose to 54.0% from cellulose with 0.5% mass fraction potassium treatment. The decrease in oil yield was accompanied by increased yield of char and gases produced via a catalyzed dehydration reaction. The predicted char and gas yield from cellulose were 3.7% and 8.4%, respectively. Introducing 0.5% mass fraction potassium treatment resulted in an increase of char yield to 12.1% and gas yield to 33.9%. The validation of the cellulose pyrolysis mechanism with experimental data from a fluidized-bed reactor, after this correction for potassium, showed good agreement with our results, with differences in product yields of up to 5%

  3. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    Science.gov (United States)

    Fedorenko, S. G.; Burshtein, A. I.

    2014-09-01

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

  4. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    Energy Technology Data Exchange (ETDEWEB)

    Fedorenko, S. G. [Voevodsky Institute of Chemical Kinetics and Combustion, Novosibirsk (Russian Federation); Burshtein, A. I. [Weizmann Institute of Science, 76100, Rehovot (Israel)

    2014-09-21

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

  5. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    International Nuclear Information System (INIS)

    Fedorenko, S. G.; Burshtein, A. I.

    2014-01-01

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics

  6. Reaction kinetics of oxygen on single-phase alloys, oxidation of nickel and niobium alloys

    International Nuclear Information System (INIS)

    Lalauze, Rene

    1973-01-01

    This research thesis first addresses the reaction kinetics of oxygen on alloys. It presents some generalities on heterogeneous reactions (conventional theory, theory of jumps), discusses the core reaction (with the influence of pressure), discusses the influence of metal self-diffusion on metal oxidation kinetics (equilibrium conditions at the interface, hybrid diffusion regime), reports the application of the hybrid diffusion model to the study of selective oxidation of alloys (Wagner model, hybrid diffusion model) and the study of the oxidation kinetics of an alloy forming a solid solution of two oxides. The second part reports the investigation of the oxidation of single phase nickel and niobium alloys (phase α, β and γ)

  7. application of ascorbic acid 2-phosphate as a new voltammetric

    African Journals Online (AJOL)

    a

    acid 2-phosphate (AAP) as a new voltammetric substrate has been described in this paper. In the alkaline buffer .... ALP labeled goat anti-rabbit ..... Classical Michaelis-Menten kinetic experiments were carried out to measure the maximum.

  8. Kinetics of reactions of chromium, molybdenum and tungsten hexacarbonyls with hydroxylamine and trimethylamine oxide

    International Nuclear Information System (INIS)

    Maksakov, V.A.; Ershova, V.A.

    1994-01-01

    Mechanism of M(CO) 6 (M = Cr, Mo, W) reaction with hydroxylamine was studied. On the basis of kinetic data it was ascertained that as a result of the reaction CO oxidation to CO 2 and intramolecular transfer of amine formed to the central atom of metal occur. Mechanisms of M(CO) 6 reactions with hydroxylamine and trimethylamine oxide are compared

  9. Evaluation of deltamethrin kinetics and dosimetry in the maturing rat using a PBPK model

    International Nuclear Information System (INIS)

    Tornero-Velez, Rogelio; Mirfazaelian, Ahmad; Kim, Kyu-Bong; Anand, Sathanandam S.; Kim, Hyo J.; Haines, Wendy T.; Bruckner, James V.; Fisher, Jeffrey W.

    2010-01-01

    Immature rats are more susceptible than adults to the acute neurotoxicity of pyrethroid insecticides like deltamethrin (DLM). A companion kinetics study (Kim et al., in press) revealed that blood and brain levels of the neuroactive parent compound were inversely related to age in rats 10, 21, 40 and 90 days old. The objective of the current study was to modify a physiologically based pharmacokinetic (PBPK) model of DLM disposition in the adult male Sprague-Dawley rat (Mirfazaelian et al., 2006), so blood and target organ dosimetry could be accurately predicted during maturation. Age-specific organ weights and age-dependent changes in the oxidative and hydrolytic clearance of DLM were modeled with a generalized Michaelis-Menten model for growth and the summary equations incorporated into the PBPK model. The model's simulations compared favorably with empirical DLM time-courses in plasma, blood, brain and fat for the four age-groups evaluated (10, 21, 40 and 90 days old). PND 10 pups' area under the 24-h brain concentration time curve (AUC 0-24h ) was 3.8-fold higher than that of the PND 90 adults. Our maturing rat PBPK model allows for updating with age- and chemical-dependent parameters, so pyrethroid dosimetry can be forecast in young and aged individuals. Hence, this model provides a methodology for risk assessors to consider age-specific adjustments to oral Reference Doses on the basis of PK differences.

  10. Rapid Determination of Enzyme Kinetics from Fluorescence: Overcoming the Inner Filter Effect

    Science.gov (United States)

    Palmier, Mark O.; Van Doren, Steven R.

    2007-01-01

    Fluorescence change is convenient for monitoring enzyme kinetics. Unfortunately, it looses linearity as the absorbance of the fluorescent substrate increases with concentration. When the sum of absorbance at excitation and emission wavelengths exceeds 0.08, this inner filtering effect (IFE) alters apparent initial velocities, Km, and kcat. The IFE distortion of apparent initial velocities can be corrected without doing fluorophore dilution assays. Using the substrate’s extinction coefficients at excitation and emission wavelengths, the inner filter effect can be modeled during curve fitting for more accurate Michaelis-Menten parameters. A faster and simpler approach is to derive kcat and Km from progress curves. Strategies to obtain reliable and reproducible estimates of kcat and Km from only two or three progress curves are illustrated using matrix metalloproteinase-12 and alkaline phosphatase. Accurate estimates of concentration of enzyme active sites and specificity constant kcat/Km (from one progress curve with [S] ≪ Km) confer accuracy, freedom of choices of [S], and robustness to kcat and Km globally fitted to a few progress curves. The economies of the progress curve approach make accurate kcat and Km more accessible from fluorescence measurements. PMID:17706587

  11. Bayesian inference of chemical kinetic models from proposed reactions

    KAUST Repository

    Galagali, Nikhil; Marzouk, Youssef M.

    2015-01-01

    © 2014 Elsevier Ltd. Bayesian inference provides a natural framework for combining experimental data with prior knowledge to develop chemical kinetic models and quantify the associated uncertainties, not only in parameter values but also in model

  12. Student Research in Rocket and Plume-Reaction Kinetics

    National Research Council Canada - National Science Library

    Fontijn, Arthur

    1998-01-01

    Semi-empirical configuration interaction (SECI) theory has been extended to predict activation barriers for combustion reactions of boron group halide oxidation reactions, Good agreement with experiments has been obtained...

  13. CHEMICAL REACTIONS ON ADSORBING SURFACE: KINETIC LEVEL OF DESCRIPTION

    Directory of Open Access Journals (Sweden)

    P.P.Kostrobii

    2003-01-01

    Full Text Available Based on the effective Hubbard model we suggest a statistical description of reaction-diffusion processes for bimolecular chemical reactions of gas particles adsorbed on the metallic surface. The system of transport equations for description of particles diffusion as well as reactions is obtained. We carry out the analysis of the contributions of all physical processes to the formation of diffusion coefficients and chemical reactions constants.

  14. Kinetic Monte Carlo studies of the reaction kinetics of crystal defects that diffuse one-dimensionally with occasional transverse migration

    DEFF Research Database (Denmark)

    Heinisch, H.L.; Trinkaus, H.; Singh, Bachu Narain

    2007-01-01

    The reaction kinetics of the various species of mobile defects in irradiated materials are crucially dependent on the dimensionality of their migration. Sink strengths for one-dimensionally (1D) gliding interstitial loops undergoing occasional direction changes have been described analytically...

  15. Kinetic Studies of Oxidative Coupling of Methane Reaction on Model Catalysts

    KAUST Repository

    Khan, Abdulaziz M.

    2016-01-01

    the process to be commercialized despite the fact that great number of attempts to prepare catalysts were conducted so that it can be economically viable. Due to these limitations, understanding the mechanism and kinetics of the reaction can be utilized

  16. Constrained reaction volume approach for studying chemical kinetics behind reflected shock waves

    KAUST Repository

    Hanson, Ronald K.; Pang, Genny A.; Chakraborty, Sreyashi; Ren, Wei; Wang, Shengkai; Davidson, David Frank

    2013-01-01

    We report a constrained-reaction-volume strategy for conducting kinetics experiments behind reflected shock waves, achieved in the present work by staged filling in a shock tube. Using hydrogen-oxygen ignition experiments as an example, we

  17. Steady-state cerebral glucose concentrations and transport in the human brain

    OpenAIRE

    Gruetter, R.; Ugurbil, K.; Seaquist, E. R.

    1998-01-01

    Understanding the mechanism of brain glucose transport across the blood- brain barrier is of importance to understanding brain energy metabolism. The specific kinetics of glucose transport nave been generally described using standard Michaelis-Menten kinetics. These models predict that the steady- state glucose concentration approaches an upper limit in the human brain when the plasma glucose level is well above the Michaelis-Menten constant for half-maximal transport, K(t). In experiments wh...

  18. Learning the Fundamentals of Kinetics and Reaction Engineering with the Catalytic Oxidation of Methane

    Science.gov (United States)

    Cybulskis, Viktor J.; Smeltz, Andrew D.; Zvinevich, Yury; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.

    2016-01-01

    Understanding catalytic chemistry, collecting and interpreting kinetic data, and operating chemical reactors are critical skills for chemical engineers. This laboratory experiment provides students with a hands-on supplement to a course in chemical kinetics and reaction engineering. The oxidation of methane with a palladium catalyst supported on…

  19. A kinetic model for the glucose/glycine Maillard reaction pathways

    NARCIS (Netherlands)

    Martins, S.I.F.S.; Boekel, van M.A.J.S.

    2005-01-01

    A comprehensive kinetic model for the glucose/glycine Maillard reaction is proposed based on an approach called multiresponse kinetic modelling. Special attention was paid to reactants, intermediates and end products: -fructose, N-(1-deoxy--fructos-1-yl)-glycine (DFG), 1-deoxy-2,3-hexodiulose and

  20. A kinetic study on non-catalytic reactions in hydroprocessing Boscan crude oil

    Energy Technology Data Exchange (ETDEWEB)

    A. Marafi; E. Kam; A. Stanislaus [Kuwait Institute for Scientific Research, Safat (Kuwait). Petroleum Refining Department, Petroleum Research and Studies Center

    2008-08-15

    Non-catalytic hydrothermal cracking reactions are known to associate with catalytic hydrocracking reactions. In a recent study on hydroprocessing of Boscan crude over a specific catalyst system containing three distinct catalysts, it was found that hydrodesulfurization (HDS) and hydrodemetallation (HDM) reactions continued even when the catalyst is severely deactivated. Since the reactor was packed with considerable amount of inert material besides the three catalysts, it will be advantage to determine if the inert materials can also facilitate hydroprocessing reactions. A series of kinetic experiments for the inert particles was undertaken under different space velocity and temperature conditions. The extent of catalytic and non-catalytic hydroprocessing reactions was assessed. Through statistical analysis, the initial reaction rate constant, reaction order and activation energy for various hydroprocessing reactions were then determined. The absolute average deviations (AAD) of the kinetics values obtained for inert materials are less than 10%. 25 refs., 7 figs., 4 tabs.

  1. Reactions driving conformational movements (molecular motors) in gels: conformational and structural chemical kinetics.

    Science.gov (United States)

    Otero, Toribio F

    2017-01-18

    In this perspective the empirical kinetics of conducting polymers exchanging anions and solvent during electrochemical reactions to get dense reactive gels is reviewed. The reaction drives conformational movements of the chains (molecular motors), exchange of ions and solvent with the electrolyte and structural (relaxation, swelling, shrinking and compaction) gel changes. Reaction-driven structural changes are identified and quantified from electrochemical responses. The empirical reaction activation energy (E a ), the reaction coefficient (k) and the reaction orders (α and β) change as a function of the conformational energy variation during the reaction. This conformational energy becomes an empirical magnitude. E a , k, α and β include and provide quantitative conformational and structural information. The chemical kinetics becomes structural chemical kinetics (SCK) for reactions driving conformational movements of the reactants. The electrochemically stimulated conformational relaxation model describes empirical results and some results from the literature for biochemical reactions. In parallel the development of an emerging technological world of soft, wet, multifunctional and biomimetic tools and anthropomorphic robots driven by reactions of the constitutive material, as in biological organs, can be now envisaged being theoretically supported by the kinetic model.

  2. Kinetic study of the dehydration reaction of lithium sulfate monohydrate crystals using microscopy and modeling

    Energy Technology Data Exchange (ETDEWEB)

    Lan, Shuiquan [Department of Mechanical Engineering, Eindhoven University of Technology, Den Dolech 2, 5612AZ Eindhoven (Netherlands); Zondag, Herbert [Department of Mechanical Engineering, Eindhoven University of Technology, Den Dolech 2, 5612AZ Eindhoven (Netherlands); Energy research Center of the Netherlands – ECN, P.O. Box 1, 1755ZG Petten (Netherlands); Steenhoven, Anton van [Department of Mechanical Engineering, Eindhoven University of Technology, Den Dolech 2, 5612AZ Eindhoven (Netherlands); Rindt, Camilo, E-mail: c.c.m.rindt@tue.nl [Department of Mechanical Engineering, Eindhoven University of Technology, Den Dolech 2, 5612AZ Eindhoven (Netherlands)

    2015-12-10

    Highlights: • Kinetics of Li{sub 2}SO{sub 4}·H{sub 2}O single crystals were modeled based on elementary processes. • Kinetics of nucleation and nuclei growth were studied by using optical microscopy. • A novel experiment was designed to visualize the reaction front into crystal bulk. • Fractional conversion was calculated and compared with TGA-experiments. - Abstract: Simulation of gas–solid reactions occurring in industrial processes requires a robust kinetic model to be applicable in a wide range of complicated reaction conditions. However, in literature it is often seen that even the same reaction under specific controlled conditions is interpreted with different kinetic models. In the present work, a phenomenological model based on nucleation and nuclei growth processes is presented to study the kinetics of the dehydration reaction of lithium sulfate monohydrate single crystals. The two elementary processes of the reaction, nucleation and nuclei growth, are characterized and quantified as a function of temperature by using optical microscopy experiments. The in-situ measured characteristics of the dehydration reaction provided confirmatory evidence that the rate of nucleation obeys an exponential law and the rate of nuclei growth is approximately constant. With knowledge acquired from the optical observations as inputs of the kinetic model, the fractional conversion of the dehydration reaction was calculated and compared with experimental results from thermogravimetric analysis (TGA). A satisfactory comparison was found both in isothermal and non-isothermal conditions. It is demonstrated that this knowledge-based model has a great potential to represent the gas–solid reaction kinetics in a wide range of process conditions regarding temperature, pressure and particle geometry.

  3. 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

  4. Use of Competition Kinetics with Fast Reactions of Grignard Reagents

    DEFF Research Database (Denmark)

    Holm, Torkil

    2000-01-01

    small.This is concluded from experiments in which results obtained by competition kinetics are compared with results obtained directly by flow stream procedures. A clearer picture of the reactivity ratios is obtained when the highly reactive reagent is highly diluted with its competitor. A fast reagent...

  5. Stochastic simulation of biological reactions, and its applications for studying actin polymerization.

    Science.gov (United States)

    Ichikawa, Kazuhisa; Suzuki, Takashi; Murata, Noboru

    2010-11-30

    Molecular events in biological cells occur in local subregions, where the molecules tend to be small in number. The cytoskeleton, which is important for both the structural changes of cells and their functions, is also a countable entity because of its long fibrous shape. To simulate the local environment using a computer, stochastic simulations should be run. We herein report a new method of stochastic simulation based on random walk and reaction by the collision of all molecules. The microscopic reaction rate P(r) is calculated from the macroscopic rate constant k. The formula involves only local parameters embedded for each molecule. The results of the stochastic simulations of simple second-order, polymerization, Michaelis-Menten-type and other reactions agreed quite well with those of deterministic simulations when the number of molecules was sufficiently large. An analysis of the theory indicated a relationship between variance and the number of molecules in the system, and results of multiple stochastic simulation runs confirmed this relationship. We simulated Ca²(+) dynamics in a cell by inward flow from a point on the cell surface and the polymerization of G-actin forming F-actin. Our results showed that this theory and method can be used to simulate spatially inhomogeneous events.

  6. The effects of one-dimensional glide on the reaction kinetics of interstitial clusters

    DEFF Research Database (Denmark)

    Heinisch, H.L.; Singh, B.N.; Golubov, S.I.

    2000-01-01

    is therefore 'mixed 1D/3D migration' along a 3D path consisting of 1D segments, The defect reaction kinetics under mixed 1D/3D diffusion are different from pure 1D diffusion and pure 3D diffusion, both of which can be formulated within analytical rate theory models of microstructure evolution under irradiation....... Atomic-scale kinetic Monte Carlo (kMC) defect migration simulations are used to investigate the effects of mixed 1D/3D migration on defect reaction kinetics as a guide for implementing mixed 1D/3D migration into the analytical rate theory. The functional dependence of the sink strength on the size...

  7. Kinetic isotope effects in reaction of ferment oxidation of tritium-labelled D-galactosamine

    International Nuclear Information System (INIS)

    Akulov, G.P.; Korsakova, N.A.

    1992-01-01

    Primary, secondary and intramolecular kinetic isotopic effects in reaction of ferment oxidation of D-galactosamine labelled by tritium in position 6, were measured. When comparing values of the effects with previously obtained results for similar reaction D-[6- 3 H]galactose, it was ascertained that the presence of aminogroup in galactopyranosyl mainly affects kinetics of substrate-ferment complex formation stage. The possibility to use kinetic isotope effects for increase in molar activity of D-galactosamine, labelled by tritium in position 6, is shown

  8. Modelling the Effects of Ageing Time of Starch on the Enzymatic Activity of Three Amylolytic Enzymes

    Science.gov (United States)

    Guerra, Nelson P.; Pastrana Castro, Lorenzo

    2012-01-01

    The effect of increasing ageing time (t) of starch on the activity of three amylolytic enzymes (Termamyl, San Super, and BAN) was investigated. Although all the enzymatic reactions follow michaelian kinetics, v max decreased significantly (P enzymes and the release of the reaction products to the medium. A similar effect was observed when the enzymatic reactions were carried out with unaged starches supplemented with different concentrations of gelatine [G]. The inhibition in the amylolytic activities was best mathematically described by using three modified forms of the Michaelis-Menten model, which included a term to consider, respectively, the linear, exponential, and hyperbolic inhibitory effects of t and [G]. PMID:22666116

  9. Kinetic modelling of reactions in heated disaccharide-casein systems

    NARCIS (Netherlands)

    Brands, C.M.J.; Boekel, van M.A.J.S.

    2003-01-01

    The reactions occurring in disaccharide-casein reaction mixtures during heating at 120 degreesC and pH 6.8 were studied. The existence of two main degradation routes were established: (1) Isomerisation of the aldose sugars lactose and maltose in their ketose isomers lactulose and maltulose,

  10. Transport Properties of a Kinetic Model for Chemical Reactions without Barriers

    International Nuclear Information System (INIS)

    Alves, Giselle M.; Kremer, Gilberto M.; Soares, Ana Jacinta

    2011-01-01

    A kinetic model of the Boltzmann equation for chemical reactions without energy barrier is considered here with the aim of evaluating the reaction rate and characterizing the transport coefficient of shear viscosity for the reactive system. The Chapman-Enskog solution of the Boltzmann equation is used to compute the chemical reaction effects, in a flow regime for which the reaction process is close to the final equilibrium state. Some numerical results are provided illustrating that the considered chemical reaction without energy barrier can induce an appreciable influence on the reaction rate and on the transport coefficient of shear viscosity.

  11. Diffusion and reaction in microbead agglomerates.

    Science.gov (United States)

    Nunes Kirchner, Carolina; Träuble, Markus; Wittstock, Gunther

    2010-04-01

    Scanning electrochemical microscopy has been used to analyze the flux of p-aminonophenol (PAP) produced by agglomerates of polymeric microbeads modified with galactosidase as a model system for the bead-based heterogeneous immunoassays. With the use of mixtures of enzyme-modified and bare beads in defined ratio, agglomerates with different saturation levels of the enzyme modification were produced. The PAP flux depends on the intrinsic kinetics of the galactosidase, the local availability of the substrate p-aminophenyl-beta-D-galactopyranoside (PAPG), and the external mass transport conditions in the surrounding of the agglomerate and the internal mass transport within the bead agglomerate. The internal mass transport is influenced by the diffusional shielding of the modified beads by unmodified beads. SECM in combination with optical microscopy was used to determine experimentally the external flux. These data are in quantitative agreement with boundary element simulation considering the SECM microelectrode as an interacting probe and treating the Michaelis-Menten kinetics of the enzyme as nonlinear boundary conditions with two independent concentration variables [PAP] and [PAPG]. The PAPG concentration at the surface of the bead agglomerate was taken as a boundary condition for the analysis of the internal mass transport condition as a function of the enzyme saturation in the bead agglomerate. The results of this analysis are represented as PAP flux per contributing modified bead and the flux from freely suspended galactosidase-modified beads. These numbers are compared to the same number from the SECM experiments. It is shown that depending on the enzyme saturation level a different situation can arise where either beads located at the outer surface of the agglomerate dominate the contribution to the measured external flux or where the contribution of buried beads cannot be neglected for explaining the measured external flux.

  12. SABIO-RK: A data warehouse for biochemical reactions and their kinetics

    Directory of Open Access Journals (Sweden)

    Krebs Olga

    2007-03-01

    Full Text Available Systems biology is an emerging field that aims at obtaining a system-level understanding of biological processes. The modelling and simulation of networks of biochemical reactions have great and promising application potential but require reliable kinetic data. In order to support the systems biology community with such data we have developed SABIO-RK (System for the Analysis of Biochemical Pathways - Reaction Kinetics, a curated database with information about biochemical reactions and their kinetic properties, which allows researchers to obtain and compare kinetic data and to integrate them into models of biochemical networks. SABIO-RK is freely available for academic use at http://sabio.villa-bosch.de/SABIORK/.

  13. Kinetics of subdiffusion-assisted reactions: non-Markovian stochastic Liouville equation approach

    International Nuclear Information System (INIS)

    Shushin, A I

    2005-01-01

    Anomalous specific features of the kinetics of subdiffusion-assisted bimolecular reactions (time-dependence, dependence on parameters of systems, etc) are analysed in detail with the use of the non-Markovian stochastic Liouville equation (SLE), which has been recently derived within the continuous-time random-walk (CTRW) approach. In the CTRW approach, subdiffusive motion of particles is modelled by jumps whose onset probability distribution function is of a long-tailed form. The non-Markovian SLE allows for rigorous describing of some peculiarities of these reactions; for example, very slow long-time behaviour of the kinetics, non-analytical dependence of the reaction rate on the reactivity of particles, strong manifestation of fluctuation kinetics showing itself in very slowly decreasing behaviour of the kinetics at very long times, etc

  14. Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification

    International Nuclear Information System (INIS)

    Li, Jianhua; Peng, Jianbiao; Zhang, Ya; Ji, Yuefei; Shi, Huanhuan; Mao, Liang; Gao, Shixiang

    2016-01-01

    Highlights: • Enzymatic treatment of triclosan in water by soybean and horseradish peroxidases. • pH, H_2O_2 concentration and enzyme dosage affected the removal efficiency of TCS. • The removal of TCS by SBP was more efficient than that of HRP. • K_C_A_T and K_C_A_T/K_M values for SBP toward TCS were much higher than those for HRP. • Polymers formed via radical coupling mechanism were nontoxic to the growth of alga. - Abstract: This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H_2O_2 concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H_2O_2 concentration, while the optimal pH and H_2O_2 concentration were 7.0 and 8 μM, respectively. 98% TCS was removed with only 0.1 U mL"−"1 SBP in 30 min reaction time, while an HRP dose of 0.3 U mL"−"1 was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (K_C_A_T) and catalytic efficiency (K_C_A_T/K_M) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via C−C and C−O coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water/wastewater treatment.

  15. Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jianhua; Peng, Jianbiao [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Zhang, Ya [Nanjing Institute of Environmental Sciences, Ministry of Environmental Protection of the People’s Republic of China, Nanjing 210042 (China); Ji, Yuefei [College of Resources and Environmental Science, Nanjing Agricultural University, Nanjing 210095 (China); Shi, Huanhuan; Mao, Liang [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Gao, Shixiang, E-mail: ecsxg@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China)

    2016-06-05

    Highlights: • Enzymatic treatment of triclosan in water by soybean and horseradish peroxidases. • pH, H{sub 2}O{sub 2} concentration and enzyme dosage affected the removal efficiency of TCS. • The removal of TCS by SBP was more efficient than that of HRP. • K{sub CAT} and K{sub CAT}/K{sub M} values for SBP toward TCS were much higher than those for HRP. • Polymers formed via radical coupling mechanism were nontoxic to the growth of alga. - Abstract: This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H{sub 2}O{sub 2} concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H{sub 2}O{sub 2} concentration, while the optimal pH and H{sub 2}O{sub 2} concentration were 7.0 and 8 μM, respectively. 98% TCS was removed with only 0.1 U mL{sup −1} SBP in 30 min reaction time, while an HRP dose of 0.3 U mL{sup −1} was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (K{sub CAT}) and catalytic efficiency (K{sub CAT}/K{sub M}) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via C−C and C−O coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water

  16. In vivo measurements of brain glucose transport using the reversible michaelis-menten model and simultaneous measurements of cerebral blood flow changes during hypoglycemia

    OpenAIRE

    Choi, I.-Y.; Lee, S.-P.; Kim, S.-G.; Gruetter, R.

    2001-01-01

    Glucose is the major substrate that sustains normal brain function. When the brain glucose concentration approaches zero, glucose transport across the blood-brain barrier becomes rate limiting for metabolism during, for example, increased metabolic activity and hypoglycemia. Steady-state brain glucose concentrations in α-chloralose anesthetized rats were measured noninvasively as a function of plasma glucose. The relation between brain and plasma glucose was linear at 4.5 to 30 mmol/L plasma ...

  17. At the centennial of Michaelis and Menten, competing Michaelis-Menten steps explain effect of GLP-1 on blood-brain transfer and metabolism of glucose

    DEFF Research Database (Denmark)

    Jensen, Michael Gejl; Rungby, Jørgen; Brock, Birgitte

    2014-01-01

    Glucagon-like peptide-1 (GLP-1) is a potent insulinotropic incretin hormone with pancreatic and extrapancreatic effects. Studies reveal significant effects in regions of brain tissue that regulate appetite and satiety. The effects cause that mimetics of GLP-1 serves as treatment of type 2 diabete...

  18. Generic Schemes for Single-Molecule Kinetics. 3: Self-Consistent Pathway Solutions for Nonrenewal Processes.

    Science.gov (United States)

    Piephoff, D Evan; Cao, Jianshu

    2018-04-23

    We recently developed a pathway analysis framework (paper 1) for describing single-molecule kinetics for renewal (i.e., memoryless) processes based on the decomposition of a kinetic scheme into generic structures. In our approach, waiting time distribution functions corresponding to such structures are expressed in terms of self-consistent pathway solutions and concatenated to form measurable probability distribution functions (PDFs), affording a simple way to decompose and recombine a network. Here, we extend this framework to nonrenewal processes, which involve correlations between events, and employ it to formulate waiting time PDFs, including the first-passage time PDF, for a general kinetic network model. Our technique does not require the assumption of Poissonian kinetics, permitting a more general kinetic description than the usual rate approach, with minimal topological restrictiveness. To demonstrate the usefulness of this technique, we provide explicit calculations for our general model, which we adapt to two generic schemes for single-enzyme turnover with conformational interconversion. For each generic scheme, wherein the intermediate state(s) need not undergo Poissonian decay, the functional dependence of the mean first-passage time on the concentration of an external substrate is analyzed. When conformational detailed balance is satisfied, the enzyme turnover rate (related to the mean first-passage time) reduces to the celebrated Michaelis-Menten functional form, consistent with our previous work involving a similar scheme with all rate processes, thereby establishing further generality to this intriguing result. Our framework affords a general and intuitive approach for evaluating measurable waiting time PDFs and their moments, making it a potentially useful kinetic tool for a wide variety of single-molecule processes.

  19. Kinetics of diffusion-controlled and ballistically-controlled reactions

    International Nuclear Information System (INIS)

    Redner, S.

    1995-01-01

    The kinetics of diffusion-controlled two-species annihilation, A+B → O and single-species ballistically-controlled annihilation, A+A → O are investigated. For two-species annihilation, we describe the basic mechanism that leads to the formation of a coarsening mosaic of A- and B-domains. The implications of this picture on the distribution of reactants is discussed. For ballistic annihilation, dimensional analysis shows that the concentration and rms velocity decay as c∼t -α and v∼t -β , respectively, with α+β = 1 in any spatial dimension. Analysis of the Boltzmann equation for the evolution of the velocity distribution yields accurate predictions for the kinetics. New phenomena associated with discrete initial velocity distributions and with mixed ballistic and diffusive reactant motion are also discussed. (author)

  20. On the Mathematical Structure of Balanced Chemical Reaction Networks Governed by Mass Action Kinetics

    NARCIS (Netherlands)

    Schaft, Arjan van der; Rao, Shodhan; Jayawardhana, Bayu

    2013-01-01

    Motivated by recent progress on the interplay between graph theory, dynamics, and systems theory, we revisit the analysis of chemical reaction networks described by mass action kinetics. For reaction networks possessing a thermodynamic equilibrium we derive a compact formulation exhibiting at the

  1. Kinetics of the Coupled Gas-Iron Reactions Involving Silicon and ...

    African Journals Online (AJOL)

    The kinetic study of coupled gas-iron reactions at 15600 has been carried out for the system involving liquid iron containing carbon and silicon and a gas phase consisting carbon monoxide, silicon monoxide and carbon dioxide. The coupled reactions are: (1) 200(g) = CO2 + C. (2) SiO (g) + CO (g) = Si ¸ CO (g). (3) SiO (g) + ...

  2. Microsecond time-scale kinetics of transient biochemical reactions

    NARCIS (Netherlands)

    Mitic, S.; Strampraad, M.J.F.; Hagen, W.R.; de Vries, S.

    2017-01-01

    To afford mechanistic studies in enzyme kinetics and protein folding in the microsecond time domain we have developed a continuous-flow microsecond time-scale mixing instrument with an unprecedented dead-time of 3.8 ± 0.3 μs. The instrument employs a micro-mixer with a mixing time of 2.7 μs

  3. Using ground reaction force to predict knee kinetic asymmetry following anterior cruciate ligament reconstruction.

    Science.gov (United States)

    Dai, B; Butler, R J; Garrett, W E; Queen, R M

    2014-12-01

    Asymmetries in sagittal plane knee kinetics have been identified as a risk factor for anterior cruciate ligament (ACL) re-injury. Clinical tools are needed to identify the asymmetries. This study examined the relationships between knee kinetic asymmetries and ground reaction force (GRF) asymmetries during athletic tasks in adolescent patients following ACL reconstruction (ACL-R). Kinematic and GRF data were collected during a stop-jump task and a side-cutting task for 23 patients. Asymmetry indices between the surgical and non-surgical limbs were calculated for GRF and knee kinetic variables. For the stop-jump task, knee kinetics asymmetry indices were correlated with all GRF asymmetry indices (P kinetic asymmetry indices were correlated with the peak propulsion vertical GRF and vertical GRF impulse asymmetry indices (P kinetic asymmetries and therefore may assist in optimizing rehabilitation outcomes and minimizing re-injury rates. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  4. Evaluation of sources of variation on in vitro fermentation kinetics of feedstuffs in a gas production system.

    Science.gov (United States)

    Keim, Juan P; Alvarado-Gilis, Christian; Arias, Rodrigo A; Gandarillas, Mónica; Cabanilla, Jaime

    2017-10-01

    The aim of this study was to evaluate the effect of different sources of variation in gas production technique on the in vitro gas production kinetics of feedstuffs. Triplicates of commercial concentrate, grass silage, grass hay and grass pasture were incubated in three experiments: experiment 1 assessed two agitation methods; experiment 2 evaluated different rumen inocula (pooled or different donor cows for each incubation run); and experiment 3 used Goering-Van Soest or Mould buffers for media preparation. Gas production data were fitted into the Michaelis-Menten model and then subjected to analysis of variance. Gas production (GP) at 48 h and asymptote gas production (A) were lower when bottles were continuously under horizontal movement. Time to produce half and 75% of A, and A were affected by rumen inocula, while buffer type affected time to produce half and 25% of A and GP. No interactions between substrates and sources of variation were observed, suggesting that the effects of substrates on GP parameters were not modified. It is concluded that comparison of numerical data from in vitro experiments that follow different protocols must be done carefully. However, the ranking of different substrates is more robust and less affected by the sources of variation. © 2017 Japanese Society of Animal Science.

  5. Mechanistic interpretation of glass reaction: Input to kinetic model development

    International Nuclear Information System (INIS)

    Bates, J.K.; Ebert, W.L.; Bradley, J.P.; Bourcier, W.L.

    1991-05-01

    Actinide-doped SRL 165 type glass was reacted in J-13 groundwater at 90 degree C for times up to 278 days. The reaction was characterized by both solution and solid analyses. The glass was seen to react nonstoichiometrically with preferred leaching of alkali metals and boron. High resolution electron microscopy revealed the formation of a complex layer structure which became separated from the underlying glass as the reaction progressed. The formation of the layer and its effect on continued glass reaction are discussed with respect to the current model for glass reaction used in the EQ3/6 computer simulation. It is concluded that the layer formed after 278 days is not protective and may eventually become fractured and generate particulates that may be transported by liquid water. 5 refs., 5 figs. , 3 tabs

  6. Photocatalytic Water-Splitting Reaction from Catalytic and Kinetic Perspectives

    KAUST Repository

    Hisatomi, Takashi; Takanabe, Kazuhiro; Domen, Kazunari

    2014-01-01

    Abstract: Some particulate semiconductors loaded with nanoparticulate catalysts exhibit photocatalytic activity for the water-splitting reaction. The photocatalysis is distinct from the thermal catalysis because photocatalysis involves photophysical

  7. KEMOD: A mixed chemical kinetic and equilibrium model of aqueous and solid phase geochemical reactions

    International Nuclear Information System (INIS)

    Yeh, G.T.; Iskra, G.A.

    1995-01-01

    This report presents the development of a mixed chemical Kinetic and Equilibrium MODel in which every chemical species can be treated either as a equilibrium-controlled or as a kinetically controlled reaction. The reaction processes include aqueous complexation, adsorption/desorption, ion exchange, precipitation/dissolution, oxidation/reduction, and acid/base reactions. Further development and modification of KEMOD can be made in: (1) inclusion of species switching solution algorithms, (2) incorporation of the effect of temperature and pressure on equilibrium and rate constants, and (3) extension to high ionic strength

  8. Kinetics based reaction optimization of enzyme catalysed reduction of formaldehyde to methanol with synchronous cofactor regeneration

    DEFF Research Database (Denmark)

    Marpani, Fauziah Binti; Sárossy, Zsuzsa; Pinelo, Manuel

    2017-01-01

    regeneration of the reducing equivalents during reaction is required. Herein, we report the optimization of the enzymatic conversion of formaldehyde (CHOH) to CH3 OH by alcohol dehydrogenase, the final step of the enzymatic redox reaction of CO2 to CH3 OH, with kinetically synchronous enzymatic cofactor...... regeneration using either glucose dehydrogenase (System I) or xylose dehydrogenase (System II). A mathematical model of the enzyme kinetics was employed to identify the best reaction set-up for attaining optimal cofactor recycling rate and enzyme utilization efficiency. Targeted process optimization...... experiments were conducted to verify the kinetically modelled results. Repetitive reaction cycles were shown to enhance the yield of CH3 OH, increase the total turnover number (TTN) and the biocatalytic productivity rate (BPR) value for both system I and II whilst minimizing the exposure of the enzymes...

  9. Kinetics and optimization on discoloration of dyeing wastewater by schorl-catalyzed fenton-like reaction

    Directory of Open Access Journals (Sweden)

    Xu Huan-Yan

    2014-01-01

    Full Text Available Kinetics and optimization on the discoloration of an active commercial dye, Argazol Blue BFBR (ABB by heterogeneous Fenton-like reaction catalyzed by natural schorl were investigated in this study. Kinetic investigations revealed that the first-order kinetic model was more favorable to describe the discoloration of ABB at different reaction conditions than the second-order and Behnajady-Modirshahla-Ghanbery models. The relationship between the reaction rate constant k and reaction temperature T followed the Arrhenius equation, with the apparent activation energy Ea of 51.31kJ•mol-1. The central composite design under the response surface methodology was employed for the experimental design and optimization of the ABB discoloration process. The significance of a second order polynomial model for predicting the optimal values of ABB discoloration was evaluated by the analysis of variance and 3D response surface plots for the interactions between two variables were constructed. Then, the optimum conditions were determined.

  10. Explaining the atypical reaction profiles of heme enzymes with a novel mechanistic hypothesis and kinetic treatment.

    Directory of Open Access Journals (Sweden)

    Kelath Murali Manoj

    Full Text Available Many heme enzymes show remarkable versatility and atypical kinetics. The fungal extracellular enzyme chloroperoxidase (CPO characterizes a variety of one and two electron redox reactions in the presence of hydroperoxides. A structural counterpart, found in mammalian microsomal cytochrome P450 (CYP, uses molecular oxygen plus NADPH for the oxidative metabolism (predominantly hydroxylation of substrate in conjunction with a redox partner enzyme, cytochrome P450 reductase. In this study, we employ the two above-mentioned heme-thiolate proteins to probe the reaction kinetics and mechanism of heme enzymes. Hitherto, a substrate inhibition model based upon non-productive binding of substrate (two-site model was used to account for the inhibition of reaction at higher substrate concentrations for the CYP reaction systems. Herein, the observation of substrate inhibition is shown for both peroxide and final substrate in CPO catalyzed peroxidations. Further, analogy is drawn in the "steady state kinetics" of CPO and CYP reaction systems. New experimental observations and analyses indicate that a scheme of competing reactions (involving primary product with enzyme or other reaction components/intermediates is relevant in such complex reaction mixtures. The presence of non-selective reactive intermediate(s affords alternate reaction routes at various substrate/product concentrations, thereby leading to a lowered detectable concentration of "the product of interest" in the reaction milieu. Occam's razor favors the new hypothesis. With the new hypothesis as foundation, a new biphasic treatment to analyze the kinetics is put forth. We also introduce a key concept of "substrate concentration at maximum observed rate". The new treatment affords a more acceptable fit for observable experimental kinetic data of heme redox enzymes.

  11. 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.

  12. Ab initio chemical kinetics for the HCCO + OH reaction

    Science.gov (United States)

    Mai, Tam V.-T.; Raghunath, P.; Le, Xuan T.; Huynh, Lam K.; Nam, Pham-Cam; Lin, M. C.

    2014-01-01

    The mechanism for the reaction of HCCO and OH has been investigated at different high-levels of theory. The reaction was found to occur on singlet and triplet potential energy surfaces with multiple accessible paths. Rate constants predicted by variational RRKM/ME calculations show that the reaction on both surfaces occurs primarily by barrierless OH attack at both C atoms producing excited intermediates which fragment to produce predominantly CO and 1,3HCOH with kS = 3.12 × 10-8T-0.59exp[-73.0/T] and kT = 6.29 × 10-11T0.13exp[108/T] cm3 molecule-1 s-1 at T = 300-2000 K, independent of pressure at P < 76 000 Torr.

  13. The role of chain carriers in fusion reaction kinetics

    International Nuclear Information System (INIS)

    Harms, A.A.; Krenciglowa, E.M.

    1980-01-01

    The role of chain carriers as contributors to multiplicative closed cycles in advanced fusion fuels is examined. Emphasis is placed on rate processes which can be used to characterize critical/supercritical/subcritical tendencies of arbitrary closed fusion cycles. Temporal trajectories for the chain carriers which describe both increasing and decreasing multiplicative processes have been found to exist and identified according to their fusion fuel cycle characteristics. Practical criteria to ensure the attainment of steady-state fusion reaction processes have been formulated in terms of fusion reaction rate relationships. (author)

  14. A study of butyl acetate synthesis. 4-reaction kinetics

    OpenAIRE

    Álvaro Orjuela Londoño; Fernando Leiva Lenis; Luis Alejandro Boyacá Mendivelso; Gerardo Rodríguez Niño; Luis María Carballo Suárez

    2006-01-01

    This work was aimed at studying liquid-phase acetic acid and butyl alcohol esterification reaction (P atm =0.76 Bar),using an ion exchange resin (Lewatit K-2431) as catalyst. The effect of the absence of internal and external mass transport on catalyst particles was established in the research conditions used here. A set of assays to determine the effect of catalyst load (0.5%, 1%, 2% w/w) temperature (73°C, 80°C, 87°C) and molar ratio (1:2, 1:1, 2:1 acid/alcohol) on reaction rate was carrie...

  15. Kinetics of the decomposition reaction of phosphorite concentrate

    Directory of Open Access Journals (Sweden)

    Huang Run

    2014-01-01

    Full Text Available Apatite is the raw material, which is mainly used in phosphate fertilizer, and part are used in yellow phosphorus, red phosphorus, and phosphoric acid in the industry. With the decrease of the high grade phosphorite lump, the agglomeration process is necessary for the phosphorite concentrate after beneficiation process. The decomposition behavior and the phase transformation are of vital importance for the agglomeration process of phosphorite. In this study, the thermal kinetic analysis method was used to study the kinetics of the decomposition of phosphorite concentrate. The phosphorite concentrate was heated under various heating rate, and the phases in the sample heated were examined by the X-ray diffraction method. It was found that the main phases in the phosphorite are fluorapatiteCa5(PO43F, quartz SiO2,and dolomite CaMg(CO32.The endothermic DSC peak corresponding to the mass loss caused by the decomposition of dolomite covers from 600°C to 850°C. The activation energy of the decomposition of dolomite, which increases with the increase in the extent of conversion, is about 71.6~123.6kJ/mol. The mechanism equation for the decomposition of dolomite agrees with the Valensi equation and G-B equation.

  16. Kinetics Analysis of Synthesis Reaction of Struvite With Air-Flow Continous Vertical Reactors

    Science.gov (United States)

    Edahwati, L.; Sutiyono, S.; Muryanto, S.; Jamari, J.; Bayuseno, dan A. P.

    2018-01-01

    Kinetics reaction is a knowledge about a rate of chemical reaction. The differential of the reaction rate can be determined from the reactant material or the formed material. The reaction mechanism of a reactor may include a stage of reaction occurring sequentially during the process of converting the reactants into products. In the determination of reaction kinetics, the order of reaction and the rate constant reaction must be recognized. This study was carried out using air as a stirrer as a medium in the vertical reactor for crystallization of struvite. Stirring is one of the important aspects in struvite crystallization process. Struvite crystals or magnesium ammonium phosphate hexahydrates (MgNH4PO4·6H2O) is commonly formed in reversible reactions and can be generated as an orthorhombic crystal. Air is selected as a stirrer on the existing flow pattern in the reactor determining the reaction kinetics of the crystal from the solution. The experimental study was conducted by mixing an equimolar solution of 0.03 M NH4OH, MgCl2 and H3PO4 with a ratio of 1: 1: 1. The crystallization process of the mixed solution was observed in an inside reactor at the flow rate ranges of 16-38 ml/min and the temperature of 30°C was selected in the study. The air inlet rate was kept constant at 0.25 liters/min. The pH solution was adjusted to be 8, 9 and 10 by dropping wisely of 1 N KOH solution. The crystallization kinetics was examined until the steady state of the reaction was reached. The precipitates were filtered and dried at a temperature for subsequent material characterization, including Scanning Electron Microscope (SEM) and XRD (X-Ray diffraction) method. The results show that higher flow rate leads to less mass of struvite.

  17. Online Measurement of Oxygen-Dependent Enzyme Reaction Kinetics

    DEFF Research Database (Denmark)

    Meissner, Murray Peter; Nordblad, Mathias; Woodley, John M

    2018-01-01

    accurate measurement of the oxygen mass balance in the gas-phase of a reactor. The method was successfully validated and demonstrated using two model reactions: firstly the oxidation of glucose by glucose oxidase and secondly the Baeyer-Villiger oxidation of macrocyclic ketones to lactones. Initial...

  18. The kinetics of substitution reaction of oxydiacetate and ...

    Indian Academy of Sciences (India)

    molar ratio 1:1 and the ternary complex Cu(R)B were recorded to confirm that ... tion, the values of the rate constants were determined. Figure 2. .... Table 4. The free enthalpy of activation values for the substitution reaction of CuODA with bipy.

  19. Kinetics of thermal decomposition and kinetics of substitution reaction of nano uranyl Schiff base complexes

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Zeinali, A.; Dušek, Michal; Eigner, Václav

    2014-01-01

    Roč. 46, č. 12 (2014), s. 718-729 ISSN 0538-8066 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl * Schiff base * kinetics * anticancer activity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.517, year: 2014

  20. 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

  1. Investigation of the kinetics of the reactions of oxidation, nitration, and hydrogenation of uranium

    International Nuclear Information System (INIS)

    Adda, Y.

    1955-06-01

    Various physico-chemical methods have been used to investigate the kinetics of the oxidation hydridation and nitridation of uranium. The experimental results show that the kinetics of these reactions are influenced by many factors also the Pilling and Bedworth rule is valid only under very limited conditions. The disagreement between this rule and the experimental results could be explained by the existence of numerous mechanical faults in the compounds obtained by the dry corrosion of the metal. (author) [fr

  2. An investigation of the general regularity of size dependence of reaction kinetics of nanoparticles

    International Nuclear Information System (INIS)

    Cui, Zixiang; Duan, Huijuan; Xue, Yongqiang; Li, Ping

    2015-01-01

    In the processes of preparation and application of nanomaterials, the chemical reactions of nanoparticles are often involved, and the size of nanoparticles has dramatic influence on the reaction kinetics. Nevertheless, there are many conflicts on regularities of size dependence of reaction kinetic parameters, and these conflicts have not been explained so far. In this paper, taking the reaction of nano-ZnO (average diameter is from 20.96 to 53.31 nm) with acrylic acid solution as a system, the influence regularities of the particle size on the kinetic parameters were researched. The regularities were consistent with that in most literatures, but inconsistent with that in a few of literatures, the reasons for the conflicts were interpreted. The reasons can be attributed to two factors: one is improper data processing for fewer data points, and the other is the difference between solid particles and porous particles. A general regularity of the size dependence of reaction kinetics for solid particles was obtained. The regularity shows that with the size of nanoparticles decreasing, the rate constant and the reaction order increase, while the apparent activation energy and the pre-exponential factor decrease; and the relationships of the logarithm of rate constant, the logarithm of pre-exponential factor, and the apparent activation energy to the reciprocal of the particle size are linear, respectively

  3. Optimization and kinetic studies of sea mango (Cerbera odollam) oil for biodiesel production via supercritical reaction

    International Nuclear Information System (INIS)

    Ang, Gaik Tin; Ooi, San Nee; Tan, Kok Tat; Lee, Keat Teong; Mohamed, Abdul Rahman

    2015-01-01

    Highlights: • Sea mango oil as feedstock for biodiesel via non-catalytic supercritical reaction. • Extracted sea mango oil with high FFA could produce high yield of FAME. • Employment of Response Surface Methodology for optimization of FAME. • Kinetic study for reversible transesterification and esterification reactions. - Abstract: Sea mango (Cerbera odollam) oil, which is rich in free fatty acids, was utilized to produce fatty acid methyl esters (FAME) via supercritical transesterification reaction. Sea mango oil was extracted from seeds and was subsequently reacted with methanol in a batch-type supercritical reactor. Response surface methodology (RSM) analysis was used to optimize important parameters, including reaction temperature, reaction time and the molar ratio of methanol to oil. The optimum conditions were found as 380 °C, 40 min and 45:1 mol/mol, respectively, to achieve 78% biodiesel content. The first kinetic modelling of FAME production from sea mango oil incorporating reversible transesterification and reversible esterification was verified simultaneously. The kinetic parameters, including reaction rate constants, k, the pre-exponential constant, A, and the activation energy, Ea, for transesterification and esterification were determined using an ordinary differential equation (ODE45) solver. The highest activation energy of 40 kJ/mol and the lowest reaction rate constant of 2.50 × 10 −5 dm 3 /mol s verified that the first stepwise reaction of TG to produce DG was the rate-limiting step

  4. Multiresponse kinetic modelling of Maillard reaction and caramelisation in a heated glucose/wheat flour system.

    Science.gov (United States)

    Kocadağlı, Tolgahan; Gökmen, Vural

    2016-11-15

    The study describes the kinetics of the formation and degradation of α-dicarbonyl compounds in glucose/wheat flour system heated under low moisture conditions. Changes in the concentrations of glucose, fructose, individual free amino acids, lysine and arginine residues, glucosone, 1-deoxyglucosone, 3-deoxyglucosone, 3,4-dideoxyglucosone, 5-hydroxymethyl-2-furfural, glyoxal, methylglyoxal and diacetyl concentrations were determined to form a multiresponse kinetic model for isomerisation and degradation reactions of glucose. Degradation of Amadori product mainly produced 1-deoxyglucosone. Formation of 3-deoxyglucosone proceeded directly from glucose and also Amadori product degradation. Glyoxal formation was predominant from glucosone while methylglyoxal and diacetyl originated from 1-deoxyglucosone. Formation of 5-hydroxymethyl-2-furfural from fructose was found to be a key step. Multi-response kinetic modelling of Maillard reaction and caramelisation simultaneously indicated quantitatively predominant parallel and consecutive pathways and rate limiting steps by estimating the reaction rate constants. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Kinetic parameters of hydroprocessing reactions in a flow reactor

    Energy Technology Data Exchange (ETDEWEB)

    Raychaudhuri, U.; Banerjee, T.S.; Ghar, R.N. (Indian Institute of Technology, Kharagpur (India))

    1994-01-01

    The change in distillation properties of a blend of light and heavy distillates over a commercial hydrotreating catalyst was studied using a small packed bed reactor. The results were interpreted assuming a pseudo-component model that took into account the physical and chemical complexity of the system. A first order series-parallel reaction mechanism was found to be valid for the operating conditions involved. Pore diffusion effects were also taken into consideration. 8 refs., 7 figs., 1 tab.

  6. Chlorination of tramadol: Reaction kinetics, mechanism and genotoxicity evaluation.

    Science.gov (United States)

    Cheng, Hanyang; Song, Dean; Chang, Yangyang; Liu, Huijuan; Qu, Jiuhui

    2015-12-01

    Tramadol (TRA) is one of the most detected analgesics in environmental matrices, and it is of high significance to study the reactivity of TRA during chlorination considering its potential toxicity to the environment. The chlorine/TRA reaction is first order with respect to the TRA concentration, and a combination of first-order and second-order with respect to chlorine concentration. The pH dependence of the observed rate constants (kobs) showed that the TRA oxidation reactivity increased with increasing pH. kobs can be quantitatively described by considering all active species including Cl2, Cl2O and HOCl, and the individual rate constants of HOCl/TRA(0), HOCl/TRAH(+), Cl2/TRA and Cl2O/TRA reactions were calculated to be (2.61±0.29)×10(3)M(-1)s(-1), 14.73±4.17M(-1)s(-1), (3.93±0.34)×10(5)M(-1)s(-1) and (5.66±1.83)×10(6)M(-1)s(-1), respectively. Eleven degradation products were detected with UPLC-Q-TOF-MS, and the corresponding structures of eight products found under various pH conditions were proposed. The amine group was proposed to be the initial attack site under alkaline pH conditions, where reaction of the deprotonated amine group with HOCl is favorable. Under acidic and neutral pH conditions, however, two possible reaction pathways were proposed. One is an electrophilic substitution on the aromatic ring, and another is an electrophilic substitution on the nitrogen, leading to an N-chlorinated intermediate, which can be further oxidized. Finally, the SOS/umu test showed that the genotoxicity of TRA chlorination products increased with increasing dosage of chlorine, which was mostly attributed to the formation of some chlorine substitution products. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. 1D to 3D diffusion-reaction kinetics of defects in crystals

    DEFF Research Database (Denmark)

    Trinkaus, H.; Heinisch, H.L.; Barashev, A.V.

    2002-01-01

    Microstructural features evolving in crystalline solids from diffusion-reaction kinetics of mobile components depend crucially on the dimension of the underlying diffusion process which is commonly assumed to be three-dimensional (3D). In metals, irradiation-induced displacement cascades produce...... clusters of self-interstitials performing 1D diffusion. Changes between equivalent 1D diffusion paths and transversal diffusion result in diffusion-reaction kinetics between one and three dimensions. An analytical approach suggests a single-variable function (master curve) interpolating between the 1D...

  8. Configuration of a pulse radiolysis system for the study of gas-phase reactions and kinetic investigations of the reactions of hydroxyl radicals with methyl and ethyl radicals

    International Nuclear Information System (INIS)

    Fagerstroem, K.

    1993-01-01

    The work that is presented in this thesis deals with the assembling and testing of a pulse radiolysis system for kinetic studies of gas-phase reactions as well as with the kinetics of the gas-phase reactions of hydroxyl radicals with methyl and ethyl radicals. These radicals are very important as these are formed at an early stage in hydrocarbon combustion processes. The two studied reactions are key reactions in those processes. (6 refs., 4 figs., 2 tabs.)

  9. Reaction diffusion and solid state chemical kinetics handbook

    CERN Document Server

    Dybkov, V I

    2010-01-01

    This monograph deals with a physico-chemical approach to the problem of the solid-state growth of chemical compound layers and reaction-diffusion in binary heterogeneous systems formed by two solids; as well as a solid with a liquid or a gas. It is explained why the number of compound layers growing at the interface between the original phases is usually much lower than the number of chemical compounds in the phase diagram of a given binary system. For example, of the eight intermetallic compounds which exist in the aluminium-zirconium binary system, only ZrAl3 was found to grow as a separate

  10. Glycerol acetals, kinetic study of the reaction between glycerol and formaldehyde

    International Nuclear Information System (INIS)

    Agirre, I.; Garcia, I.; Requies, J.; Barrio, V.L.; Gueemez, M.B.; Cambra, J.F.; Arias, P.L.

    2011-01-01

    The acetalization reaction between glycerol and formaldehyde using Amberlyst 47 acidic ion exchange resin was studied. These acetals can be obtained from renewable sources (bioalcohols and bioalcohol derived aldehydes) and seem to be good candidates for different applications such as oxygenated diesel additives. A preliminary kinetic study was performed in a batch stirred tank reactor studying the influence of different process parameters like temperature, feed composition and the stirring speed. A pseudo homogenous kinetic model able to explain the reaction mechanism was adjusted. Thus, the corresponding order of reaction was determined. Amberlyst 47 acidic ion exchange resin showed a fairly good behavior allowing 100% of selectivity towards acetals formation. However, the studied acetalization reaction showed high thermodynamic limitations achieving glycerol conversions around 50% using a stoichiometric feed ratio at 353 K. The product is a mixture of two isomers (1,3-Dioxan-5-ol and 1,3-dioxolane-4-methanol) and the conversion of 1,3-dioxolane-4-methanol into 1,3-Dioxan-5-ol was also observed. -- Highlights: → The reaction between glycerol and acetaldehyde shows thermodynamic limitations. → Amberlyst 47 ion exchange resins show 100% of selectivity. → A pseudo-homogeneous kinetic model is able to predict the reaction progress. → Isomerization reactions were observed from dioxalanes to dioxanes.

  11. 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.

  12. Self-triggering reaction kinetics between nitrates and aluminium powder

    International Nuclear Information System (INIS)

    Demichela, Micaela

    2007-01-01

    During the night between the 19 and 20 September 2003, a loud explosion occurred at about 3 km from the town of Carignano that was clearly heard at a distance of some tens of kilometres. The explosion almost completely destroyed most of the laboratories of the Panzera Company that were used for the production of fireworks. The results of the research activities that were carried out using a differential scanning calorimeter (DSC) on the same raw materials that made up the pyrotechnical mixture that exploded are reported in this paper. This activity was carried out to identify the dynamics of the accident. It proved possible to verify how the event was produced because of a slow exothermic reaction which, after about 8 h, caused the self-triggering of 120 kg of finished product. The detonation can therefore be put down to a runaway reaction in the solid phase, whose primogenial causes can be attributed to a still craftsman type production system, not conformed to the rigorous controls and inspections as those required by a safety management system for major risk plants, as the Panzera Company was

  13. [Investigations on the physiology of the glands of carnivorous plants : IV. The kinetics of chloride secretion by the gland tissue of Nepenthes].

    Science.gov (United States)

    Lüttge, U

    1966-03-01

    The transport of chloride in isolated tissue from Nepenthes pitchers was investigated using (36)Cl(-), an Aminco-Cotlove chloride-titrator for the determinations of Cl(-) concentrations, and KCN and AsO 4 (-) -as metabolic inhibitors.The tissue was brought in contact with different experimental solutions (=medium). The surface corresponding to the outside of the pitchers was cut with a razor blade to remove the cutinized epidermal layer. At this surface the Cl(-) uptake from the medium is a metabolic process which depends on the Cl(-)-concentration of the medium in a manner that corresponds to the MICHAELIS-MENTEN kinetics. The Michaelis-constant of this transport step was 3×10(-2)M. The Cl(-)-efflux into the medium, however, is a passive process.The opposite surface of the tissue slices (corresponding to the inside of the pitchers) carries the glands. The chloride secretion taking place here is also dependent on metabolism. In vitro it occurs even when a high gradient of chloride concentration has been set up between the medium and the solution which is in contact with the glands. In vivo the Cl(-)-concentration of the pitcher fluid and the amount of Cl(-) per gram of tissue water are almost equal.The rôle of chloride in the physiology of Nepenthes is still under investigation, A correlation between the chloride content of the pitcher fluid and its enzymatic activity (Casein-test), however, could already be demonstrated.

  14. Comparative study on ion-isotopic exchange reaction kinetics by application of tracer technique

    International Nuclear Information System (INIS)

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

    2007-01-01

    The radioactive isotopes 131 I and 82 Br were used to trace the ion-isotopic exchange reactions using industrial grade ion exchange resins Amberlite IRA-400. The experiments were performed to understand the effect of temperature and concentration of ionic solution on kinetics of exchange reactions. Both the exchange reactions were greatly influenced by rise in temperature, which result in higher percentage of ions exchanged. For bromide ion-isotopic exchange reactions, the calculated values of specific reaction rate/min -1 , and amount of ions exchanged/mmol were obtained higher than that for iodide ion-isotopic exchange reactions under identical experimental conditions. The observed variation in the results for two ion-isotopic exchange reactions was due to the difference in the ionic size of bromide and iodide ions. (orig.)

  15. Kinetic characterization of a novel acid ectophosphatase from Enterobacter asburiae.

    Science.gov (United States)

    Sato, Vanessa Sayuri; Galdiano Júnior, Renato F; Rodrigues, Gisele Regina; Lemos, Eliana G M; Pizauro Junior, João Martins

    2016-02-01

    Expression of acid ectophosphatase by Enterobacter asburiae, isolated from Cattleya walkeriana (Orchidaceae) roots and identified by the 16S rRNA gene sequencing analysis, was strictly regulated by phosphorus ions, with its optimal activity being observed at an inorganic phosphate concentration of 7 mM. At the optimum pH 3.5, intact cells released p-nitrophenol at a rate of 350.76 ± 13.53 nmol of p-nitrophenolate (pNP)/min/10(8) cells. The membrane-bound enzyme was obtained by centrifugation at 100,000 × g for 1 h at 4 °C. p-Nitrophenylphosphate (pNPP) hydrolysis by the enzyme follows "Michaelis-Menten" kinetics with V = 61.2 U/mg and K0.5 = 60 μM, while ATP hydrolysis showed V = 19.7 U/mg, K0.5 = 110 μM, and nH = 1.6 and pyrophosphate hydrolysis showed V = 29.7 U/mg, K0.5 = 84 μM, and nH = 2.3. Arsenate and phosphate were competitive inhibitors with K i = 0.6 mM and K i = 1.8 mM, respectively. p-Nitrophenyl phosphatase (pNPPase) activity was inhibited by vanadate, while p-hydroxymercuribenzoate, EDTA, calcium, copper, and cobalt had no inhibitory effects. Magnesium ions were stimulatory (K0.5 = 2.2 mM and nH = 0.5). Production of an acid ectophosphatase can be a mechanism for the solubilization of mineral phosphates by microorganisms such as Enterobacter asburiae that are versatile in the solubilization of insoluble minerals, which, in turn, increases the availability of nutrients for plants, particularly in soils that are poor in phosphorus.

  16. Metabolomics on integrated circuit

    OpenAIRE

    Cheah, Boon Chong; MacDonald, Alasdair I.; Barrett, Michael P.; Cumming, David R.S.

    2017-01-01

    We have demonstrated a chip-based diagnostics tool for the quantification of metabolites, using specific enzymes, to study enzyme kinetics and calculate the Michaelis-Menten constant. An array of 256×256 ion-sensitive field effect transistors (ISFETs) fabricated in a complementary metal oxide semiconductor (CMOS) process is used for this prototype. We have used hexokinase enzyme reaction on the ISFET CMOS chip with glucose concentration in the physiological range of 0.05 mM – 231 mM and succe...

  17. Conductometric Studies Of Kinetics Of Ionic Reaction Between Ag And Cl- In Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Md. Rezwan Miah

    2017-01-01

    Full Text Available In the present report conductometric studies on the kinetic of formation of AgCl by ionic reaction between Ag and Clamp61485 in aqueous solution have been presented. The order of the mentioned reaction was determined by a new conductometric approach using half-life method. The obtained result showed that the reaction follows a second-order kinetics. The second-order rate constant of the reaction was obtained conductometrically using different initial concentrations of the reactants in the range of 2.5-5.0 mM. The average value of the rate constant was obtained as 20.648 L molamp614851 samp614851 at 25 amp61616C.

  18. Thermo-Kinetic Investigation of Comparative Ligand Effect on Cysteine Iron Redox Reaction

    Directory of Open Access Journals (Sweden)

    Masood Ahmad Rizvi

    2015-03-01

    Full Text Available Transition metal ions in their free state bring unwanted biological oxidations generating oxidative stress. The ligand modulated redox potential can be indispensable in prevention of such oxidative stress by blocking the redundant bio-redox reactions. In this study we investigated the comparative ligand effect on the thermo-kinetic aspects of biologically important cysteine iron (III redox reaction using spectrophotometric and potentiometric methods. The results were corroborated with the complexation effect on redox potential of iron(III-iron(II redox couple. The selected ligands were found to increase the rate of cysteine iron (III redox reaction in proportion to their stability of iron (II complex (EDTA < terpy < bipy < phen. A kinetic profile and the catalytic role of copper (II ions by means of redox shuttle mechanism for the cysteine iron (III redox reaction in presence of 1,10-phenanthroline (phen ligand is also reported.

  19. Reaction kinetics of resveratrol with tert-butoxyl radicals

    International Nuclear Information System (INIS)

    Džeba, Iva; Pedzinski, Tomasz; Mihaljević, Branka

    2012-01-01

    The rate constant for the reaction of t-butoxyl radicals with resveratrol was studied under pseudo-first order conditions. The rate constant was determined by measuring the phenoxyl radical formation rate at 390 nm as function of resveratrol concentration in acetonitrile. The rate constant was determined to be 6.5×10 8 M −1 s −1 . This high value indicates the high reactivity consistent with the strong antioxidant activity of resveratrol. - Highlights: ► tert-butoxyl radicals were generated directly using laser flash photolysis. ► Rate constant was determined by the phenoxyl radical formation rate in acetonitrile. ► Rate constant was determined to be 6.5×10 8 M −1 s −1 .

  20. 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...

  1. Thermo-Kinetic Investigation of Comparative Ligand Effect on Cysteine Iron Redox Reaction

    OpenAIRE

    Rizvi, Masood Ahmad; Teshima, Norio; Maqsood, Syed Raashid; Akhoon, Showket Ahmad; Peerzada, Ghulam Mustafa

    2015-01-01

    Transition metal ions in their free state bring unwanted biological oxidations generating oxidative stress. The ligand modulated redox potential can be indispensable in prevention of such oxidative stress by blocking the redundant bio-redox reactions. In this study we investigated the comparative ligand effect on the thermo-kinetic aspects of biologically important cysteine iron (III) redox reaction using spectrophotometric and potentiometric methods. The results were corroborated...

  2. Kinetic modeling and fitting software for interconnected reaction schemes: VisKin.

    Science.gov (United States)

    Zhang, Xuan; Andrews, Jared N; Pedersen, Steen E

    2007-02-15

    Reaction kinetics for complex, highly interconnected kinetic schemes are modeled using analytical solutions to a system of ordinary differential equations. The algorithm employs standard linear algebra methods that are implemented using MatLab functions in a Visual Basic interface. A graphical user interface for simple entry of reaction schemes facilitates comparison of a variety of reaction schemes. To ensure microscopic balance, graph theory algorithms are used to determine violations of thermodynamic cycle constraints. Analytical solutions based on linear differential equations result in fast comparisons of first order kinetic rates and amplitudes as a function of changing ligand concentrations. For analysis of higher order kinetics, we also implemented a solution using numerical integration. To determine rate constants from experimental data, fitting algorithms that adjust rate constants to fit the model to imported data were implemented using the Levenberg-Marquardt algorithm or using Broyden-Fletcher-Goldfarb-Shanno methods. We have included the ability to carry out global fitting of data sets obtained at varying ligand concentrations. These tools are combined in a single package, which we have dubbed VisKin, to guide and analyze kinetic experiments. The software is available online for use on PCs.

  3. Kinetic studies on the reaction between dicyanocobinamide and hypochlorous acid.

    Directory of Open Access Journals (Sweden)

    Dhiman Maitra

    Full Text Available Hypochlorous acid (HOCl is a potent oxidant generated by myeloperoxidase (MPO, which is an abundant enzyme used for defense against microbes. We examined the potential role of HOCl in corrin ring destruction and subsequent formation of cyanogen chloride (CNCl from dicyanocobinamide ((CN2-Cbi. Stopped-flow analysis revealed that the reaction consists of at least three observable steps, including at least two sequential transient intermediates prior to corrin ring destruction. The first two steps were attributed to sequential replacement of the two cyanide ligands with hypochlorite, while the third step was the destruction of the corrin ring. The formation of (OCl(CN-Cbi and its conversion to (OCl2-Cbi was fitted to a first order rate equation with second order rate constants of 0.002 and 0.0002 µM(-1 s(-1, respectively. The significantly lower rate of the second step compared to the first suggests that the replacement of the first cyanide molecule by hypochlorite causes an alteration in the ligand trans effects changing the affinity and/or accessibility of Co toward hypochlorite. Plots of the apparent rate constants as a function of HOCl concentration for all the three steps were linear with Y-intercepts close to zero, indicating that HOCl binds in an irreversible one-step mechanism. Collectively, these results illustrate functional differences in the corrin ring environments toward binding of diatomic ligands.

  4. Modelling and simulation of a transketolase mediated reaction: Sensitivity analysis of kinetic parameters

    DEFF Research Database (Denmark)

    Sayar, N.A.; Chen, B.H.; Lye, G.J.

    2009-01-01

    In this paper we have used a proposed mathematical model, describing the carbon-carbon bond format ion reaction between beta-hydroxypyruvate and glycolaldehyde to synthesise L-erythrulose, catalysed by the enzyme transketolase, for the analysis of the sensitivity of the process to its kinetic...

  5. Flow chemistry kinetic studies reveal reaction conditions for ready access to unsymmetrical trehalose analogues.

    Science.gov (United States)

    Patel, Mitul K; Davis, Benjamin G

    2010-10-07

    Monofunctionalization of trehalose, a widely-found symmetric plant disaccharide, was studied in a microreactor to give valuable kinetic insights that have allowed improvements in desymmetrization yields and the development of a reaction sequence for large scale monofunctionalizations that allow access to probes of trehalose's biological function.

  6. Kinetic isotope effect in the reaction of dehydration of fructose into 5-hydroxymethylfurfural

    International Nuclear Information System (INIS)

    Grin', S.A.; Tsimbaliev, S.R.; Gel'fand, S.Yu.

    1993-01-01

    Kinetic isotopic effect in the reaction of fructose dehydration into 5- hydroxymethylfurfural was determined. The results suggest hydrogen participation in the limiting stage of the process. The assumption that proton addition to 4, 5, 6 -trihydroxy - 2- on - hexal is the limiting stage is made

  7. Variable elimination in chemical reaction networks with mass-action kinetics

    DEFF Research Database (Denmark)

    Feliu, Elisenda; Wiuf, C.

    2012-01-01

    We consider chemical reaction networks taken with mass-action kinetics. The steady states of such a system are solutions to a system of polynomial equations. Even for small systems the task of finding the solutions is daunting. We develop an algebraic framework and procedure for linear elimination...

  8. On the graph and systems analysis of reversible chemical reaction networks with mass action kinetics

    NARCIS (Netherlands)

    Rao, Shodhan; Jayawardhana, Bayu; Schaft, Arjan van der

    2012-01-01

    Motivated by the recent progresses on the interplay between the graph theory and systems theory, we revisit the analysis of reversible chemical reaction networks described by mass action kinetics by reformulating it using the graph knowledge of the underlying networks. Based on this formulation, we

  9. Optically Controlled Electron-Transfer Reaction Kinetics and Solvation Dynamics : Effect of Franck-Condon States

    NARCIS (Netherlands)

    Gupta, Kriti; Patra, Aniket; Dhole, Kajal; Samanta, Alok Kumar; Ghosh, Swapan K.

    2017-01-01

    Experimental results for optically controlled electron-transfer reaction kinetics (ETRK) and nonequilibrium solvation dynamics (NESD) of Coumarin 480 in DMPC vesicle show their dependence on excitation wavelength λex. However, the celebrated Marcus theory and linear-response-theory-based approaches

  10. Toward a Kinetic Model for Acrylamide Formation in a Glucose-Asparagine Reaction System

    NARCIS (Netherlands)

    Knol, J.J.; Loon, W.A.M.; Linssen, J.P.H.; Ruck, A.L.; Boekel, van M.A.J.S.

    2005-01-01

    A kinetic model for the formation of acrylamide in a glucose-asparagine reaction system is pro-posed. Equimolar solutions (0.2 M) of glucose and asparagine were heated at different tempera-tures (120-200 C) at pH 6.8. Besides the reactants, acrylamide, fructose, and melanoidins were quantified after

  11. The renneting of milk : a kinetic study of the enzymic and aggregation reactions

    NARCIS (Netherlands)

    Hooydonk, van A.C.M.

    1987-01-01

    The rennet-induced clotting of milk was studied under various conditions. The kinetics of the enzymic and aggregation reactions was analysed separately and, where possible, related to the physico-chemical properties of the casein micelle and its environment.

    The effects of important

  12. Determining Li+-Coupled Redox Targeting Reaction Kinetics of Battery Materials with Scanning Electrochemical Microscopy.

    Science.gov (United States)

    Yan, Ruiting; Ghilane, Jalal; Phuah, Kia Chai; Pham Truong, Thuan Nguyen; Adams, Stefan; Randriamahazaka, Hyacinthe; Wang, Qing

    2018-02-01

    The redox targeting reaction of Li + -storage materials with redox mediators is the key process in redox flow lithium batteries, a promising technology for next-generation large-scale energy storage. The kinetics of the Li + -coupled heterogeneous charge transfer between the energy storage material and redox mediator dictates the performance of the device, while as a new type of charge transfer process it has been rarely studied. Here, scanning electrochemical microscopy (SECM) was employed for the first time to determine the interfacial charge transfer kinetics of LiFePO 4 /FePO 4 upon delithiation and lithiation by a pair of redox shuttle molecules FcBr 2 + and Fc. The effective rate constant k eff was determined to be around 3.70-6.57 × 10 -3 cm/s for the two-way pseudo-first-order reactions, which feature a linear dependence on the composition of LiFePO 4 , validating the kinetic process of interfacial charge transfer rather than bulk solid diffusion. In addition, in conjunction with chronoamperometry measurement, the SECM study disproves the conventional "shrinking-core" model for the delithiation of LiFePO 4 and presents an intriguing way of probing the phase boundary propagations induced by interfacial redox reactions. This study demonstrates a reliable method for the kinetics of redox targeting reactions, and the results provide useful guidance for the optimization of redox targeting systems for large-scale energy storage.

  13. Investigation of Coal-biomass Catalytic Gasification using Experiments, Reaction Kinetics and Computational Fluid Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Battaglia, Francine [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Agblevor, Foster [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Klein, Michael [Univ. of Delaware, Newark, DE (United States); Sheikhi, Reza [Northeastern Univ., Boston, MA (United States)

    2015-12-31

    A collaborative effort involving experiments, kinetic modeling, and computational fluid dynamics (CFD) was used to understand co-gasification of coal-biomass mixtures. The overall goal of the work was to determine the key reactive properties for coal-biomass mixed fuels. Sub-bituminous coal was mixed with biomass feedstocks to determine the fluidization and gasification characteristics of hybrid poplar wood, switchgrass and corn stover. It was found that corn stover and poplar wood were the best feedstocks to use with coal. The novel approach of this project was the use of a red mud catalyst to improve gasification and lower gasification temperatures. An important results was the reduction of agglomeration of the biomass using the catalyst. An outcome of this work was the characterization of the chemical kinetics and reaction mechanisms of the co-gasification fuels, and the development of a set of models that can be integrated into other modeling environments. The multiphase flow code, MFIX, was used to simulate and predict the hydrodynamics and co-gasification, and results were validated with the experiments. The reaction kinetics modeling was used to develop a smaller set of reactions for tractable CFD calculations that represented the experiments. Finally, an efficient tool was developed, MCHARS, and coupled with MFIX to efficiently simulate the complex reaction kinetics.

  14. Gas phase polymerization of propylene. Reaction kinetics and molecular weight distribution

    NARCIS (Netherlands)

    Meier, G.B.; Weickert, G.; van Swaaij, Willibrordus Petrus Maria

    2001-01-01

    Gas-phase polymerizations have been executed at different temperatures, pressures, and hydrogen concentrations using Me2Si[Ind]2ZrCl2 / methylaluminoxane / SiO2(Pennsylvania Quarts) as a catalyst. The reaction rate curves have been described by a kinetic model, which takes into account the initially

  15. Kinetic investigation of the chlorine reduction reaction on electrochemically oxidised ruthenium

    International Nuclear Information System (INIS)

    Thomassen, M.; Karlsen, C.; Borresen, B.; Tunold, R.

    2006-01-01

    The rate and mechanism of the electroreduction of chlorine on electrooxidised ruthenium has been investigated with focus on the effect of solution pH. Current/potential curves for the reduction process in solutions with constant chloride concentration of 1.0 mol dm -3 and varying H + concentration have been obtained with the use of the rotating disk electrode technique (RDE). It was found that the chlorine reduction rate is highly inhibited in solutions with high H + concentrations and that it can be satisfactorily described by the Erenburg mechanism, previously suggested for the chlorine evolution on RuO 2 and RTO. The expression of the kinetic current as a function of chlorine and H + concentration was obtained by solving the elementary rate equations of the kinetic mechanism. The kinetic constants obtained from the correlation of the kinetic current expression to the experimental data were used to simulate the dependence of the surface coverages and elementary reaction rates on overpotential

  16. The redox reaction kinetics of Sinai ore for chemical looping combustion applications

    International Nuclear Information System (INIS)

    Ksepko, Ewelina; Babiński, Piotr; Nalbandian, Lori

    2017-01-01

    Highlights: • Redox reaction kinetics of Fe-Mn-rich Sinai ore was determined by TGA. • The most suitable model for reduction was D3, while R3 for oxidation. • Activation energies 35.3 and 16.70 kJ/mole were determined for reduction and oxidation. • Repetitive redox reactions favor the formation of spinel phases in Sinai ore. • Multiple redox cycles induce formation of extensive porosity of the particles. - Abstract: The objective of this work was to study the use of Sinai ore, a Fe–Mn-based ore from Egypt, as a low-cost oxygen carrier (OC) in Chemical Looping Combustion (CLC). The Sinai ore was selected because it possesses relatively high amounts of iron and manganese oxides. Furthermore, those oxides have low cost, very favorable environmental and thermodynamic properties for the CLC process. The performance of the Sinai ore as an OC in CLC was compared to that of ilmenite (Norway Tellnes mine), the most extensively studied naturally occurring Fe-based mineral. The kinetics of the reduction and oxidation reactions with the two minerals were studied using a thermogravimetric analyzer (TGA). Experiments were conducted under isothermal conditions, with multiple redox cycles, at temperatures between 750 and 950 °C. For the reduction and oxidation reactions, different concentrations of CH_4 (10–25 vol.%) and O_2 (5–20 vol.%) were applied, respectively. The kinetic parameters, such as the activation energy (E_a), pre-exponential factor (A_0), and reaction order (n), were determined for the redox reactions. Furthermore, models of the redox reactions were selected by means of a model-fitting method. For the Sinai ore, the D3 model (3-dimensional diffusion) was suitable for modeling reduction reaction kinetics. The calculated E_a was 35.3 kJ/mole, and the reaction order was determined to be approximately 0.76. The best fit for the oxidation reaction was obtained for the R3 model (shrinking core). The oxidation (regeneration) reaction E_a was equal to 16

  17. Bench-scale Kinetics Study of Mercury Reactions in FGD Liquors

    Energy Technology Data Exchange (ETDEWEB)

    Gary Blythe; John Currie; David DeBerry

    2008-03-31

    This document is the final report for Cooperative Agreement DE-FC26-04NT42314, 'Kinetics Study of Mercury Reactions in FGD Liquors'. The project was co-funded by the U.S. DOE National Energy Technology Laboratory and EPRI. The objective of the project has been to determine the mechanisms and kinetics of the aqueous reactions of mercury absorbed by wet flue gas desulfurization (FGD) systems, and develop a kinetics model to predict mercury reactions in wet FGD systems. The model may be used to determine optimum wet FGD design and operating conditions to maximize mercury capture in wet FGD systems. Initially, a series of bench-top, liquid-phase reactor tests were conducted and mercury species concentrations were measured by UV/visible light spectroscopy to determine reactant and byproduct concentrations over time. Other measurement methods, such as atomic absorption, were used to measure concentrations of vapor-phase elemental mercury, that cannot be measured by UV/visible light spectroscopy. Next, a series of bench-scale wet FGD simulation tests were conducted. Because of the significant effects of sulfite concentration on mercury re-emission rates, new methods were developed for operating and controlling the bench-scale FGD experiments. Approximately 140 bench-scale wet FGD tests were conducted and several unusual and pertinent effects of process chemistry on mercury re-emissions were identified and characterized. These data have been used to develop an empirically adjusted, theoretically based kinetics model to predict mercury species reactions in wet FGD systems. The model has been verified in tests conducted with the bench-scale wet FGD system, where both gas-phase and liquid-phase mercury concentrations were measured to determine if the model accurately predicts the tendency for mercury re-emissions. This report presents and discusses results from the initial laboratory kinetics measurements, the bench-scale wet FGD tests, and the kinetics modeling

  18. SurfKin: an ab initio kinetic code for modeling surface reactions.

    Science.gov (United States)

    Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

    2014-10-05

    In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. Copyright © 2014 Wiley Periodicals, Inc.

  19. A kinetic study of the reaction of water vapor and carbon dioxide on uranium

    International Nuclear Information System (INIS)

    Santon, J.P.

    1964-09-01

    The kinetic study of the reaction of water vapour and carbon dioxide with uranium has been performed by thermogravimetric methods at temperatures between 160 and 410 deg G in the first case, 350 and 1050 deg C in the second: Three sorts of uranium specimens were used: uranium powder, thin evaporated films, and small spheres obtained from a plasma furnace. The experimental results led in the case of water vapour, to a linear rate of reaction controlled by diffusion at the lower temperatures, and by a surface reaction at the upper ones. In the case of carbon dioxide, a parabolic law has been found, controlled by diffusional processes. (author) [fr

  20. Kinetics of heterogeneous chemical reactions: a theoretical model for the accumulation of pesticides in soil.

    Science.gov (United States)

    Lin, S H; Sahai, R; Eyring, H

    1971-04-01

    A theoretical model for the accumulation of pesticides in soil has been proposed and discussed from the viewpoint of heterogeneous reaction kinetics with a basic aim to understand the complex nature of soil processes relating to the environmental pollution. In the bulk of soil, the pesticide disappears by diffusion and a chemical reaction; the rate processes considered on the surface of soil are diffusion, chemical reaction, vaporization, and regular pesticide application. The differential equations involved have been solved analytically by the Laplace-transform method.

  1. Kinetics of the Br2-CH3CHO Photochemical Chain Reaction

    Science.gov (United States)

    Nicovich, J. M.; Shackelford, C. J.; Wine, P. H.

    1997-01-01

    Time-resolved resonance fluorescence spectroscopy was employed in conjunction with laser flash photolysis of Br2 to study the kinetics of the two elementary steps in the photochemical chain reaction nBr2 + nCH3CHO + hv yields nCH3CBrO + nHBr. In the temperature range 255-400 K, the rate coefficient for the reaction Br((sup 2)P(sub 3/2)) + CH3CHO yields CH3CO + HBr is given by the Arrhenius expression k(sub 6)(T) = (1.51 +/- 0.20) x 10(exp -11) exp(-(364 +/- 41)/T)cu cm/(molecule.s). At 298 K, the reaction CH3CO + Br2 yields CH3CBrO + Br proceeds at a near gas kinetic rate, k(sub 7)(298 K) = (1.08 +/- 0.38) x 10(exp -10)cu cm/(molecule.s).

  2. Confining Domains Lead to Reaction Bursts: Reaction Kinetics in the Plasma Membrane

    Science.gov (United States)

    Kalay, Ziya; Fujiwara, Takahiro K.; Kusumi, Akihiro

    2012-01-01

    Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity. PMID:22479350

  3. Confining domains lead to reaction bursts: reaction kinetics in the plasma membrane.

    Directory of Open Access Journals (Sweden)

    Ziya Kalay

    Full Text Available Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity.

  4. Hydrolysis of Surfactants Containing Ester Bonds: Modulation of Reaction Kinetics and Important Aspects of Surfactant Self-Assembly

    Science.gov (United States)

    Lundberg, Dan; Stjerndahl, Maria

    2011-01-01

    The effects of self-assembly on the hydrolysis kinetics of surfactants that contain ester bonds are discussed. A number of examples on how reaction rates and apparent reaction orders can be modulated by changes in the conditions, including an instance of apparent zero-order kinetics, are presented. Furthermore, it is shown that the examples on…

  5. Using a Multi-Tier Diagnostic Test to Explore the Nature of Students' Alternative Conceptions on Reaction Kinetics

    Science.gov (United States)

    Yan, Yaw Kai; Subramaniam, R.

    2018-01-01

    This study focused on grade 12 students' understanding of reaction kinetics. A 4-tier diagnostic instrument was developed for this purpose and administered to 137 students in the main study. Findings showed that reaction kinetics is a difficult topic for these students, with a total of 25 alternative conceptions (ACs) being uncovered. Except for…

  6. Kinetics of the hydrogen production reaction in a copper-chlorine water splitting plant

    International Nuclear Information System (INIS)

    Zamfirescu, C.; Naterer, G.F.; Dincer, I.

    2009-01-01

    The exothermic reaction of HCl with particulate Cu occurs during hydrogen production step in the thermochemical copper-chlorine (Cu-Cl) water splitting cycle. In this paper, this chemical reaction is modeled kinetically, and a parametric study is performed to determine the influences of particle size, temperature and molar ratios on the reaction kinetics. It is determined that the residence time of copper particles varies between 10 and 100 s, depending on the operating conditions. The hydrogen conversion at equilibrium varies between 55 and 85%, depending on the reaction temperature. The heat flux at the particle surface, caused by the exothermic enthalpy of reaction, reaches about 3,000 W/m 2 when the particle shrinks to 0.1% from its initial size. A numerical algorithm is developed to solve the moving boundary Stefan problem with a chemical reaction. It predicts the shrinking of copper particles based on the hypothesis that the chemical reaction and heat transfer are decoupled. The model allows for estimation of the temperature of the copper particle, assumed spherical, in the radial direction. The maximum temperature at the interface is higher than the melting point of CuCl by 10-50 o C, depending on the assumed operating conditions. (author)

  7. Kinetics based reaction optimization of enzyme catalyzed reduction of formaldehyde to methanol with synchronous cofactor regeneration.

    Science.gov (United States)

    Marpani, Fauziah; Sárossy, Zsuzsa; Pinelo, Manuel; Meyer, Anne S

    2017-12-01

    Enzymatic reduction of carbon dioxide (CO 2 ) to methanol (CH 3 OH) can be accomplished using a designed set-up of three oxidoreductases utilizing reduced pyridine nucleotide (NADH) as cofactor for the reducing equivalents electron supply. For this enzyme system to function efficiently a balanced regeneration of the reducing equivalents during reaction is required. Herein, we report the optimization of the enzymatic conversion of formaldehyde (CHOH) to CH 3 OH by alcohol dehydrogenase, the final step of the enzymatic redox reaction of CO 2 to CH 3 OH, with kinetically synchronous enzymatic cofactor regeneration using either glucose dehydrogenase (System I) or xylose dehydrogenase (System II). A mathematical model of the enzyme kinetics was employed to identify the best reaction set-up for attaining optimal cofactor recycling rate and enzyme utilization efficiency. Targeted process optimization experiments were conducted to verify the kinetically modeled results. Repetitive reaction cycles were shown to enhance the yield of CH 3 OH, increase the total turnover number (TTN) and the biocatalytic productivity rate (BPR) value for both system I and II whilst minimizing the exposure of the enzymes to high concentrations of CHOH. System II was found to be superior to System I with a yield of 8 mM CH 3 OH, a TTN of 160 and BPR of 24 μmol CH 3 OH/U · h during 6 hr of reaction. The study demonstrates that an optimal reaction set-up could be designed from rational kinetics modeling to maximize the yield of CH 3 OH, whilst simultaneously optimizing cofactor recycling and enzyme utilization efficiency. © 2017 Wiley Periodicals, Inc.

  8. A kinetic reaction model for biomass pyrolysis processes in Aspen Plus

    International Nuclear Information System (INIS)

    Peters, Jens F.; Banks, Scott W.; Bridgwater, Anthony V.; Dufour, Javier

    2017-01-01

    Highlights: • Predictive kinetic reaction model applicable to any lignocellulosic feedstock. • Calculates pyrolysis yields and product composition as function of reactor conditions. • Detailed modelling of product composition (33 model compounds for the bio-oil). • Good agreement with literature regarding yield curves and product composition. • Successful validation with pyrolysis experiments in bench scale fast pyrolysis rig. - Abstract: This paper presents a novel kinetic reaction model for biomass pyrolysis processes. The model is based on the three main building blocks of lignocellulosic biomass, cellulose, hemicellulose and lignin and can be readily implemented in Aspen Plus and easily adapted to other process simulation software packages. It uses a set of 149 individual reactions that represent the volatilization, decomposition and recomposition processes of biomass pyrolysis. A linear regression algorithm accounts for the secondary pyrolysis reactions, thus allowing the calculation of slow and intermediate pyrolysis reactions. The bio-oil is modelled with a high level of detail, using up to 33 model compounds, which allows for a comprehensive estimation of the properties of the bio-oil and the prediction of further upgrading reactions. After showing good agreement with existing literature data, our own pyrolysis experiments are reported for validating the reaction model. A beech wood feedstock is subjected to pyrolysis under well-defined conditions at different temperatures and the product yields and compositions are determined. Reproducing the experimental pyrolysis runs with the simulation model, a high coincidence is found for the obtained fraction yields (bio-oil, char and gas), for the water content and for the elemental composition of the pyrolysis products. The kinetic reaction model is found to be suited for predicting pyrolysis yields and product composition for any lignocellulosic biomass feedstock under typical pyrolysis conditions

  9. 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).

  10. BGK-type models in strong reaction and kinetic chemical equilibrium regimes

    International Nuclear Information System (INIS)

    Monaco, R; Bianchi, M Pandolfi; Soares, A J

    2005-01-01

    A BGK-type procedure is applied to multi-component gases undergoing chemical reactions of bimolecular type. The relaxation process towards local Maxwellians, depending on mass and numerical densities of each species as well as common velocity and temperature, is investigated in two different cases with respect to chemical regimes. These cases are related to the strong reaction regime characterized by slow reactions, and to the kinetic chemical equilibrium regime where fast reactions take place. The consistency properties of both models are stated in detail. The trend to equilibrium is numerically tested and comparisons for the two regimes are performed within the hydrogen-air and carbon-oxygen reaction mechanism. In the spatial homogeneous case, it is also shown that the thermodynamical equilibrium of the models recovers satisfactorily the asymptotic equilibrium solutions to the reactive Euler equations

  11. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

    2018-03-01

    In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

  12. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

    2018-06-01

    In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

  13. Kinetic study of the annealing reactions in Cu-Ni-Fe alloys

    International Nuclear Information System (INIS)

    Donoso, E.

    2014-01-01

    The thermal aging of a Cu-45Ni-4Fe, Cu-34Ni-11Fe and Cu-33Ni-22Fe alloys tempered from 1173 K have been studied from Differential Scanning Calorimetry (DSC) and microhardness measurements. The analysis of DSC curves, from room temperature to 950 K, shows the presence of one exothermic reaction associated to the formation of FeNi 3 phase nucleating from a modulate structure, and one endothermic peak attributed to dissolution of this phase. Kinetic parameters were obtained using the usual Avrami-Erofeev equation, modified Kissinger method and integrated kinetic functions. Microhardness measurements confirmed the formation and dissolution of the FeNi 3 phase. (Author)

  14. Mechanistic kinetic modeling generates system-independent P-glycoprotein mediated transport elementary rate constants for inhibition and, in combination with 3D SIM microscopy, elucidates the importance of microvilli morphology on P-glycoprotein mediated efflux activity.

    Science.gov (United States)

    Ellens, Harma; Meng, Zhou; Le Marchand, Sylvain J; Bentz, Joe

    2018-06-01

    In vitro transporter kinetics are typically analyzed by steady-state Michaelis-Menten approximations. However, no clear evidence exists that these approximations, applied to multiple transporters in biological membranes, yield system-independent mechanistic parameters needed for reliable in vivo hypothesis generation and testing. Areas covered: The classical mass action model has been developed for P-glycoprotein (P-gp) mediated transport across confluent polarized cell monolayers. Numerical integration of the mass action equations for transport using a stable global optimization program yields fitted elementary rate constants that are system-independent. The efflux active P-gp was defined by the rate at which P-gp delivers drugs to the apical chamber, since as much as 90% of drugs effluxed by P-gp partition back into nearby microvilli prior to reaching the apical chamber. The efflux active P-gp concentration was 10-fold smaller than the total expressed P-gp for Caco-2 cells, due to their microvilli membrane morphology. The mechanistic insights from this analysis are readily extrapolated to P-gp mediated transport in vivo. Expert opinion: In vitro system-independent elementary rate constants for transporters are essential for the generation and validation of robust mechanistic PBPK models. Our modeling approach and programs have broad application potential. They can be used for any drug transporter with minor adaptations.

  15. Kinetics of ion/molecule reactions in Xe++acteone system

    International Nuclear Information System (INIS)

    Vinogradov, P.S.; Misharin, A.S.

    2002-01-01

    A reaction of Xe+ ion with acetone and subsequent transformations of the product ions at a buffer gas pressure (He) of 1.1 Torr were studied by the flow reactor technique mass spectrometry. A kinetic scheme describing the evolution of the ionic composition has been determined. The rate constants of the key reactions involved in the scheme have been evaluated. A channel of the production of acetone cation in A state in a charge transfer reaction was observed. A production of slowly reacting isomer of the acetone cation in secondary reactions was detected. Its product in the reaction with acetone is the 'nonprotonated dimer'. The kinetics of the production of ternary ions - ( CH 3 CO + CH 3 COCH 3 )(m/e=101), CH 3 COCH 3 H + (m/e=59) as well as the production of ions of the fourth generation ( CH 3 CO + (CH 3 COCH 3 ) 2 ) (m/e=159) and (CH 3 COCH 3 ) 2 H + was observed. CH 3 CO + ion (m/e=43) was found as the main reaction product. The main pathways scheme of ionic transformations is shown. (nevyjel)

  16. Strain-induced structural changes and chemical reactions. 1: Thermomechanical and kinetic models

    International Nuclear Information System (INIS)

    Levitas, V.I.; Nesterenko, V.F.; Meyers, M.A.

    1998-01-01

    Strain-induced chemical reactions were observed recently (Nesterenko et al) in experiments in the shear band in both Ti-Si and Nb-Si mixtures. Reactions can start in the solid state or after melting of at least one component. One of the aims is to find theoretically whether there are possible macroscopic mechanisms of mechanical intensification of the above and other chemical reactions due to plastic shear in the solid state. Continuum thermodynamical theory of structural changes with an athermal kinetics, which includes martensitic phase transformations, plastic strain-induced chemical reactions and polymorphic transformations, is developed at finite strains. The theory includes kinematics, criterion of structural change and extremum principle for determination of all unknown variable parameters for the case with neglected elastic strains. Thermodynamically consistent kinetic theory of thermally activated structural changes is suggested. The concept of the effective temperature is introduced which takes into account that temperature can vary significantly (on 1,000 K) during the chemical reactions under consideration. The theory will be applied in Part 2 of the paper for the description of chemical reactions in the shear band

  17. Effects of growth rate, cell size, motion, and elemental stoichiometry on nutrient transport kinetics.

    Science.gov (United States)

    Flynn, Kevin J; Skibinski, David O F; Lindemann, Christian

    2018-04-01

    Nutrient acquisition is a critical determinant for the competitive advantage for auto- and osmohetero- trophs alike. Nutrient limited growth is commonly described on a whole cell basis through reference to a maximum growth rate (Gmax) and a half-saturation constant (KG). This empirical application of a Michaelis-Menten like description ignores the multiple underlying feedbacks between physiology contributing to growth, cell size, elemental stoichiometry and cell motion. Here we explore these relationships with reference to the kinetics of the nutrient transporter protein, the transporter rate density at the cell surface (TRD; potential transport rate per unit plasma-membrane area), and diffusion gradients. While the half saturation value for the limiting nutrient increases rapidly with cell size, significant mitigation is afforded by cell motion (swimming or sedimentation), and by decreasing the cellular carbon density. There is thus potential for high vacuolation and high sedimentation rates in diatoms to significantly decrease KG and increase species competitive advantage. Our results also suggest that Gmax for larger non-diatom protists may be constrained by rates of nutrient transport. For a given carbon density, cell size and TRD, the value of Gmax/KG remains constant. This implies that species or strains with a lower Gmax might coincidentally have a competitive advantage under nutrient limited conditions as they also express lower values of KG. The ability of cells to modulate the TRD according to their nutritional status, and hence change the instantaneous maximum transport rate, has a very marked effect upon transport and growth kinetics. Analyses and dynamic models that do not consider such modulation will inevitably fail to properly reflect competitive advantage in nutrient acquisition. This has important implications for the accurate representation and predictive capabilities of model applications, in particular in a changing environment.

  18. Kinetics of free radical decay reactions in lactic acid homo and copolymers irradiated to sterilization dose

    International Nuclear Information System (INIS)

    Kantoglu, O.; Ozbey, T.; Gueven, O.

    1995-01-01

    The kinetics of free radical decay reactions of poly(L-Lactic acid), poly(DL-Lactic acid) and random copolymer of lactic and glycolic acid have been investigated for decays taking place in air and in vacuum. The change in ESR lines of γ-irradiated polymers have been followed over a long time period. The decay has been found to follow neither simple first-order nor second-order kinetics. Various kinetic approaches including composite first or second-order mechanisms and diffusion-controlled first or second-order equations were determined to be also unsatisfactory. The decay of radicals in bulk irradiated lactic acid homo and copolymers was found to be best described when the second-order non-classical equation with time dependent rate constant approach was used. (Author)

  19. On the ultrafast kinetics of the energy and electron transfer reactions in photosystem I

    Energy Technology Data Exchange (ETDEWEB)

    Slavov, Chavdar Lyubomirov

    2009-07-09

    The subject of the current work is one of the main participants in the light-dependent phase of oxygenic photosynthesis, Photosystem I (PS I). This complex carries an immense number of cofactors: chlorophylls (Chl), carotenoids, quinones, etc, which together with the protein entity exhibit several exceptional properties. First, PS I has an ultrafast light energy trapping kinetics with a nearly 100% quantum efficiency. Secondly, both of the electron transfer branches in the reaction center are suggested to be active. Thirdly, there are some so called 'red' Chls in the antenna system of PS I, absorbing light with longer wavelengths than the reaction center. These 'red' Chls significantly modify the trapping kinetics of PS I. The purpose of this thesis is to obtain better understanding of the above-mentioned, specific features of PS I. This will not merely cast more light on the mechanisms of energy and electron transfer in the complex, but also will contribute to the future developments of optimized artificial light-harvesting systems. In the current work, a number of PS I complexes isolated from different organisms (Thermosynechococcus elongatus, Chlamydomonas reinhardtii, Arabidopsis thaliana) and possessing distinctive features (different macroorganisation, monomers, trimers, monomers with a semibelt of peripheral antenna attached; presence of 'red' Chls) is investigated. The studies are primarily focused on the electron transfer kinetics in each of the cofactor branches in the PS I reaction center, as well as on the effect of the antenna size and the presence of 'red' Chls on the trapping kinetics of PS I. These aspects are explored with the help of several ultrafast optical spectroscopy methods: (i) time-resolved fluorescence ? single photon counting and synchroscan streak camera; and (ii) ultrafast transient absorption. Physically meaningful information about the molecular mechanisms of the energy trapping in PS I is

  20. Deviation from the kinetic law of mass action for reactions induced by binary encounters in liquid solutions

    International Nuclear Information System (INIS)

    Doktorov, Alexander B; Kipriyanov, Alexey A

    2007-01-01

    In considering the irreversible chemical reaction A+B→ C+B in liquid solutions two many-particle approaches to the derivation of binary non-Markovian kinetic equations are compared: simple superposition decoupling and a method of extracting 'pair' channels from three-particle correlation evolution. It is shown that both methods provide an almost identical description of this reaction. However, in studies of reversible reactions in liquid solutions only the channel extraction method gives a correct physically clear description of the reaction though it consists of a sequence of steps: the development of integral encounter theory (IET), effective pairs approximation (EPA), modified encounter theory (MET), and the final regular form (RF) of kinetic equations. It is shown that the rate equations often encountered in the literature correspond to the independence of transient channels of 'scattering' in the bimolecular reversible reaction (A+B -B), while the independent transient channel of 'decay' in the reversible reactionA+B -C is defined solely by time integral convolution. In the general case transient channels in non-Markovian theory are not independent, and their interference manifests itself as a non-Markovian inhomogeneous source in binary non-Markovian kinetic equations in regular form. Based on the derived equations new universal kinetics (independent of models) of chemical equilibrium attainment have been obtained. It is shown that these kinetics can differ essentially from the kinetics corresponding to the kinetic law of mass action of formal chemical kinetics

  1. Heterogeneous photocatalysis of real textile wastewater: evaluation of reaction kinetics and characterization.

    Science.gov (United States)

    Sahoo, Chittaranjan; Gupta, Ashok K; Pillai, Indu M Sasidharan

    2012-01-01

    Real textile wastewater collected from the cotton dyeing bath of a fabric dyeing and finishing plant was subjected to heterogeneous photocatalysis using Ag(+) doped TiO(2) under UV irradiation in a batch reactor. The photocatalysts were characterized by FESEM, XRD, EDS, FTIR, DRS and BET analyses. The kinetics of the reaction was also evaluated. Colour removal was more than 88%, 94% and 99%, respectively for undiluted, 2 times diluted and 5 times diluted wastewater with Ag(+) doped TiO(2) (2.5 g/L) after UV irradiation for 360 minutes. The COD removal for undiluted, 2 times diluted and 5 times diluted wastewater was 47%, 70% and 92%, respectively under similar conditions. The reaction followed Langmuir-Hinshelwood pseudo first order kinetic model and the data fitted well to polynomial regression analysis.

  2. Constrained reaction volume approach for studying chemical kinetics behind reflected shock waves

    KAUST Repository

    Hanson, Ronald K.

    2013-09-01

    We report a constrained-reaction-volume strategy for conducting kinetics experiments behind reflected shock waves, achieved in the present work by staged filling in a shock tube. Using hydrogen-oxygen ignition experiments as an example, we demonstrate that this strategy eliminates the possibility of non-localized (remote) ignition in shock tubes. Furthermore, we show that this same strategy can also effectively eliminate or minimize pressure changes due to combustion heat release, thereby enabling quantitative modeling of the kinetics throughout the combustion event using a simple assumption of specified pressure and enthalpy. We measure temperature and OH radical time-histories during ethylene-oxygen combustion behind reflected shock waves in a constrained reaction volume and verify that the results can be accurately modeled using a detailed mechanism and a specified pressure and enthalpy constraint. © 2013 The Combustion Institute.

  3. Reaction kinetics and modeling of photoinitiated cationic polymerization of an alicyclic based diglycidyl ether

    International Nuclear Information System (INIS)

    Harikrishna, R.; Ponrathnam, S.; Tambe, S.S.

    2014-01-01

    Highlights: • Photocationic polymerization of alicyclic based diglycidyl ether was carried out. • Kinetic parameters were influenced by gelation and diffusional restrictions. • Applicability of autocatalytic model was established by nonlinear regression. • System showed higher activation energy than cycloaliphatic and aromatic diepoxides. -- Abstract: Photoinitiated cationic polymerization of cycloaliphatic diepoxides had received tremendous attention, while studies with lesser polymerizable diglycidyl ethers are comparatively less reported. The present work deals with the photoinitiated cationic polymerization of cyclohexane dimethanol diglycidyl ether followed by estimation of kinetic parameters. The effects of concentration of photoinitiator and temperature on curing performance were studied using photo differential scanning calorimeter or photo DSC with polychromatic radiation. It was observed that the rate of polymerization as well as ultimate conversion increased with increasing concentration of photoinitiator and temperature. The influences of gelation as well as diffusional restrictions have remarkable effect on cure performance. The kinetic parameters as per autocatalytic kinetic model were studied by Levenberg–Marquardt nonlinear regression method instead of conventional linear method for obtaining more accurate values of apparent rate constant. It was observed that the model fits with data from initial stages to almost towards the end of the reaction. The activation energy was found to be higher than the values reported for more reactive cycloaliphatic diepoxides. The value of pre-exponential factor increased with increase in activation energy showing influence of gelation at early stages of reaction

  4. Ion-neutral gas reactions in a collision/reaction cell in inductively coupled plasma mass spectrometry: Correlation of ion signal decrease to kinetic rate constants

    Energy Technology Data Exchange (ETDEWEB)

    Gray, Patrick J. [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States); Department of Chemistry, The Ohio State University, 120 18th Avenue, Columbus, OH 43210 (United States); Olesik, John W., E-mail: olesik.2@osu.edu [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States)

    2015-03-01

    Reaction gas flow rate dependent Ar{sub 2}{sup +} and Ar{sup +} signals are correlated to fundamental kinetic rate coefficients. A simple calculation, assuming that gas exits the reaction cell due only to effusion, is described to estimate the gas pressure in the reaction cell. The value of the product of the kinetic rate constant and the ion residence time in the reaction cell can be determined from experimental measurement of the decrease in an ion signal as a function of reaction gas flow rate. New kinetic rate constants are determined for the reaction of CH{sub 3}F with Ar{sup +} and Ar{sub 2}{sup +}. - Highlights: • How to determine pressure and the product of the kinetic rate constant times the ion residence time in reaction cell • Relate measured ICP-DRC-MS signals versus gas flow rate to kinetic rate constants measured previously using SIFT-MS • Describe how to determine previously unmeasured kinetic rate constants using ICP-DRC-MS.

  5. Morphological impact on the reaction kinetics of size-selected cobalt oxide nanoparticles

    International Nuclear Information System (INIS)

    Bartling, Stephan; Meiwes-Broer, Karl-Heinz; Barke, Ingo; Pohl, Marga-Martina

    2015-01-01

    Apart from large surface areas, low activation energies are essential for efficient reactions, particularly in heterogeneous catalysis. Here, we show that not only the size of nanoparticles but also their detailed morphology can crucially affect reaction kinetics, as demonstrated for mass-selected, soft-landed, and oxidized cobalt clusters in a 6 nm to 18 nm size range. The method of reflection high-energy electron diffraction is extended to the quantitative determination of particle activation energies which is applied for repeated oxidation and reduction cycles at the same particles. We find unexpectedly small activation barriers for the reduction reaction of the largest particles studied, despite generally increasing barriers for growing sizes. We attribute these observations to the interplay of reaction-specific material transport with a size-dependent inner particle morphology

  6. Kinetics of the reaction between H· and superheated water probed with muonium

    Energy Technology Data Exchange (ETDEWEB)

    Alcorn, C. [Mount Allison Univ., Sackville, NB (Canada); Brodovitch, J.-C. [Simon Fraser Univ., Burnaby, BC (Canada); Ghandi, K.; Kennedy, A. [Mount Allison Univ., Sackville, NB (Canada); Percival, P.W. [Simon Fraser Univ., Burnaby, BC (Canada); TRIUMF, Vancouver, BC (Canada); Smith, M. [Mount Allison Univ., Sackville, NB (Canada)

    2011-07-01

    Safe operation of a supercritical water cooled reactor requires knowledge of the reaction kinetics of transient species formed by the radiolysis of water in the temperature range 300-650{sup o}C. By using a light isotope of the H·atom, it is possible to study its chemistry in water over this range of temperatures. Arguably, the most important reaction to study is that of the H·atom with the bulk solvent. This reaction could provide an in situ source of H{sub 2} gas, which is added to CANDU reactors to suppress oxidative corrosion. The work described here concerns studies of the reaction of muonium with H{sub 2}O and D{sub 2}O at temperatures up to 450{sup o}C.

  7. Kinetics of the reaction between H· and superheated water probed with muonium

    International Nuclear Information System (INIS)

    Alcorn, C.; Brodovitch, J.-C.; Ghandi, K.; Kennedy, A.; Percival, P.W.; Smith, M.

    2011-01-01

    Safe operation of a supercritical water cooled reactor requires knowledge of the reaction kinetics of transient species formed by the radiolysis of water in the temperature range 300-650"oC. By using a light isotope of the H·atom, it is possible to study its chemistry in water over this range of temperatures. Arguably, the most important reaction to study is that of the H·atom with the bulk solvent. This reaction could provide an in situ source of H_2 gas, which is added to CANDU reactors to suppress oxidative corrosion. The work described here concerns studies of the reaction of muonium with H_2O and D_2O at temperatures up to 450"oC.

  8. Hydrolysis reaction of 2,4-dichlorophenoxyacetic acid. A kinetic and computational study

    Science.gov (United States)

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

    2015-10-01

    The degradation of the 2,4-dichlorophenoxyacetic acid in aqueous solution is an hydrolysis reaction. Two products are identified: 2,4-dichlorophenol and glycolic acid. Reaction is investigated as a function of pH and temperature, and it is first-order kinetics and pH-dependent. Reaction is modeled in gas phase, where a proton catalyses the reaction. Critical points of PES are calculated at B3LYP/6-311++G(3df,2p), and aug-cc-pvqz//6-311++G(3df,2p) levels plus ZPE at 6-311++G(3df,2p) level. The activation barrier is 21.2 kcal/mol. Theoretical results agree with the experimental results. A second mechanism related with a Cl2Phsbnd Osbnd CH2sbnd COOH⋯H2O complex is found, but with a rate limiting step of 38.4 kcal/mol.

  9. Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

    2015-01-01

    ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

  10. Kinetics of the reaction of CH3O2 radicals with NO2

    DEFF Research Database (Denmark)

    Wallington, T.J.; Nielsen, O.J.; Sehested, K.

    1999-01-01

    The kinetics of the gas-phase reaction of CH3O2 radicals with NO2 were studied at 295 K in 0.5-14 arm of SF6 diluent using pulse radiolysis combined with time-resolved UV-VIS spectroscopy. Rate data were obtained by following the loss of CH3O2 using a monitoring wavelength of 260 nm. The results...

  11. Preclusion of switch behavior in reaction networks with mass-action kinetics

    DEFF Research Database (Denmark)

    Feliu, Elisenda; Wiuf, C.

    2012-01-01

    We study networks taken with mass-action kinetics and provide a Jacobian criterion that applies to an arbitrary network to preclude the existence of multiple positive steady states within any stoichiometric class for any choice of rate constants. We are concerned with the characterization...... precludes the existence of degenerate steady states. Further, we relate injectivity of a network to that of the network obtained by adding outflow, or degradation, reactions for all species....

  12. The kinetics of the reduction reaction of plutonium(IV) with N,N-dimethylhydroxylamine

    International Nuclear Information System (INIS)

    Yanxin Chen; Honbing Tang; Jinping Liu; Hui He

    2011-01-01

    The kinetics of reduction reactions between N,N-dimethylhydroxylamine (DMHAN) and plutonium(IV) in nitric acid solution have been studied spectrophotometrically. The kinetic equation of the reaction is determined to be -d[Pu(IV)]/dt = k 0 [Pu(IV)][DMHAN] 1.18 /[H + ] 2.22 at the beginning, where, the rate constant of the reaction (k 0 ) is 10.5 ± 1.8(mol/L) 1.04 s -1 at 14.5 deg C. By regressing of the time-concentration curve of the reaction, The complete rate equation is calculated as -d[Pu(IV)] / dt = k[Pu(IV)] 2 [DMHAN] 1.18 /[H + ] 2.22 / 8.12[Pu(III)]+95.9[Pu(IV)] with the reaction constant k about 1,000(mol/L) 1.04 s -1 at 14.5 deg C and an ionic strength (μ) of 4.0 mol/L. (author)

  13. Reactions of plutonium and uranium with water: Kinetics and potential hazards

    International Nuclear Information System (INIS)

    Haschke, J.M.

    1995-12-01

    The chemistry and kinetics of reactions between water and the metals and hydrides of plutonium and uranium are described in an effort to consolidate information for assessing potential hazards associated with handling and storage. New experimental results and data from literature sources are presented. Kinetic dependencies on pH, salt concentration, temperature and other parameters are reviewed. Corrosion reactions of the metals in near-neutral solutions produce a fine hydridic powder plus hydrogen. The corrosion rate for plutonium in sea water is a thousand-fold faster than for the metal in distilled water and more than a thousand-fold faster than for uranium in sea water. Reaction rates for immersed hydrides of plutonium and uranium are comparable and slower than the corrosion rates for the respective metals. However, uranium trihydride is reported to react violently if a quantity greater than twenty-five grams is rapidly immersed in water. The possibility of a similar autothermic reaction for large quantities of plutonium hydride cannot be excluded. In addition to producing hydrogen, corrosion reactions convert the massive metals into material forms that are readily suspended in water and that are aerosolizable and potentially pyrophoric when dry. Potential hazards associated with criticality, environmental dispersal, spontaneous ignition and explosive gas mixtures are outlined

  14. Kinetic study of the reaction of uranium with various carbon-containing gases

    International Nuclear Information System (INIS)

    Feron, G.

    1963-09-01

    The kinetic study of the reaction U + CO 2 and U + CO has been performed by a thermogravimetric method on a spherical uranium powder, in temperature ranges respectively from 460 to 690 deg. C and from 570 to 850 deg. C. The reaction with carbon dioxide leads to uranium dioxide. A carbon deposition takes place at the same time. The global reactions is the result of two reactions: U + 2 CO 2 → UO 2 + 2 CO U + CO 2 → UO 2 + C The reaction with carbon monoxide leads to a mixture of dioxide UO 2 , dicarbide UC 2 and free carbon. The main reaction can be written. U + CO → 1/2 UO 2 + 1/2 UC 2 The free carbon results of the disproportionation of the carbon monoxide. A remarkable separation of the two phases UO 2 and UC 2 can be observed. A mechanism accounting for the phenomenon has been proposed. The two reactions U + CO 2 and U + CO begin with a long germination period, after which, the reaction velocity seems to be limited in both cases by the ionic diffusion of oxygen through the uranium dioxide. (author) [fr

  15. Kinetics of the high temperature oxygen exchange reaction on 238PuO2 powder

    International Nuclear Information System (INIS)

    Whiting, Christofer E.; Du, Miting; Felker, L. Kevin; Wham, Robert M.; Barklay, Chadwick D.; Kramer, Daniel P.

    2015-01-01

    Oxygen exchange reactions performed on PuO 2 suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO 2 . Previous CeO 2 surrogate studies exhibit similar behavior, confirming that CeO 2 is a good qualitative surrogate for PuO 2 , in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO 2 oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO 2 Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

  16. SABIO-RK: an updated resource for manually curated biochemical reaction kinetics

    Science.gov (United States)

    Rey, Maja; Weidemann, Andreas; Kania, Renate; Müller, Wolfgang

    2018-01-01

    Abstract SABIO-RK (http://sabiork.h-its.org/) is a manually curated database containing data about biochemical reactions and their reaction kinetics. The data are primarily extracted from scientific literature and stored in a relational database. The content comprises both naturally occurring and alternatively measured biochemical reactions and is not restricted to any organism class. The data are made available to the public by a web-based search interface and by web services for programmatic access. In this update we describe major improvements and extensions of SABIO-RK since our last publication in the database issue of Nucleic Acid Research (2012). (i) The website has been completely revised and (ii) allows now also free text search for kinetics data. (iii) Additional interlinkages with other databases in our field have been established; this enables users to gain directly comprehensive knowledge about the properties of enzymes and kinetics beyond SABIO-RK. (iv) Vice versa, direct access to SABIO-RK data has been implemented in several systems biology tools and workflows. (v) On request of our experimental users, the data can be exported now additionally in spreadsheet formats. (vi) The newly established SABIO-RK Curation Service allows to respond to specific data requirements. PMID:29092055

  17. Bacillus anthracis o-succinylbenzoyl-CoA synthetase: reaction kinetics and a novel inhibitor mimicking its reaction intermediate.

    Science.gov (United States)

    Tian, Yang; Suk, Dae-Hwan; Cai, Feng; Crich, David; Mesecar, Andrew D

    2008-11-25

    o-Succinylbenzoyl-CoA (OSB-CoA) synthetase (EC 6.2.1.26) catalyzes the ATP-dependent condensation of o-succinylbenzoate (OSB) and CoA to form OSB-CoA, the fourth step of the menaquinone biosynthetic pathway in Bacillus anthracis. Gene knockout studies have highlighted this enzyme as a potential target for the discovery of new antibiotics. Here we report the first studies on the kinetic mechanism of B. anthracis OSB-CoA synthetase, classifying it as an ordered bi uni uni bi ping-pong mechanism. Through a series of pre-steady-state and steady-state kinetic studies in conjunction with direct binding studies, it is demonstrated that CoA, the last substrate to bind, strongly activates the first half-reaction after the first round of turnover. The activation of the first half-reaction is most likely achieved by CoA stabilizing conformations of the enzyme in the "F" form, which slowly isomerize back to the E form. Thus, the kinetic mechanism of OSB-CoA synthetase may be more accurately described as an ordered bi uni uni bi iso ping-pong mechanism. The substrate specificity of OSB-CoA synthetase was probed using a series of OSB analogues with alterations in the carboxylate groups. OSB-CoA shows a strong preference for OSB over all of the analogues tested as none were active except 4-[2-(trifluoromethyl)phenyl]-4-oxobutyric acid which exhibited a 100-fold decrease in k(cat)/K(m). On the basis of an understanding of OSB-CoA synthetase's kinetic mechanism and substrate specificity, a reaction intermediate analogue of OSB-AMP, 5'-O-{N-[2-(trifluoromethyl)phenyl]-4-oxobutyl}adenosine sulfonamide (TFMP-butyl-AMS), was designed and synthesized. This inhibitor was found to be an uncompetitive inhibitor to CoA and a mixed-type inhibitor to ATP and OSB with low micromolar inhibition constants. Collectively, these results should serve as an important forerunner to more detailed and extensive inhibitor design studies aimed at developing lead compounds against the OSB-CoA synthetase

  18. Bacillus anthracis o-succinylbenzoyl-CoA synthetase: reaction kinetics and a novel inhibitor mimicking its reaction intermediate †

    Science.gov (United States)

    Tian, Yang; Suk, Dae-Hwan; Cai, Feng; Crich, David; Mesecar, Andrew D.

    2009-01-01

    O-succinylbenzoyl-CoA (OSB-CoA) synthetase (EC 6.2.1.26) catalyzes the ATP-dependent condensation of o-succinylbenzoate (OSB) and CoA to form OSB-CoA, the fourth step of the menaquinone biosynthetic pathway in Bacillus anthracis. Gene knockout studies have highlighted this enzyme as a potential target for the discovery of new antibiotics. Here we report the first studies on the kinetic mechanism of B. anthracis OSB-CoA synthetase, classifying it as an ordered Bi Uni Uni Bi ping-pong mechanism. Through a series of pre-steady-state and steady-state kinetic studies in conjunction with direct-binding studies, it is demonstrated that CoA, the last substrate to bind, strongly activates the first half-reaction after the first round of turnover. The activation of the first-half reaction is most likely achieved by CoA stabilizing conformations of the enzyme in the ‘F’ form, which slowly isomerize back to the E form. Thus, the kinetic mechanism of OSB-CoA synthetase may be more accurately described as an ordered Bi Uni Uni Bi Iso ping-pong mechanism. The substrate specificity of OSB-CoA synthetase was probed using a series of OSB analogs with alterations in the carboxylate groups. OSB-CoA shows a strong preference for OSB over all of the analogs tested as none were active except 4-(2-trifluoromethylphenyl)-4-oxobutyric acid which exhibited a 100-fold decrease in kcat/Km. Based on an understanding of OSB-CoA synthetase’s kinetic mechanism and substrate specificity, a reaction intermediate analog of OSB-AMP, 5’-O-(N-(2-trifluoromethylphenyl)-4-oxobutyl) adenosine sulfonamide (TFMP-butyl-AMS), was designed and synthesized. This inhibitor was found to be an uncompetitive inhibitor to CoA and a mixed-type inhibitor to ATP and OSB with low micromolar inhibition constants. Collectively, these results should serve as an important forerunner to more detailed and extensive inhibitor design studies aimed at developing lead compounds against the OSB-CoA synthetase class of

  19. Studies on the kinetics of absorption of phosphorus by rice (Orysa sativa L.) and beans (Phaseolus vulgaris L.)

    International Nuclear Information System (INIS)

    Baraibar, A.; Villamil, J.; Fiore, M.F.; Marcondes, R.F.; Muraoka, T.; Cabral, C.P.; Malavolta, M.L.; Malavolta, E.

    1987-01-01

    Three experiments were conducted under controlled conditions with the objectives of evaluating the effect of different concentrations of phosphorus and on the presence of other ions on the kinetic of absorption. Excised roots of rice and bean were placed in aereated solutions containing increasing concentrations of NaH 2 PO 4 (10 -7 M to 5x10 -2 M) during 90 minutes. The rate of absorption (v = umols P/g dry matter) and the kinetic constants Vmax and Km were determined. Similar procedure was used to to evaluate the interaction of Mg +2 , Al +3 , K + , N-NH 4 + , N-NO 3 - and N-ureia in the uptake of phosphorus during 120 minutes. In another experiment, the effect of the presence of Mg +2 and/for Al +3 in the uptake and redistribution of phosphorus, was evaluated by varying the external concentration (1 ppm, 5 ppm, 10 ppm and 20 ppm) during a period of 17 hours, and utilizing whole rice plants. It was observed a dual mechanism, with two phases following the Michaelis-Menten kinetics and with transition phase 1 - 50 x 10 -5 M. The best explanation of the experimental data was obtained, by transforming the data in accordance with HOFSTEE (1952). Bean was more efficient than rice in the first phase of uptake (higher Vmax). Al 3 had a clear stimulatory effect on the uptake of phosphorus, promoting, however, the anion fixation in the root at lower concentrations. At the highest concentrations (20 ppm) of phosphorus this effect was not evident. No effect on the uptake was observed with Mg +2 , K + and different forms of nitrogen. Urea could have a depressive effect although, not significant. Possible mechanisms involved are discussed. (author) [pt

  20. Study of kinetics of reaction of lithium deuteride powder with O2, CO2 and water vapor

    International Nuclear Information System (INIS)

    Li Gan; Lu Guangda; Jing Wenyong; Qin Cheng

    2004-01-01

    The kinetics of reaction of lithium deuteride powder with O 2 , CO 2 and water vapor is studied. The experimental results show that lithium deuteride reacts with O 2 and CO 2 at very small reaction rate but with water vapor at comparatively larger rate at room temperature (≅28 degree C). The reaction process with water vapor could be described using the unreacted shrinking core model. The second-order kinetics is appropriate for the chemical reaction on the surface of lithium deuteride and reaction rate constant is 0.281 kPa -1 ·min -1

  1. Reaction kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers

    International Nuclear Information System (INIS)

    Gokcen, Dincer; Bae, Sang-Eun; Brankovic, Stanko R.

    2011-01-01

    The study of the kinetics of metal deposition via surface limited red-ox replacement of underpotentially deposited metal monolayers is presented. The model system was Pt submonolayer deposition on Au(1 1 1) via red-ox replacement of Pb and Cu UPD monolayers on Au(1 1 1). The kinetics of a single replacement reaction was studied using the formalism of the comprehensive analytical model developed to fit the open circuit potential transients from deposition experiments. The practical reaction kinetics parameters like reaction half life, reaction order and reaction rate constant are determined and discussed with their relevance to design and control of deposition experiments. The effects of transport limitation and the role of the anions/electrolyte on deposition kinetics are investigated and their significance to design of effective deposition process is discussed.

  2. Kinetic study of the reaction of chlorine atoms with hydroxyacetone in gas-phase

    Science.gov (United States)

    Stoeffler, Clara; Joly, Lilian; Durry, Georges; Cousin, Julien; Dumelié, Nicolas; Bruyant, Aurélien; Roth, Estelle; Chakir, Abdelkhaleq

    2013-12-01

    In this letter the kinetics of the reaction of hydroxyacetone CH3C(O)CH2OH with Cl atoms is investigated using the relative rate technique. Experiments are carried out in a 65 L multipass photoreactor in the temperature range of 281-350 K. A mid-infrared spectrometer based on a quantum cascade laser in external cavity emitting at 9.5 μm is used to analyze the reactants. The determined rate coefficient for the investigated reaction is (1.7 ± 0.3) × 10-11exp(381.5 ± 57.3/T). The results are presented and discussed in terms of precision and compared with those obtained previously. The impact of Cl atoms on the atmospheric life time of hydroxyacetone is also discussed. Developing analytical techniques to quantify this compound in the atmosphere. Several methods of measurement have been used including the technique of proton transfer mass spectrometry (PTR-MS) [2] and derivatization with a chemical agent such as dinitrophenylhydrazine (DNPH) [3,4] followed by GC/MS or HPLC analyses. The HA amount in the troposphere was found to be in the order of a few hundred parts per trillion by volume [4], Performing laboratory experiments in order to study the HA reactivity with atmospheric oxidants. The first study on the kinetic of the reaction between OH radicals and HA was made by Dagault et al. [5] whose work was performed at room temperature by flash photolysis-resonance fluorescence. The determined rate constant implies a lifetime of a few days for HA relative to oxidation by OH radicals. Orlando et al. performed mechanistic and kinetics studies of the reaction of HA with OH radicals and Cl atoms at room temperature using a relative method [6]. Products detection was performed using FTIR spectroscopy. Moreover, these authors studied the photolysis of HA to determine its quantum yield and UV absorption spectrum. These studies showed that HA is principally removed from the atmosphere by reaction with OH radicals. Kinetic studies of the reaction of OH radicals with HA as a

  3. A Microscale Approach to Chemical Kinetics in the General Chemistry Laboratory: The Potassium Iodide Hydrogen Peroxide Iodine-Clock Reaction

    Science.gov (United States)

    Sattsangi, Prem D.

    2011-01-01

    A microscale laboratory for teaching chemical kinetics utilizing the iodine clock reaction is described. Plastic pipets, 3 mL volume, are used to store and deliver precise drops of reagents and the reaction is run in a 24 well plastic tray using a total 60 drops of reagents. With this procedure, students determine the rate of reaction and the…

  4. A kinetic model for chemical reactions without barriers: transport coefficients and eigenmodes

    International Nuclear Information System (INIS)

    Alves, Giselle M; Kremer, Gilberto M; Marques, Wilson Jr; Soares, Ana Jacinta

    2011-01-01

    The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman–Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal–diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode

  5. A kinetic model for chemical reactions without barriers: transport coefficients and eigenmodes

    Science.gov (United States)

    Alves, Giselle M.; Kremer, Gilberto M.; Marques, Wilson, Jr.; Jacinta Soares, Ana

    2011-03-01

    The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman-Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal-diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode.

  6. A Kinetic Study of the Gas-Phase Reaction of OH with Br2

    Science.gov (United States)

    Bryukov, Mikhail G.; Dellinger, Barry; Knyazev, Vadim D.

    2011-01-01

    An experimental, temperature-dependent kinetic study of the gas-phase reaction of the hydroxyl radical with molecular bromine (reaction 1) has been performed using a pulsed laser photolysis/pulsed-laser-induced fluorescence technique over a wide temperature range of 297 – 766 K, and at pressures between 6.68 and 40.29 kPa of helium. The experimental rate coefficients for reaction 1 demonstrate no correlation with pressure and exhibit a negative temperature dependence with a slight negative curvature in the Arrhenius plot. A non-linear least-squares fit with two floating parameters of the temperature dependent k1(T) data set using an equation of the form k1(T) = ATn yields the recommended expression k1(T) = 1.85×10−9T − 0.66 cm3 molecule−1 s−1 for the temperature dependence of the reaction 1 rate coefficient. The potential energy surface (PES) of reaction 1 was investigated using quantum chemistry methods. The reaction proceeds through formation of a weakly bound OH···Br2 complex and a PES saddle point with an energy below that of the reactants. Temperature dependence of the reaction rate coefficient was modeled using the RRKM method on the basis of the calculated PES. PMID:16854030

  7. Kinetics of barium sulphate reaction crystallization in crystallizers with internal circulation

    Directory of Open Access Journals (Sweden)

    J. Koralewska

    2008-06-01

    Full Text Available Kinetic calculation results describing the observed nucleation and growth rates of barium sulphate crystals precipitated in an integrated reaction-crystallization process in a barium sulphate-ammonium chloride-water system are presented and analyzed. The scope of experiments included two continuous model DTM-type crystallizers (Draft Tube Magma with internal circulation of the suspension forced by a liquid jet-pump device responsible for stable and intensive enough ascending/descending flow of BaSO4 crystal magma in a mixing chamber. For comparison purposes the experimental data corresponding to a continuous DT (Draft Tube crystallizer with propeller agitator are presented and discussed. The various types of laboratory crystallizers used were fed with concentrated water solution of barium chloride (of 10 or 24 mass % and - in a stoichiometric proportion - crystalline ammonium sulphate, assuming isothermal (348 K and hydrodynamic (average residence time of suspension in a crystallizer: 900 s process conditions. The observed nucleation and growth rates of barium sulphate crystals were estimated on the basis of crystal size distributions (CSDs using convenient calculation scheme derived for an MSMPR (Mixed Suspension Mixed Product Removal model approach. Considering the experimental population density distribution courses, a size-dependent growth (SDG phenomenon was taken into account in the kinetic calculations. Five SDG kinetic models recommended in the accessible literature were used for kinetic parameter values estimation. It was proved statistically, that Rojkowski’s two SDG models (hyperbolic and exponential best suit for our own experimental data description. The experimental data presented can be practically applied for improving the constructions of liquid jet-pump DTM crystallizers recommended for reaction crystallization of sparingly soluble inorganic salts (especially for high concentrations of reaction substrates in the modern

  8. Aspartate aminotransferase: the kinetic barriers facing the covalent intermediates on the reaction pathway

    International Nuclear Information System (INIS)

    Kirsch, J.F.; Julin, D.A.; McLeish, M.; Wiesinger, H.

    1986-01-01

    The intermediates, aldimine (A), quinonoid (Q) and ketimine (K), along the transaminase reaction coordinate were probed by isotope transfer and solvent exchange kinetics. Less than 0.003% of 3 H is transferred from C/sub α/[ 3 H]-aspartate to pyridoxamine phosphate in the cytoplasmic aspartate aminotransferase (cAATase) reaction implying either that Q does not exist as a kinetically competent intermediate or that there is a rapid exchange of isotope with solvent. The ratio of the rate constants for C/sub α/ hydrogen exchange vs keto acid product formation (k/sub exge//k/sub prod/) are 2.5 and 0.5 for the reactions of cAATase with C/sub α/ [ 2 H]-aspartate and mitochondrial (m) AATase with C/sub α/[ 2 H]-glutamate respectively. The latter reaction was also probed from the α-keto-glutarate side with carbonyl 0-18 enriched keto acid. This experiment gave k/sub exge//k/sub prod/ = 1.0 for oxygen-18 exchange in α-ketoglutarate versus amino acid formation. The two exchange experiments with mAATase are interpreted in terms of a model in which the rate constant for diffusion of water from the active site is comparable with those for product forming steps

  9. Searching out the hydrogen absorption/desorption limiting reaction factors: Strategies allowing to increase kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Zeaiter, Ali, E-mail: ali.zeaiter@femto-st.fr; Chapelle, David; Nardin, Philippe

    2015-10-05

    Highlights: • A macro scale thermodynamic model that simulates the response of a FeTi-X hydride tank is performed, and validated experimentally. • A sensibility study to identify the most influent input variables that can changes very largely the reaction rate. - Abstract: Hydrogen gas has become one of the most promising energy carriers. Main breakthrough concerns hydrogen solid storage, specially based on intermetallic material use. Regarding the raw material abundance and cost, the AB type alloy FeTi is an auspicious candidate to store hydrogen. Its absorption/desorption kinetics is a basic hindrance to common use, compared with more usual hydrides. First, discussions based on literature help us identifying the successive steps leading to metal hydriding, and allow to introduce the physical parameters which drive or limit the reaction. This analysis leads us to suggest strategies in order to increase absorption/desorption kinetics. Attention is then paid to a thermofluidodynamic model, allowing to describe a macroscopic solid storage reactor. Thus, we can achieve a simulation which describes the overall reaction inside the hydrogen reactor and, by varying the sub-mentioned parameters (thermal conductivity, the powder granularity, environment heat exchange…), we attempt to hierarchy the reaction limiting factors. These simulations are correlated to absorption/desorption experiments for which pressure, temperature and hydrogen flow are recorded.

  10. Thermodynamic and kinetic analysis of the reaction between biological catecholamines and chlorinated methylperoxy radicals

    Science.gov (United States)

    Dimić, Dušan S.; Milenković, Dejan A.; Marković, Jasmina M. Dimitrić; Marković, Zoran S.

    2018-05-01

    The antiradical potency of catecholamines (dopamine, epinephrine, norepinephrine, L-DOPA), metabolites of dopamine (homovanillic acid, 3-methoxytyramine and 3,4-dihydroxyphenylacetic acid) and catechol towards substituted methylperoxy radicals is investigated. The thermodynamic parameters, together with the kinetic approach, are used to determine the most probable mechanism of action. The natural bond orbital and quantum theory of atoms in molecules are utilised to explain the highest reactivity of trichloromethylperoxy radical. The preferred mechanism is dependent both on the thermodynamic and kinetic parameters . The number of chlorine atoms on radical, the presence of intra-molecular hydrogen bond and number of hydroxy groups attached to the aromatic ring significantly influence the mechanism. The results suggest that sequential proton loss electron transfer (SPLET) is the most probable for reaction with methylperoxy and hydrogen atom transfer (HAT) for reaction with trichloromethylperoxy radicals, with a gradual transition between SPLET and HAT for other two radicals. Due to the significant deprotonation of molecules containing the carboxyl group, the respective anions are also investigated. The HAT and SPLET mechanisms are highly competitive in reaction with MP radical, while the dominant mechanism towards chlorinated radicals is HAT. The reactions in methanol and benzene are also discussed.

  11. Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

    International Nuclear Information System (INIS)

    Basilevsky, M. V.; Mitina, E. A.; Odinokov, A. V.; Titov, S. V.

    2013-01-01

    The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ 0 =ℏω 0 /k B T where ω 0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ 0 0 ≫ 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T→ 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the

  12. Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

    Energy Technology Data Exchange (ETDEWEB)

    Basilevsky, M. V.; Mitina, E. A. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); Odinokov, A. V. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); National Research Nuclear University “MEPhI,” 31, Kashirskoye shosse, Moscow (Russian Federation); Titov, S. V. [Karpov Institute of Physical Chemistry, 3-1/12, Building 6, Obuha pereulok, Moscow (Russian Federation)

    2013-12-21

    The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ{sub 0}=ℏω{sub 0}/k{sub B}T where ω{sub 0} is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ{sub 0} < 1 − 3) and for low (ξ{sub 0}≫ 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T→ 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the

  13. 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.

  14. Reaction kinetics in open reactors and serial transfers between closed reactors

    Science.gov (United States)

    Blokhuis, Alex; Lacoste, David; Gaspard, Pierre

    2018-04-01

    Kinetic theory and thermodynamics of reaction networks are extended to the out-of-equilibrium dynamics of continuous-flow stirred tank reactors (CSTR) and serial transfers. On the basis of their stoichiometry matrix, the conservation laws and the cycles of the network are determined for both dynamics. It is shown that the CSTR and serial transfer dynamics are equivalent in the limit where the time interval between the transfers tends to zero proportionally to the ratio of the fractions of fresh to transferred solutions. These results are illustrated with a finite cross-catalytic reaction network and an infinite reaction network describing mass exchange between polymers. Serial transfer dynamics is typically used in molecular evolution experiments in the context of research on the origins of life. The present study is shedding a new light on the role played by serial transfer parameters in these experiments.

  15. Non-equilibrium reactive flux: A unified framework for slow and fast reaction kinetics.

    Science.gov (United States)

    Bose, Amartya; Makri, Nancy

    2017-10-21

    The flux formulation of reaction rate theory is recast in terms of the expectation value of the reactive flux with an initial condition that corresponds to a non-equilibrium, factorized reactant density. In the common case of slow reactive processes, the non-equilibrium expression reaches the plateau regime only slightly slower than the equilibrium flux form. When the reactants are described by a single quantum state, as in the case of electron transfer reactions, the factorized reactant density describes the true initial condition of the reactive process. In such cases, the time integral of the non-equilibrium flux expression yields the reactant population as a function of time, allowing characterization of the dynamics in cases where there is no clear separation of time scales and thus a plateau regime cannot be identified. The non-equilibrium flux offers a unified approach to the kinetics of slow and fast chemical reactions and is ideally suited to mixed quantum-classical methods.

  16. Experimental study of the reactions of limonene with OH and OD radicals: kinetics and products.

    Science.gov (United States)

    Braure, Tristan; Bedjanian, Yuri; Romanias, Manolis N; Morin, Julien; Riffault, Véronique; Tomas, Alexandre; Coddeville, Patrice

    2014-10-09

    The kinetics of the reactions of limonene with OH and OD radicals has been studied using a low-pressure flow tube reactor coupled with a quadrupole mass spectrometer: OH + C10H16 → products (1), OD + C10H16 → products (2). The rate constants of the title reactions were determined using four different approaches: either monitoring the kinetics of OH (OD) radicals or limonene consumption in excess of limonene or of the radicals, respectively (absolute method), and by the relative rate method using either the reaction OH (OD) + Br2 or OH (OD) + DMDS (dimethyl disulfide) as the reference one and following HOBr (DOBr) formation or DMDS and limonene consumption, respectively. As a result of the absolute and relative measurements, the overall rate coefficients, k1 = (3.0 ± 0.5) × 10(-11) exp((515 ± 50)/T) and k2 = (2.5 ± 0.6) × 10(-11) exp((575 ± 60)/T) cm(3) molecule(-1) s(-1), were determined at a pressure of 1 Torr of helium over the temperature ranges 220-360 and 233-353 K, respectively. k1 was found to be pressure independent over the range 0.5-5 Torr. There are two possible pathways for the reaction between OH (OD) and limonene: addition of the radical to one of the limonene double bonds (reactions 1a and 2a ) and abstraction of a hydrogen atom (reactions 1b and 2b ), resulting in the formation of H2O (HOD). Measurements of the HOD yield as a function of temperature led to the following branching ratio of the H atom abstraction channel: k2b/k2 = (0.07 ± 0.03) × exp((460 ± 140)/T) for T = (253-355) K.

  17. Characterization of excited-state reactions with instant spectra of fluorescence kinetics

    International Nuclear Information System (INIS)

    Tomin, Vladimir I.; Ushakou, Dzmitryi V.

    2015-01-01

    Comprehensible knowledge of the excited-state proton transfer processes in organic compounds is overwhelmingly important not only for physics, but also chemistry and Life Sciences, since they play a key role in main processes of photosynthesis and functioning of biological organisms. Moreover compounds with Excited-State Intramolecular Proton Transfer (ESIPT) are in the focus of the interest of scientists throughout the world, because dual fluorescence spectra of such objects corresponding to two forms of molecular structure (normal and photoproduct) are very sensitive to characteristics of molecular microenvironment. This property allows to use such substances as fluorescent probes for diverse applications in chemistry and Life Sciences. But at the same time studying of proton transfer processes is not simple, because this process is characterized by extremely fast times (on picoseconds time scale and less order) and very often contribution of reverse reactions is essentially complicates an interpretation of observed properties of dual fluorescence. Hence, understanding of a role of reversible reactions is crucial for a comprehensive description of all processes accompanying excited state reactions. We discuss new approach for treatment ESIPT reaction on the basis of experimentally measured instant spectra of dual fluorescence and temporal behavior of ratiometric signal of normal to tautomer form intensities. Simple analytical expressions show in transparent way how to distinguish a degree of reverse reaction contribution to ratiometric signal. A validation of the approach under consideration is fulfilled with two different flavonols – 3-hydroxyflavone and 4′-(Dimethylamino)-3-hydroxyflavone – representing two extreme cases in affecting reversible reaction on dual emission. A comparing of new approach and traditional method when we analyze kinetics of separate the N* and T* fluorescence bands decays, has been carried out. - Highlights: • The excited

  18. Characterization of excited-state reactions with instant spectra of fluorescence kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Tomin, Vladimir I., E-mail: tomin@apsl.edu.pl; Ushakou, Dzmitryi V.

    2015-10-15

    Comprehensible knowledge of the excited-state proton transfer processes in organic compounds is overwhelmingly important not only for physics, but also chemistry and Life Sciences, since they play a key role in main processes of photosynthesis and functioning of biological organisms. Moreover compounds with Excited-State Intramolecular Proton Transfer (ESIPT) are in the focus of the interest of scientists throughout the world, because dual fluorescence spectra of such objects corresponding to two forms of molecular structure (normal and photoproduct) are very sensitive to characteristics of molecular microenvironment. This property allows to use such substances as fluorescent probes for diverse applications in chemistry and Life Sciences. But at the same time studying of proton transfer processes is not simple, because this process is characterized by extremely fast times (on picoseconds time scale and less order) and very often contribution of reverse reactions is essentially complicates an interpretation of observed properties of dual fluorescence. Hence, understanding of a role of reversible reactions is crucial for a comprehensive description of all processes accompanying excited state reactions. We discuss new approach for treatment ESIPT reaction on the basis of experimentally measured instant spectra of dual fluorescence and temporal behavior of ratiometric signal of normal to tautomer form intensities. Simple analytical expressions show in transparent way how to distinguish a degree of reverse reaction contribution to ratiometric signal. A validation of the approach under consideration is fulfilled with two different flavonols – 3-hydroxyflavone and 4′-(Dimethylamino)-3-hydroxyflavone – representing two extreme cases in affecting reversible reaction on dual emission. A comparing of new approach and traditional method when we analyze kinetics of separate the N* and T* fluorescence bands decays, has been carried out. - Highlights: • The excited

  19. Substrate and pH-Dependent Kinetic Profile of 3-Mercaptopropionate Dioxygenase from Pseudomonas aeruginosa.

    Science.gov (United States)

    Fellner, Matthias; Aloi, Sekotilani; Tchesnokov, Egor P; Wilbanks, Sigurd M; Jameson, Guy N L

    2016-03-08

    Thiol dioxygenases catalyze the synthesis of sulfinic acids in a range of organisms from bacteria to mammals. A thiol dioxygenase from the bacterium Pseudomonas aeruginosa oxidizes both 3-mercaptopropionic acid and cysteine, with a ∼70 fold preference for 3-mercaptopropionic acid over all pHs. This substrate reactivity is widened compared to other thiol dioxygenases and was exploited in this investigation of the residues important for activity. A simple model incorporating two protonation events was used to fit profiles of the Michaelis-Menten parameters determined at different pH values for both substrates. The pKs determined using plots of k(cat)/Km differ at low pH, but not in a way easily attributable to protonation of the substrate alone and share a common value at higher pH. Plots of k(cat) versus pH are also quite different at low pH showing the monoprotonated ES complexes with 3-mercaptopropionic acid and cysteine have different pKs. At higher pH, k(cat) decreases sigmoidally with a similar pK regardless of substrate. Loss of reactivity at high pH is attributed to deprotonation of tyrosine 159 and its influence on dioxygen binding. A mechanism is proposed by which deprotonation of tyrosine 159 both blocks oxygen binding and concomitantly promotes cystine formation. Finally, the role of tyrosine 159 was further probed by production of a G95C variant that is able to form a cysteine-tyrosine crosslink homologous to that found in mammalian cysteine dioxygenases. Activity of this variant is severely impaired. Crystallography shows that when un-crosslinked, the cysteine thiol excludes tyrosine 159 from its native position, while kinetic analysis shows that the thioether bond impairs reactivity of the crosslinked form.

  20. Purification, Kinetic, and Thermodynamic Characteristics of an Exo-polygalacturonase from Penicillium notatum with Industrial Perspective.

    Science.gov (United States)

    Amin, Faiza; Bhatti, Haq Nawaz; Bilal, Muhammad; Asgher, Muhammad

    2017-09-01

    An extracellular exo-polygalacturonase (exo-PG) produced by Penicillium notatum was purified (3.07-folds) by ammonium sulfate fractionation, ion exchange, and gel filtration chromatography. Two distinct isoforms of the enzyme, namely exo-PGI and exo-PGII, were identified during column purification with molecular weights of 85 and 20 kDa, respectively, on sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). The enzyme displayed its optimum activity at pH 6.0 and 50 °C and was found to be stable in the slightly acidic pH (ranging from 4.5 to 6.0). Michaelis-Menten parameters, i.e., K m (app) and V max for pectin hydrolysis, were calculated to be 16.6 mg/mL and 20 μmol/mL/min, respectively. The enzyme followed biphasic deactivation kinetics. Phase I of the exo-PGI showed half-lives of 6.83 and 2.39 min at 55 and 80 °C, respectively, whereas phase II of the enzyme exhibited a half-life of 63.57 and 22.72 min at 55 and 80 °C, respectively. The activation energy for denaturation was 51.66 and 44.06 kJ/mol for phase I and phase II of the exo-PGI, respectively. The enzyme activity was considerably enhanced by Mn 2+ , whereas exposure to a hydrophobic environment (urea and sodium azide solution) drastically suppressed the enzyme activity. Results suggest that exo-PGI might be considered as a potential candidate for various applications, particularly in the food and textile industries.

  1. Microbial ureolysis in the seawater-catalysed urine phosphorus recovery system: Kinetic study and reactor verification.

    Science.gov (United States)

    Tang, Wen-Tao; Dai, Ji; Liu, Rulong; Chen, Guang-Hao

    2015-12-15

    Our previous study has confirmed the feasibility of using seawater as an economical precipitant for urine phosphorus (P) precipitation. However, we still understand very little about the ureolysis in the Seawater-based Urine Phosphorus Recovery (SUPR) system despite its being a crucial step for urine P recovery. In this study, batch experiments were conducted to investigate the kinetics of microbial ureolysis in the seawater-urine system. Indigenous bacteria from urine and seawater exhibited relatively low ureolytic activity, but they adapted quickly to the urine-seawater mixture during batch cultivation. During cultivation, both the abundance and specific ureolysis rate of the indigenous bacteria were greatly enhanced as confirmed by a biomass-dependent Michaelis-Menten model. The period for fully ureolysis was decreased from 180 h to 2.5 h after four cycles of cultivation. Based on the successful cultivation, a lab-scale SUPR reactor was set up to verify the fast ureolysis and efficient P recovery in the SUPR system. Nearly complete urine P removal was achieved in the reactor in 6 h without adding any chemicals. Terminal Restriction Fragment Length Polymorphism (TRFLP) analysis revealed that the predominant groups of bacteria in the SUPR reactor likely originated from seawater rather than urine. Moreover, batch tests confirmed the high ureolysis rates and high phosphorus removal efficiency induced by cultivated bacteria in the SUPR reactor under seawater-to-urine mixing ratios ranging from 1:1 to 9:1. This study has proved that the enrichment of indigenous bacteria in the SUPR system can lead to sufficient ureolytic activity for phosphate precipitation, thus providing an efficient and economical method for urine P recovery. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Unravelling the kinetics of the formation of acrylamide in the Maillard reaction of fructose and asparagine by multiresponse modelling

    NARCIS (Netherlands)

    Knol, J.J.; Linssen, J.P.H.; Boekel, van M.A.J.S.

    2010-01-01

    A kinetic model for the formation of acrylamide in a fructose–asparagine reaction system at initial pH 5.5 is proposed, based on an approach called multiresponse kinetic modelling. The formation of acetic acid and formic acid from the degradation of fructose and its isomer glucose was included in

  3. Golden rule kinetics of transfer reactions in condensed phase: the microscopic model of electron transfer reactions in disordered solid matrices.

    Science.gov (United States)

    Basilevsky, M V; Odinokov, A V; Titov, S V; Mitina, E A

    2013-12-21

    The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ0 = ℏω0/k(B)T where ω0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ0 regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T → 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the existing theories of the ET. Our alternative dynamic ET model for local

  4. HTP kinetics studies on isolated elementary combustion reactions over wide temperature ranges

    Energy Technology Data Exchange (ETDEWEB)

    Fontijn, A.; Adusei, G.Y.; Hranisavlevic, J.; Bajaj, P.N. [Rensselaer Polytechnic Institute, Troy, NY (United States)

    1993-12-01

    The goals of this project are to provide accurate data on the temperature dependence of the kinetics of elementary combustion reactions, (i) for use by combustion modelers, and (ii) to gain a better fundamental understanding of, and hence predictive ability for, the chemistry involved. Experimental measurements are made mainly by using the pseudo-static HTP (high-temperature photochemistry) technique. While continuing rate coefficient measurements, further aspects of kinetics research are being explored. Thus, starting from the data obtained, a method for predicting the temperature dependence of rate coefficients of oxygen-atom olefin experiment and confirms the underlying mechanistic assumptions. Mechanistic information of another sort, i.e. by product analysis, has recently become accessible with the inauguration of our heated flow tube mass spectrometer facility; early results are reported here. HTP experiments designed to lead to measurements of product channels by resonance fluorescence have started.

  5. 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

    The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic

  6. Thermodynamic and Kinetic Response of Microbial Reactions to High CO2.

    Science.gov (United States)

    Jin, Qusheng; Kirk, Matthew F

    2016-01-01

    Geological carbon sequestration captures CO 2 from industrial sources and stores the CO 2 in subsurface reservoirs, a viable strategy for mitigating global climate change. In assessing the environmental impact of the strategy, a key question is how microbial reactions respond to the elevated CO 2 concentration. This study uses biogeochemical modeling to explore the influence of CO 2 on the thermodynamics and kinetics of common microbial reactions in subsurface environments, including syntrophic oxidation, iron reduction, sulfate reduction, and methanogenesis. The results show that increasing CO 2 levels decreases groundwater pH and modulates chemical speciation of weak acids in groundwater, which in turn affect microbial reactions in different ways and to different extents. Specifically, a thermodynamic analysis shows that increasing CO 2 partial pressure lowers the energy available from syntrophic oxidation and acetoclastic methanogenesis, but raises the available energy of microbial iron reduction, hydrogenotrophic sulfate reduction and methanogenesis. Kinetic modeling suggests that high CO 2 has the potential of inhibiting microbial sulfate reduction while promoting iron reduction. These results are consistent with the observations of previous laboratory and field studies, and highlight the complexity in microbiological responses to elevated CO 2 abundance, and the potential power of biogeochemical modeling in evaluating and quantifying these responses.

  7. Oxidation of β-lactam antibiotics by peracetic acid: Reaction kinetics, product and pathway evaluation.

    Science.gov (United States)

    Zhang, Kejia; Zhou, Xinyan; Du, Penghui; Zhang, Tuqiao; Cai, Meiquan; Sun, Peizhe; Huang, Ching-Hua

    2017-10-15

    Peracetic acid (PAA) is a disinfection oxidant used in many industries including wastewater treatment. β-Lactams, a group of widely prescribed antibiotics, are frequently detected in wastewater effluents and surface waters. The reaction kinetics and transformation of seven β-lactams (cefalexin (CFX), cefadroxil (CFR), cefapirin (CFP), cephalothin (CFT), ampicillin (AMP), amoxicillin (AMX) and penicillin G (PG)) toward PAA were investigated to elucidate the behavior of β-lactams during PAA oxidation processes. The reaction follows second-order kinetics and is much faster at pH 5 and 7 than at pH 9 due to speciation of PAA. Reactivity to PAA follows the order of CFR ∼ CFX > AMP ∼ AMX > CFT ∼ CFP ∼ PG and is related to β-lactam's nucleophilicity. The thioether sulfur of β-lactams is attacked by PAA to generate sulfoxide products. Presence of the phenylglycinyl amino group on β-lactams can significantly influence electron distribution and the highest occupied molecular orbital (HOMO) location and energy in ways that enhance the reactivity to PAA. Reaction rate constants obtained in clean water matrix can be used to accurately model the decay of β-lactams by PAA in surface water matrix and only slightly overestimate the decay in wastewater matrix. Results of this study indicate that the oxidative transformation of β-lactams by PAA can be expected under appropriate wastewater treatment conditions. Copyright © 2017. Published by Elsevier Ltd.

  8. 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.

  9. Accurate label-free reaction kinetics determination using initial rate heat measurements

    Science.gov (United States)

    Ebrahimi, Kourosh Honarmand; Hagedoorn, Peter-Leon; Jacobs, Denise; Hagen, Wilfred R.

    2015-01-01

    Accurate label-free methods or assays to obtain the initial reaction rates have significant importance in fundamental studies of enzymes and in application-oriented high throughput screening of enzyme activity. Here we introduce a label-free approach for obtaining initial rates of enzyme activity from heat measurements, which we name initial rate calorimetry (IrCal). This approach is based on our new finding that the data recorded by isothermal titration calorimetry for the early stages of a reaction, which have been widely ignored, are correlated to the initial rates. Application of the IrCal approach to various enzymes led to accurate enzyme kinetics parameters as compared to spectroscopic methods and enabled enzyme kinetic studies with natural substrate, e.g. proteases with protein substrates. Because heat is a label-free property of almost all reactions, the IrCal approach holds promise in fundamental studies of various enzymes and in use of calorimetry for high throughput screening of enzyme activity. PMID:26574737

  10. Thermodynamic and kinetic response of microbial reactions to high CO2

    Directory of Open Access Journals (Sweden)

    Qusheng Jin

    2016-11-01

    Full Text Available Geological carbon sequestration captures CO2 from industrial sources and stores the CO2 in subsurface reservoirs, a viable strategy for mitigating global climate change. In assessing the environmental impact of the strategy, a key question is how microbial reactions respond to the elevated CO2 concentration. This study uses biogeochemical modeling to explore the influence of CO2 on the thermodynamics and kinetics of common microbial reactions in subsurface environments, including syntrophic oxidation, iron reduction, sulfate reduction, and methanogenesis. The results show that increasing CO2 levels decreases groundwater pH and modulates chemical speciation of weak acids in groundwater, which in turn affect microbial reactions in different ways and to different extents. Specifically, a thermodynamic analysis shows that increasing CO2 partial pressure lowers the energy available from syntrophic oxidation and acetoclastic methanogenesis, but raises the available energy of microbial iron reduction, hydrogenotrophic sulfate reduction and methanogenesis. Kinetic modeling suggests that high CO2 has the potential of inhibiting microbial sulfate reduction while promoting iron reduction. These results are consistent with the observations of previous laboratory and field studies, and highlight the complexity in microbiological responses to elevated CO2 abundance, and the potential power of biogeochemical modeling in evaluating and quantifying these responses.

  11. Kinetics of the reactions of bromine atoms with a series of aliphatic aldehydes at 298 K

    Energy Technology Data Exchange (ETDEWEB)

    Szilagyi, I.; Imrik, K.; Dobe, S.; Berces, T. [Magyar Tudomanyos Akademia, Budapest (Hungary). Koezponti Kemiai Kutato Intezete

    1998-01-01

    The kinetics of the reactions of Br({sup 2}P{sub 3/2}) with selected aldehydes, i.e. ethanal (1), propanal (2), 2-methyl-propanal (3), 2.2-dimethyl-propanal (4) and trichloroacetaldehyde (5) were studied at 298{+-}2 K. Rate constants for overall reactions were measured using the fast flow technique with resonance fluorescence detection of Br. Complementary determinations were carried out by the laser flash photolysis method. The following rate constants were obtained in the kinetic measurements ({+-}2{sigma}): k{sub 1}=(2.1{+-}0.2) x 10{sup 12}, k{sub 2}=(4.3{+-}0.4) x 10{sup 12}, k{sub 3}=(6.3{+-}1.4) x 10{sup 12}, k{sub 4}=(8.5{+-}0.8) x 10{sup 12}, k{sub 5}{<=}1 x 10{sup 9}, all in cm{sup 3}mol{sup -1}s{sup -1} units. The probable mechanism for the reactions of bromine atoms with aliphatic aldehydes has been discussed. (orig.)

  12. Rethinking fundamentals of enzyme action.

    Science.gov (United States)

    Northrop, D B

    1999-01-01

    Despite certain limitations, investigators continue to gainfully employ concepts rooted in steady-state kinetics in efforts to draw mechanistically relevant inferences about enzyme catalysis. By reconsidering steady-state enzyme kinetic behavior, this review develops ideas that allow one to arrive at the following new definitions: (a) V/K, the ratio of the maximal initial velocity divided by the Michaelis-Menten constant, is the apparent rate constant for the capture of substrate into enzyme complexes that are destined to yield product(s) at some later point in time; (b) the maximal velocity V is the apparent rate constant for the release of substrate from captured complexes in the form of free product(s); and (c) the Michaelis-Menten constant K is the ratio of the apparent rate constants for release and capture. The physiologic significance of V/K is also explored to illuminate aspects of antibiotic resistance, the concept of "perfection" in enzyme catalysis, and catalytic proficiency. The conceptual basis of congruent thermodynamic cycles is also considered in an attempt to achieve an unambiguous way for comparing an enzyme-catalyzed reaction with its uncatalyzed reference reaction. Such efforts promise a deeper understanding of the origins of catalytic power, as it relates to stabilization of the reactant ground state, stabilization of the transition state, and reciprocal stabilizations of ground and transition states.

  13. 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

  14. Pressure-dependent kinetics of initial reactions in iso-octane pyrolysis.

    Science.gov (United States)

    Ning, HongBo; Gong, ChunMing; Li, ZeRong; Li, XiangYuan

    2015-05-07

    This study focuses on the studies of the main pressure-dependent reaction types of iso-octane (iso-C8H18) pyrolysis, including initial C-C bond fission of iso-octane, isomerization, and β-scission reactions of the alkyl radicals produced by the C-C bond fission of iso-octane. For the C-C bond fission of iso-octane, the minimum energy potentials are calculated at the CASPT2(2e,2o)/6-31+G(d,p)//CAS(2e,2o)/6-31+G(d,p) level of theory. For the isomerization and the β-scission reactions of the alkyl radicals, the optimization of the geometries and the vibrational frequencies of the reactants, transition states, and products are performed at the B3LYP/CBSB7 level, and their single point energies are calculated by using the composite CBS-QB3 method. Variable reaction coordinate transition state theory (VRC-TST) is used for the high-pressure limit rate constant calculation and Rice-Ramsperger-Kassel-Marcus/master equation (RRKM/ME) is used to calculate the pressure-dependent rate constants of these channels with pressure varying from 0.01-100 atm. The rate constants obtained in this work are in good agreement with those available from literatures. We have updated the rate constants and thermodynamic parameters for species involved in these reactions into a current chemical kinetic mechanism and also have improved the concentration profiles of main products such as C3H6 and C4H6 in the shock tube pyrolysis of iso-octane. The results of this study provide insight into the pyrolysis of iso-octane and will be helpful in the future development of branched paraffin kinetic mechanisms.

  15. Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Trevitt, Adam J.; Goulay, Fabien; Taatjes, Craig A.; Osborn, David L.; Leone, Stephen R.

    2009-12-23

    Low temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165 and 295 K is found to be relatively constant over this temperature range, 3.9 - 4.9 x 10-10 cm3 molecule-1 s-1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a slower rate coefficient of 1.3 x 10-10 cm3 molecule-1 s-1 at 105 K. At room temperature, non-exponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta and para isomers of cyanotoluene because of their similar ionization energies and the ~;; 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn?s moon Titan (~;;100 K) and are also likely to proceed at the temperature of interstellar clouds (10-20 K).

  16. Intrinsic reaction kinetics of coal char combustion by direct measurement of ignition temperature

    International Nuclear Information System (INIS)

    Kim, Ryang-Gyoon; Jeon, Chung-Hwan

    2014-01-01

    A wire heating reactor that can use a synchronized experimental method was developed to obtain the intrinsic kinetics of large coal char particles ranging in size from 0.4 to 1 mm. This synchronization system consists of three parts: a thermocouple wire for both heating and direct measurement of the particle temperature, a photodetector sensor for determining ignition/burnout points by measuring the intensity of luminous emission from burning particles, and a high-speed camera–long-distance microscope for observing and recording the movement of luminous zone directly. Coal char ignition was found to begin at a spot on the particle's external surface and then moved across the entire particle. Moreover, the ignition point determined according to the minimum of dT/dt is a spot point and not a full growth point. The ignition temperature of the spot point rises as the particle diameter increases. A spot ignition model, which describes the ignition in terms of the internal conduction and external/internal oxygen diffusion, was then developed to evaluate the intrinsic kinetics and predict the ignition temperature of the coal char. Internal conduction was found to be important in large coal char particles because its effect becomes greater than that of oxygen diffusion as the particle diameter increases. In addition, the intrinsic kinetics of coal char obtained from the spot ignition model for two types of coal does not differ significantly from the results of previous investigators. -- Highlights: • A novel technique was used to measure the coal char particle temperature. • The ignition point determined from a dT/dt minimum is a spot ignition point. • A spot ignition model was suggested to analyze the intrinsic reaction kinetics of coal char. • Internal conduction has to be considered in order to evaluate the intrinsic kinetics for larger particle (above 1 mm)

  17. Effect of ionic strength on the kinetics of ionic and micellar reactions in aqueous solution

    International Nuclear Information System (INIS)

    Dung, M.H.; Kozak, J.J.

    1982-01-01

    The effect of electrostatic forces on the rate of reaction between ions in aqueous solutions of intermediate ionic strength is studied in this paper. We consider the kinetics of reactions involving simple ionic species (1--1 and 2--2 electrolyte systems) as well as kinetic processes mediated by the presence of micellar ions (or other charged organizates). In the regime of ionic strength considered, dielectric saturation of the solvent in the vicinity of the reacting ions must be taken into account and this is done by introducing several models to describe the recovery of the solvent from saturation to its continuum dielectric behavior. To explore the effects of ion size, charge number, and ionic strength on the overall rate constant for the process considered, we couple the traditional theory of ionic reactions in aqueous solution with calculations of the electrostatic potential obtained via solution of the nonlinear Poisson--Boltzmann equation. The great flexibility of the nonlinear Poisson--Boltzmann theory allows us to explore quantitatively the influence of each of these effects, and our simulations show that the short-range properties of the electrostatic potential affect primarily kinetically controlled processes (to varying degrees, depending on the ionic system considered) whereas the down-range properties of the potential play a (somewhat) greater role in influencing diffusion-controlled processes. A detailed examination is made of ionic strength effects over a broad range of ionic concentrations. In the regime of low ionic strength, the limiting slope and intercept of the curve describing the dependence of log k/sub D/ on I/sup 1/2//(1+I/sup 1/2/) may differ considerably from the usual Debye--Hueckel limiting relations, depending on the particular model chosen to describe local saturation effects

  18. 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

  19. Struvite Precipitation and Phosphorous Removal from Urine Synthetic Solution: Reaction Kinetic Study

    Directory of Open Access Journals (Sweden)

    Marwa Saied Shalaby

    2015-03-01

    Full Text Available Phosphorus, like oil, is a non-renewable resource that must be harvested from finite resources in the earth’s crust. An essential element for life, phosphorus is becoming increasingly scarce, contaminated, and difficult to extract. Struvite or magnesium ammonium phosphate (MgNH4PO4.6H2O is a white, crystalline phosphate mineral that can be used as a bio-available fertilizer. The main objective of this research is to indicate the most important operating parameters affecting struvite precipitation by means of chemical reaction kinetics. The present study explores struvite precipitation by chemical method under different starting molar ratios, pH and SSR. It is shown that an increase of starting Mg: PO4: NH4 with respect to magnesium (1.6:1:1 strongly influences the growth rate of struvite and so the efficiency of the phosphate removal. This was attributed to the effect of magnesium on the struvite solubility product and on the reached supersaturation Super Saturation Ratio at optimum starting molar ratio and pH. It was also shown, by using chemical precipitation method that the determined Super Saturation Ratio (SSR values of struvite, at 8, 8.5, 9, 9.5 and 10 are 1.314, 4.29, 8.89, 9.87 and 14.89 respectively are close to those presented in the literature for different origins of wastewater streams. The results show that SSR , pH, and starting molar ratio strongly influences the kinetics of precipitation and so phosphorous removal to reach 93% removal percent , 5.95 mg/lit as a minimum PO4 remained in solution, and 7.9 gm precipitated struvite from feed synthetic solution of 750 ml . The product was subjected to chemical analysis by means of EDIX-FTIR, SEM and XRD showing conformity with published literature. First-order kinetics was found to be sufficient to describe the rate data. The rates increased with increasing pH and so SSR and the apparent rate constants for the reaction were determined. © 2015 BCREC UNDIP. All rights reserved

  20. Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

    Energy Technology Data Exchange (ETDEWEB)

    Miah, Md. Rezwan, E-mail: mrmche@yahoo.co [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Masud, Jahangir [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Ohsaka, Takeo, E-mail: ohsaka@echem.titech.ac.j [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)

    2010-12-15

    In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H{sub 2}O as the final product.

  1. Kinetics of oxygen reduction reaction at tin-adatoms-modified gold electrodes in acidic media

    International Nuclear Information System (INIS)

    Miah, Md. Rezwan; Ohsaka, Takeo

    2009-01-01

    In the present report, oxygen reduction reaction (ORR) at polycrystalline gold (Au (poly)) electrode in situ modified by the underpotential deposition (upd) of Sn-adatoms is addressed. The ORR was investigated at the Sn-adatoms-modified Au (poly) electrode by the hydrodynamic voltammetric technique with a view to evaluating the various related kinetic parameters. The results demonstrated that the underpotential deposited Sn-adatoms on the Au (poly) electrode substantially promoted the activity of the electrode towards an exclusive one-step four-electron ORR forming H 2 O as the final product.

  2. Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

    International Nuclear Information System (INIS)

    Miah, Md. Rezwan; Masud, Jahangir; Ohsaka, Takeo

    2010-01-01

    In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H 2 O as the final product.

  3. Kinetics of oxygen reduction reaction at tin-adatoms-modified gold electrodes in acidic media

    Energy Technology Data Exchange (ETDEWEB)

    Miah, Md. Rezwan [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)], E-mail: mrmche@yahoo.com; Ohsaka, Takeo [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)], E-mail: ohsaka@echem.titech.ac.jp

    2009-10-01

    In the present report, oxygen reduction reaction (ORR) at polycrystalline gold (Au (poly)) electrode in situ modified by the underpotential deposition (upd) of Sn-adatoms is addressed. The ORR was investigated at the Sn-adatoms-modified Au (poly) electrode by the hydrodynamic voltammetric technique with a view to evaluating the various related kinetic parameters. The results demonstrated that the underpotential deposited Sn-adatoms on the Au (poly) electrode substantially promoted the activity of the electrode towards an exclusive one-step four-electron ORR forming H{sub 2}O as the final product.

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

    International Nuclear Information System (INIS)

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

    1975-01-01

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

  5. Kinetics of H-D exchange in olefins with complicating reactions

    International Nuclear Information System (INIS)

    Trokhimets, A.I.

    1979-01-01

    The kinetics of H-D-exchange is considered for olefins under conditions when simple and complicated exchange occur together with hydrogenation. If hydrogenation takes place in the system, it is theoretically impossible to derive the integrated rate equation for the accumulation of deuterium in the olefin. The variation of the concentration of different deuteroolefins during the process can be calculated numerically. A method is proposed for evaluating the contribution of individual steps to the overall process and determining the rate constants of the most important reactions. (author)

  6. A robust methodology for kinetic model parameter estimation for biocatalytic reactions

    DEFF Research Database (Denmark)

    Al-Haque, Naweed; Andrade Santacoloma, Paloma de Gracia; Lima Afonso Neto, Watson

    2012-01-01

    lead to globally optimized parameter values. In this article, a robust methodology to estimate parameters for biocatalytic reaction kinetic expressions is proposed. The methodology determines the parameters in a systematic manner by exploiting the best features of several of the current approaches...... parameters, which are strongly correlated with each other. State-of-the-art methodologies such as nonlinear regression (using progress curves) or graphical analysis (using initial rate data, for example, the Lineweaver-Burke plot, Hanes plot or Dixon plot) often incorporate errors in the estimates and rarely...

  7. The kinetics of the photochemical reaction cycle of deuterated bacteriorhodopsin and pharaonis halorhodopsin

    International Nuclear Information System (INIS)

    Szakacs, Julianna; Lakatos, Melinda; Varo, Gy.; Ganea, Constanta

    2005-01-01

    Kinetic isotope effects in the photochemical reaction cycle of bacteriorhodopsin and pharaonis halorhodopsin were determined in H 2 O and D 2 O at normal pH, to get insight in the proton dependent steps of the transport process. All the steps of the bacteriorhodopsin photocycle at normal pH exhibited a strong isotope effect. In the case of halorhodopsin in both the chloride and nitrate transporting conditions the photocycle was not strongly affected by the deuterium exchange. In the case of chloride, a slight slow down of the photocycle could be observed. On the opposite, in the nitrate transport conditions a reverse effect is present. (author)

  8. Nonequilibrium transition and pattern formation in a linear reaction-diffusion system with self-regulated kinetics

    Science.gov (United States)

    Paul, Shibashis; Ghosh, Shyamolina; Ray, Deb Shankar

    2018-02-01

    We consider a reaction-diffusion system with linear, stochastic activator-inhibitor kinetics where the time evolution of concentration of a species at any spatial location depends on the relative average concentration of its neighbors. This self-regulating nature of kinetics brings in spatial correlation between the activator and the inhibitor. An interplay of this correlation in kinetics and disparity of diffusivities of the two species leads to symmetry breaking non-equilibrium transition resulting in stationary pattern formation. The role of initial noise strength and the linear reaction terms has been analyzed for pattern selection.

  9. Kinetics of the monomer-dimer reaction of yeast hexokinase PI.

    Science.gov (United States)

    Hoggett, J G; Kellett, G L

    1992-10-15

    Kinetic studies of the glucose-dependent monomer-dimer reaction of yeast hexokinase PI at pH 8.0 in the presence of 0.1 M-KCl have been carried out using the fluorescence temperature-jump technique. A slow-relaxation effect was observed which was attributed from its dependence on enzyme concentration to the monomer-dimer reaction; the reciprocal relaxation times tau-1 varied from 3 s-1 at low concentrations of glucose to 42 s-1 at saturating concentrations. Rate constants for association (kass.) and dissociation (kdiss.) were determined as a function of glucose concentration using values of the equilibrium association constant of the monomer-dimer reaction derived from sedimentation ultracentrifugation studies under similar conditions, and also from the dependence of tau-2 on enzyme concentration. kass. was almost independent of glucose concentration and its value (2 x 10(5) M-1.s-1) was close to that expected for a diffusion-controlled process. The influence of glucose on the monomer-dimer reaction is entirely due to effects on kdiss., which increases from 0.21 s-1 in the absence of glucose to 25 s-1 at saturating concentrations. The monomer and dimer forms of hexokinase have different affinities and Km values for glucose, and the results reported here imply that there may be a significant lag in the response of the monomer-dimer reaction to changes in glucose concentrations in vivo with consequent hysteretic effects on the hexokinase activity.

  10. 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.

  11. Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

    Science.gov (United States)

    Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

    2017-07-06

    The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

  12. The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled.

    Science.gov (United States)

    Göppel, Tobias; Palyulin, Vladimir V; Gerland, Ulrich

    2016-07-27

    An out-of-equilibrium physical environment can drive chemical reactions into thermodynamically unfavorable regimes. Under prebiotic conditions such a coupling between physical and chemical non-equilibria may have enabled the spontaneous emergence of primitive evolutionary processes. Here, we study the coupling efficiency within a theoretical model that is inspired by recent laboratory experiments, but focuses on generic effects arising whenever reactant and product molecules have different transport coefficients in a flow-through system. In our model, the physical non-equilibrium is represented by a drift-diffusion process, which is a valid coarse-grained description for the interplay between thermophoresis and convection, as well as for many other molecular transport processes. As a simple chemical reaction, we consider a reversible dimerization process, which is coupled to the transport process by different drift velocities for monomers and dimers. Within this minimal model, the coupling efficiency between the non-equilibrium transport process and the chemical reaction can be analyzed in all parameter regimes. The analysis shows that the efficiency depends strongly on the Damköhler number, a parameter that measures the relative timescales associated with the transport and reaction kinetics. Our model and results will be useful for a better understanding of the conditions for which non-equilibrium environments can provide a significant driving force for chemical reactions in a prebiotic setting.

  13. The kinetics of dolomite reaction rim growth under isostatic and non-isostatic pressure conditions

    Science.gov (United States)

    Helpa, V.; Rybacki, E.; Morales, L. G.; Abart, R.; Dresen, G. H.

    2013-12-01

    During burial and exhumation, rocks are simultaneously exposed to metamorphic reactions and tectonic stresses. Therefore, the reaction rate of newly formed minerals may depend on chemical and mechanical driving forces. Here, we investigate the reaction kinetics of dolomite (CaMg[CO3]2) rim growth by solid-state reactions experiments on oriented calcite (CaCO3) and magnesite (MgCO3) single crystals under isostatic and non-isostatic pressure conditions. Cylindrical samples of 3-5 mm length and 7 mm diameter were drilled and polished perpendicular to the rhombohedral cleavage planes of natural clear crystals. The tests were performed using a Paterson-type deformation apparatus at P = 400 MPa confining pressure, temperatures, T, between 750 and 850°C, and reaction durations, t, of 2 - 146 h to calculate the kinetic parameters of dolomite rim growth under isostatic stress conditions. For non-isostatic reaction experiments we applied in addition differential stresses, σ, up to 40 MPa perpendicular to the contact interface at T = 750°C for 4 - 171 h duration, initiating minor inelastic deformation of calcite. The thickness of the resulting dolomite reaction rims increases linearly with the square root of time, indicating a diffusion-controlled reaction. The rims consist of two different textural domains. Granular dolomite grains (≈ 2 -5 μm grain size) form next to calcite and elongated palisade-shaped grains (1-6 μm diameter) grow perpendicular to the magnesite interface. Texture measurements with the electron backscatter diffraction technique indicate that the orientations of dolomite grains are mainly influenced by the orientation of the calcite educt crystal, in particular in the granular rim. To some extent, the texture of dolomite palisades is also influenced by the orientation of magnesite. The thickness of the two individual layers increases with temperature. At 400 MPa isostatic pressure, T = 750°C and t = 29 hours, a 5 μm thick granular dolomite layer

  14. Kinetics of the epoxy–thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components

    International Nuclear Information System (INIS)

    Loureiro, Roi Meizoso; Amarelo, Tánia Carballeira; Abuin, Senen Paz; Soulé, Ezequiel R.; Williams, Roberto J.J.

    2015-01-01

    Graphical abstract: - Highlights: • Reaction kinetics of a monoepoxy and a monothiol was studied by DSC. • Benzyldimethylamine (BDMA) was used as initiator. • Reaction exhibited a long induction period followed by a fast autocatalytic rate. • A mechanistic kinetic model provided a reasonable fitting of the kinetic behavior. • The formulation simulates the behavior of room-temperature-cure commercial epoxies. - Abstract: An analysis of the kinetics of the epoxy–thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted

  15. Kinetics of the epoxy–thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components

    Energy Technology Data Exchange (ETDEWEB)

    Loureiro, Roi Meizoso; Amarelo, Tánia Carballeira [Gairesa, Outeiro 1, Lago (Valdoviño), 15551 A Coruña (Spain); Abuin, Senen Paz, E-mail: senen@gairesa.com [Gairesa, Outeiro 1, Lago (Valdoviño), 15551 A Coruña (Spain); Soulé, Ezequiel R. [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina); Williams, Roberto J.J., E-mail: williams@fi.mdp.edu.ar [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina)

    2015-09-20

    Graphical abstract: - Highlights: • Reaction kinetics of a monoepoxy and a monothiol was studied by DSC. • Benzyldimethylamine (BDMA) was used as initiator. • Reaction exhibited a long induction period followed by a fast autocatalytic rate. • A mechanistic kinetic model provided a reasonable fitting of the kinetic behavior. • The formulation simulates the behavior of room-temperature-cure commercial epoxies. - Abstract: An analysis of the kinetics of the epoxy–thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted.

  16. Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

    Science.gov (United States)

    Basilevsky, M. V.; Odinokov, A. V.; Titov, S. V.; Mitina, E. A.

    2013-12-01

    The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ0 = ℏω0/kBT where ω0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ0 conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the existing theories of the ET. Our alternative dynamic ET model for local modes immersed in the continuum harmonic medium is formulated for both classical and quantum regimes, and accounts explicitly for the mode/medium interaction. The kinetics of the energy exchange between the local ET subsystem and the surrounding environment essentially determine the total ET rate. The efficient computer code for rate computations is elaborated on. The computations are available for a wide range of system parameters, such as the temperature, external field, local mode frequency, and characteristics of mode/medium interaction. The relation of the

  17. Reaction kinetics of irradiation prepolymerized MMA-PU IPN by 5DXC FTIR

    International Nuclear Information System (INIS)

    Wu Yiming; Zhang Zhiping; Luo Ning

    2000-01-01

    The reaction kinetics of irradiation-prepolymerized MMA-PU (polyether) IPNs have been studied by FTIR. The results indicate that the polymerization of each component in the IPN follows its normal distinct reaction mechanism with no mutual interference. Increasing the concentration of TMPTAM (crosslinking agent of PMMA) increased the formation rate of PMMA, while the formation rate of PU networks remained almost the same. Increasing the concentration of TMP (crosslinking agent of PU) increased the formation rate of PU, while the formation rate of PMMA networks decreased. The formation rate of PU was obviously faster than that of PMMA. A theory for the cage effect of the PU network has been proposed. (author)

  18. Heterogeneous reaction of particulate chlorpyrifos with NO3 radicals: Products, pathways, and kinetics

    Science.gov (United States)

    Li, Nana; Zhang, Peng; Yang, Bo; Shu, Jinian; Wang, Youfeng; Sun, Wanqi

    2014-08-01

    Chlorpyrifos is a typical chlorinated organophosphorus pesticide. The heterogeneous reaction of chlorpyrifos particles with NO3 radicals was investigated using a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and a real-time atmospheric gas analysis mass spectrometer. Chlorpyrifos oxon, 3,5,6-trichloro-2-pyridinol, O,O-diethyl O-hydrogen phosphorothioate, O,O-diethyl ester thiophosphoric acid, diethyl hydrogen phosphate and a phosphinyl disulfide compound were identified as the main degradation products. The heterogeneous reaction pathways were proposed and their kinetic processes were investigated via a mixed-phase relative rate method. The observed effective rate constant is 3.4 ± 0.2 × 10-12 cm3 molecule-1 s-1.

  19. The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

    KAUST Repository

    Ebner, Davidâ C.

    2009-12-07

    The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.

  20. Atmospheric chemistry of CF3COOH. Kinetics of the reaction with OH radicals

    DEFF Research Database (Denmark)

    Møgelberg, T.E.; Nielsen, O.J.; Sehested, J.

    1994-01-01

    Two different experimental techniques were used to study the kinetics of the reaction of OH radicals with trifluoroacetic acid, CF3COOH. Using a pulse radiolysis absolute rate technique, rate constants at 315 and 348 K were determined to be (1.6 +/- 0.4) x 10(-13) and (1.5 +/- 0.2) x 10(-13) cm3...... molecule-1 s-1, respectively. Using a long path-length FTIR relative rate technique a rate constant of (1.7 +/- 0.5) x 10(-13) cm3 molecule-1 s-1 was obtained at 296 K. In the atmosphere, reaction with OH radicals in the gas phase is estimated to account for 10%-20% of the loss of CF3COOH. The major fate...

  1. 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.

  2. The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

    KAUST Repository

    Ebner, Davidâ C.; Bagdanoff, Jeffreyâ T.; Ferreira, Ericâ M.; McFadden, Ryanâ M.; Caspi, Danielâ D.; Trend, Raissaâ M.; Stoltz, Brianâ M.

    2009-01-01

    The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.

  3. Performance of the periodic pulse technique--4. Periodic pulse reaction kinetics of oxidative dehydrogenation of isobutyraldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Hattori, T.; Ii, M.; Murakami, Y.

    1980-07-01

    The periodic pulse method was used to study the reaction mechanism and kinetics of the oxidative dehydrogenation of isobutyraldehyde (IBA) by following the formation rates of methacrolein (MA), carbon monoxide and dioxide (CO/sub x/), and other products (P) as a function of pulse widths and reactant partial pressures at 350/sup 0/C over a 2:3 antimony oxide/molybdenum trioxide catalyst. The results were consistent with a mechanism according to which IBA reacts with oxygen retained by the catalyst to form MA, causing reduction of the catalyst. The IBA also adsorbed on the surface as an oxygenated species which either reacted with gas-phase oxygen to form CO/sub x/ or desorbed as an oxygenated P. The reduced catalyst surface was reoxidized by oxygen adsorption. Implications of catalyst tailoring for increased MA yields by improving the redox mechanism and inhibiting the surface reactions, are discussed.

  4. Kinetics of the reaction between plutonium (4) and neptunium (4) in nitric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Koltunov, V S; Zhuravleva, G I; Marchenko, V I

    1976-01-01

    The kinetics of the oxidation of neptunium(IV) to neptunium(V) by tetravalent plutonium ions in solutions of HNO/sub 3/ + NaNO/sub 3/ at constant (..mu.. = 2) and variable (..mu.. = 0.7-2.0) ionic strengths of the solution was investigated by a spectrophotometric method. It was established that in the range of concentrations (Np(IV)) = (4.25-10.6) x 10/sup 13/; (Pu(IV)) = (2.6-3.9)x10/sup -3/ M; (H/sup +/) 0.37-1.91 M, a first order is observed with respect to the reagents, while the order of the reaction with respect to H/sup +/ ions is equal to -3. The average value of the true rate constant of the reaction is k = 27.9+-1.3 M/sup 2/xmin/sup -1/ at ..mu..=2 and 39/sup 0/C. It was shown that with increasing analytical concentration of HNO/sub 3/ and NO/sub 3//sup -/ ions (in a mixture of HNO/sub 3/ +HClO/sub 4/), the value of K decreases. On the basis of an invetigation of the dependence of the reaction rate on the temperature in the interval 31-44.8/sup 0/, we calculated the values of the energy (E = 34.6 kcal/mole), enthalpy (..delta..H* = 34 kcal/mole), free energy (..delta..F* = 19.6 kcal/mole, entropy (..delta..S* = 49 entropy units) of activation of the reaction and the formal ionic entropy of the activated complex (PuOOHNp/sup 5 +/)*, S* = -87 entropy units. A reaction mechanism including an interaction of hydrolyzed neptunium and plutonium ions as the rate-determining step was proposed and discusses. The results obtained are compared with data for this reaction in perchloric acid wolution and for other similar redox reactions.

  5. 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.

  6. The chemical kinetics of the reactions of lithium with steam-air mixtures

    International Nuclear Information System (INIS)

    Barnett, D.S.; Kazimi, M.S.

    1989-04-01

    This work involved the experimental and analytical determination of the consequences of lithium fires in the presence of steam. Experiments were performed to characterize the chemical reactions of lithium with steam-nitrogen and steam-air mixtures. Models were introduced in the LITFIRE code to describe lithium fires in the presence of steam inside the containment building and plasma chamber of a hypothetical fusion reactor. The code was also equipped with the capability to determine the effects of decay heat and lithium fire on the temperature response of the reactor first wall in the event of a coolant disturbance. Forty-two kinetics experiments were performed in which a stream of steam-nitrogen or steam-air was passed over and reacted with approximately three grams of lithium heated to a predetermined temperature. The lithium reaction rates with the constituent gases were measured and characterized for a wide range of lithium temperatures and gas compositions. Experiments were performed with steam molar concentrations of 5, 15 and 30% and lithium temperatures ranging from 400 to 1100 degree C, inclusive. The LITFIRE code was modified to enable it to model the interactions of lithium with steam-air atmospheres. Results of the reaction kinetics experiments were used in the reaction model, and the heat transfer model was expanded to allow it to handle condensible atmospheres. Three groups of accidents were investigated: a spill on the containment building floor, a spill inside the reactor plasma chamber, and a spill inside the plasma chamber with steam injection to the containment building simulating a steam line break. The results were compared to dry air cases under the same conditions. 23 refs., 66 figs., 18 tabs

  7. Study on the kinetics of gel formation in the radiation crosslinking reaction

    International Nuclear Information System (INIS)

    Wang Mingjun; Liu Yuming

    1988-01-01

    From the kinetic equation of gel formation obtained by the authors, the mechanism of gel formation may be interpreted clearly as follows: (1) When the degree of crosslinking q g , the system is sol and the crosslinking reaction is only carried out between the sol molecules. (q g is the gel point). (2) When q=q g , there exists a beginning point where the gel is coexisted with the sol, and the system is still sol, and the crosslinking reaction is still carried out between the sol molecules. (3) When q>q g , the crosslinking reaction exceeds the gel point and the gel is coexisted with the sol. The kinetic equation shows clearly that the transformation from sol into gel is caused by crosslinking reaction of the uncrosslinked chain units between the sol and gel molecules. As a result the sol molecules are transformed into the gel molecules gradually, and the sol fraction is reduced. When the chain units P-barw(s)S(1-s)dq in sol are crosslinked with gel, the sol fraction in the system is reduced ds (where P-barw(s) is a function of the radiation dose and s is sol frection). The degree of crosslinking per unit dose (q 0 ) is a reduced function of dose (R). The equation for calculating its value for every irradiation dose is obtained. After knowing the correlation between P-bar W(s) vs R and q 0 vs R, the distribution of gel and sol in the process of radiation crosslinking can be discussed as well

  8. 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.

  9. Material Balance And Reaction Kinetics Modeling For Penex Isomerization Process In Daura Refinery

    Directory of Open Access Journals (Sweden)

    Hamadi Adel Sharif

    2017-01-01

    Full Text Available Penex Deisohexanizer isomerization of light straight run naphtha is a significant process for petroleum refining and proved to be effective technology to produce gasoline components with a high octane number. Modeling of the chemical kinetic reactions is an important tool because it is a better tool for optimization of the experimental data into parameters used for industrial reactors. The present study deals on the isomerization process in Daura refinery. Material balance calculations were done mathematically on the unit for the kinetics prediction purpose. A kinetic mathematical model was derived for the prediction rate constants K1 and K2 and activation energy Ea at operating temperatures range 120-180°C. According to the model, the results show that with increasing of temperature leads to increased K1 directly, where the K2 values proportional inversely. The activation energy results show that Ea1(nC6

  10. Cholesterol photo-oxidation: A chemical reaction network for kinetic modeling.

    Science.gov (United States)

    Barnaba, Carlo; Rodríguez-Estrada, Maria Teresa; Lercker, Giovanni; García, Hugo Sergio; Medina-Meza, Ilce Gabriela

    2016-12-01

    In this work we studied the effect of polyunsaturated fatty acids (PUFAs) methyl esters on cholesterol photo-induced oxidation. The oxidative routes were modeled with a chemical reaction network (CRN), which represents the first application of CRN to the oxidative degradation of a food-related lipid matrix. Docosahexaenoic acid (DHA, T-I), eicosapentaenoic acid (EPA, T-II) and a mixture of both (T-III) were added to cholesterol using hematoporphyrin as sensitizer, and were exposed to a fluorescent lamp for 48h. High amounts of Type I cholesterol oxidation products (COPs) were recovered (epimers 7α- and 7β-OH, 7-keto and 25-OH), as well as 5β,6β-epoxy. Fitting the experimental data with the CRN allowed characterizing the associated kinetics. DHA and EPA exerted different effects on the oxidative process. DHA showed a protective effect to 7-hydroxy derivatives, whereas EPA enhanced side-chain oxidation and 7β-OH kinetic rates. The mixture of PUFAs increased the kinetic rates several fold, particularly for 25-OH. With respect to the control, the formation of β-epoxy was reduced, suggesting potential inhibition in the presence of PUFAs. Copyright © 2016 Elsevier Inc. All rights reserved.

  11. Assessment of sorption properties and kinetic reaction of phosphorus reactive material to limit diffuse pollution

    Directory of Open Access Journals (Sweden)

    Bus Agnieszka

    2017-09-01

    Full Text Available Assessment of sorption properties and kinetic reaction of phosphorus reactive material to limit diffuse pollution. Polonite® is an effective reactive material (manufactured from opoka rock for removing phosphorus from aqueous solutions. In conducted experiments, Polonite® of grain size of 2–5 mm was used as a potential reactive material which can be used as a filter fulfillment to reduce phosphorus diffuse pollution from agriculture areas. Kinetic and equilibrium studies (performed as a batch experiment were carried out as a function of time to evaluate the sorption properties of the material. The obtained results show that Polonite® effectively removes such contamination. All tested concentrations (0.998, 5.213, 10.965 mg P-PO4·L−1 are characterized by a better fit to pseudo-second kinetic order. The Langmuir isotherm the best reflects the mechanism of adsorption process in case of Polonite® and based on the isotherm, calculated maximum adsorption capacity equals 96.58 mg P-PO4·g−1.

  12. Ground reaction forces and knee kinetics during single and repeated badminton lunges.

    Science.gov (United States)

    Lam, Wing Kai; Ding, Rui; Qu, Yi

    2017-03-01

    Repeated movement (RM) lunge that frequently executed in badminton might be used for footwear evaluation. This study examined the influence of single movement (SM) and RM lunges on the ground reaction forces (GRFs) and knee kinetics during the braking phase of a badminton lunge step. Thirteen male university badminton players performed left-forward lunges in both SM and RM sessions. Force platform and motion capturing system were used to measure GRFs and knee kinetics variables. Paired t-test was performed to determine any significant differences between SM and RM lunges regarding mean and coefficient of variation (CV) in each variable. The kinetics results indicated that compared to SM lunges, the RM lunges had shorter contact time and generated smaller maximum loading rate of impact force, peak knee anterior-posterior force, and peak knee sagittal moment but generated larger peak horizontal resultant forces (Ps < 0.05). Additionally, the RM lunges had lower CV for peak knee medial-lateral and vertical forces (Ps < 0.05). These results suggested that the RM testing protocols had a distinct loading response and adaptation pattern during lunge and that the RM protocol showed higher within-trial reliability, which may be beneficial for the knee joint loading evaluation under different interventions.

  13. 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

  14. Surface Reaction Kinetics of Ga(1-x)In(x)P Growth During Pulsed Chemical Beam Epitaxy

    National Research Council Canada - National Science Library

    Dietz, N; Beeler, S. C; Schmidt, J. W; Tran, H. T

    2000-01-01

    ... into the surface reaction kinetics during an organometallic deposition process. These insights will allow us to move the control point closer to the point where the growth occurs, which in a chemical been epitaxy process is a surface reaction layer (SRL...

  15. A study of redox kinetic in silicate melt; Etude cinetique des reactions d'oxydoreduction dans les silicates

    Energy Technology Data Exchange (ETDEWEB)

    Magnien, V

    2005-12-15

    The aim of this thesis is to understand better iron redox reactions and mechanisms in silicate glasses and melts. Particular interest has been paid to the influence of temperature and chemical composition. For this purpose, the influence of alkali element content, iron content and network formers on the kinetics of redox reactions has been determined through XANES and Raman spectroscopy experiments performed either near the glass transition or above the liquidus temperature. As a complement, electrical conductivity and RBS spectroscopy experiments have been made to characterize the diffusivity of the species that transport electrical charges and the reaction morphology, respectively. Temperature and composition variations can induce changes in the dominating redox mechanism. At a given temperature, the parameters that exert the strongest influence on redox mechanisms are the presence or lack of divalent cations and the existing decoupling between the mobility of network former and modifier elements. Near Tg, the diffusion of divalent cations, when present in the melt, controls the kinetics of iron redox reactions along with a flux of electron holes. Composition, through the degree of polymerization and the silicate network structure, influences the kinetics and the nature of the involved cations, but not the mechanisms of the reaction. Without alkaline earth elements, the kinetics of redox reactions are controlled by the diffusion of oxygen species. With increasing temperatures, the diffusivities of all ionic species tend to become similar. The decoupling between ionic fluxes then is reduced so that several mechanisms become kinetically equivalent and can thus coexist. (author)

  16. A study of redox kinetic in silicate melt; Etude cinetique des reactions d'oxydoreduction dans les silicates

    Energy Technology Data Exchange (ETDEWEB)

    Magnien, V

    2005-12-15

    The aim of this thesis is to understand better iron redox reactions and mechanisms in silicate glasses and melts. Particular interest has been paid to the influence of temperature and chemical composition. For this purpose, the influence of alkali element content, iron content and network formers on the kinetics of redox reactions has been determined through XANES and Raman spectroscopy experiments performed either near the glass transition or above the liquidus temperature. As a complement, electrical conductivity and RBS spectroscopy experiments have been made to characterize the diffusivity of the species that transport electrical charges and the reaction morphology, respectively. Temperature and composition variations can induce changes in the dominating redox mechanism. At a given temperature, the parameters that exert the strongest influence on redox mechanisms are the presence or lack of divalent cations and the existing decoupling between the mobility of network former and modifier elements. Near Tg, the diffusion of divalent cations, when present in the melt, controls the kinetics of iron redox reactions along with a flux of electron holes. Composition, through the degree of polymerization and the silicate network structure, influences the kinetics and the nature of the involved cations, but not the mechanisms of the reaction. Without alkaline earth elements, the kinetics of redox reactions are controlled by the diffusion of oxygen species. With increasing temperatures, the diffusivities of all ionic species tend to become similar. The decoupling between ionic fluxes then is reduced so that several mechanisms become kinetically equivalent and can thus coexist. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-08-25

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

  18. Quantitative modeling of the reaction/diffusion kinetics of two-chemistry photopolymers

    Science.gov (United States)

    Kowalski, Benjamin Andrew

    Optically driven diffusion in photopolymers is an appealing material platform for a broad range of applications, in which the recorded refractive index patterns serve either as images (e.g. data storage, display holography) or as optical elements (e.g. custom GRIN components, integrated optical devices). A quantitative understanding of the reaction/diffusion kinetics is difficult to obtain directly, but is nevertheless necessary in order to fully exploit the wide array of design freedoms in these materials. A general strategy for characterizing these kinetics is proposed, in which key processes are decoupled and independently measured. This strategy enables prediction of a material's potential refractive index change, solely on the basis of its chemical components. The degree to which a material does not reach this potential reveals the fraction of monomer that has participated in unwanted reactions, reducing spatial resolution and dynamic range. This approach is demonstrated for a model material similar to commercial media, achieving quantitative predictions of index response over three orders of exposure dose (~1 to ~103 mJ cm-2) and three orders of feature size (0.35 to 500 microns). The resulting insights enable guided, rational design of new material formulations with demonstrated performance improvement.

  19. Application of adjustable pulse lasers to studying rapid reaction kinetics of excited lanthanide complexing

    Energy Technology Data Exchange (ETDEWEB)

    Gruzdev, V.P. (Gosudarstvennyj Opticheskij Inst., Leningrad (USSR))

    1983-12-01

    Using some europium (3) ion complexes new possibilities to be opened by application of adjustable pulse lasers for studying rapid reactions of electron-excited metal ion complexing are demonstrated. The 6Zh rhodamine pulse laser is used as a source of nonequilibrium photoexcitation of an array of Eu/sup 3 +/ complexes in the luminescent kinetic spectroscopy method. The following results are obtained: for the first time the rate of reaction of acetate ion substitution for water molecules of an excited (/sup 5/D/sub 0/) ion of Eu/sup 3 +/ was measured to be (0.7+-0.2)x10/sup 7/ s/sup -1/; using direct experiments the lower limit for the rate of transition of one isomeric form of the excited Eu x EDTA complex into another one in an aqueous solution is determined to be 5x10/sup 5/ s/sup -1/ at 295 K; the kinetics of the excitation energy migration beteen aqueous solvates of Eu/sup 3 +/ and EuxEDTA complexes is investigated.

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

    International Nuclear Information System (INIS)

    Yamada, Y.; Kawase, Y.

    2006-01-01

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

  1. Reaction kinetics and transformation of carbadox and structurally related compounds with aqueous chlorine.

    Science.gov (United States)

    Shah, Amisha D; Kim, Jae-Hong; Huang, Ching-Hua

    2006-12-01

    The potential release of carbadox (CDX), a commonly used antibacterial agent in swine husbandry, into water systems is of a concern due to its carcinogenic and genotoxic effects. Until this study, the reactivity of carbadox (possessing quinoxaline N,N'-dioxide and hydrazone moieties) toward aqueous chlorine has yetto be investigated in depth. Chemical reactivity, reaction kinetics, and transformation pathways of carbadox and structurally related compounds with free chlorine under typical water treatment conditions were determined. This study found that only CDX and desoxycarbadox (DCDX), a main metabolite of CDX with no ring N-oxide groups, react rapidly with free chlorine while other structurally related compounds including olaquindox, quindoxin, quinoxaline N-oxide, quinoxaline, and quinoline N-oxide do not. The reaction kinetics of CDX and DCDX with chlorine are highly pH dependent (e.g., the apparent second-order rate constant, kapp, for CDX ranges from 51.8 to 3.15 x 10(4) M(-1)s(-1) at pH 4-11). The high reactivity of CDX and DCDX to chlorine involves deprotonation of their hydrazone N-H moieties where initial chlorine attack results in a reactive intermediate that is further attacked by nucleophiles in the matrix to yield non-chlorinated, hydroxylated, and larger molecular weight byproducts. All of the CDX's byproducts retain their biologically active N-oxide groups, suggesting that they may remain as active antibacterial agents.

  2. Reaction network modelling for kinetic parameters of pyrolytic reactions of CHON extractants in nuclear fuel processing waste management. Contributed Paper IT-07

    International Nuclear Information System (INIS)

    Gaikar, Vilas G.; Thaore, Vaishali

    2014-01-01

    The recovery and purification of plutonium (Pu) from uranium (U) and of U from Thorium (Th) in spent nuclear fuel reprocessing is accomplished by processes that employ organophosphorous compounds as extractants.The main objective of the present work was to develop a suitable kinetic model and to determine the kinetic parameters of the set of reactions involved in the pyrolysis of amides by fitting the experimental data in the reaction network model. The experimental data and analysis are expected to be useful in the steam pyrolysis of amide waste in fuel reprocessing in the nuclear industry. The basic approach was to understand the reaction mechanism of the steam pyrolysis of amides and then to estimate the reaction rate constants for the generation and consumption of different species by solving the model equations, allowing for the determination of important species in the reaction network

  3. Fock space, symbolic algebra, and analytical solutions for small stochastic systems.

    Science.gov (United States)

    Santos, Fernando A N; Gadêlha, Hermes; Gaffney, Eamonn A

    2015-12-01

    Randomness is ubiquitous in nature. From single-molecule biochemical reactions to macroscale biological systems, stochasticity permeates individual interactions and often regulates emergent properties of the system. While such systems are regularly studied from a modeling viewpoint using stochastic simulation algorithms, numerous potential analytical tools can be inherited from statistical and quantum physics, replacing randomness due to quantum fluctuations with low-copy-number stochasticity. Nevertheless, classical studies remained limited to the abstract level, demonstrating a more general applicability and equivalence between systems in physics and biology rather than exploiting the physics tools to study biological systems. Here the Fock space representation, used in quantum mechanics, is combined with the symbolic algebra of creation and annihilation operators to consider explicit solutions for the chemical master equations describing small, well-mixed, biochemical, or biological systems. This is illustrated with an exact solution for a Michaelis-Menten single enzyme interacting with limited substrate, including a consideration of very short time scales, which emphasizes when stiffness is present even for small copy numbers. Furthermore, we present a general matrix representation for Michaelis-Menten kinetics with an arbitrary number of enzymes and substrates that, following diagonalization, leads to the solution of this ubiquitous, nonlinear enzyme kinetics problem. For this, a flexible symbolic maple code is provided, demonstrating the prospective advantages of this framework compared to stochastic simulation algorithms. This further highlights the possibilities for analytically based studies of stochastic systems in biology and chemistry using tools from theoretical quantum physics.

  4. REACTION KINETICS SELF-PROPOGATION REGIME DURING PRE-IGNITION PERIOD

    Directory of Open Access Journals (Sweden)

    D. D. Polishchuk

    2015-11-01

    Full Text Available Self-propagation high temperature synthesis (SHS technological regulations application is mainly limited by transformation processes taking place in the pre-ignition period. Zn-S, Zn-Se, Ti-C and 3Ni-Al small sample systems ignition experimental study was carried out under heating conditions in inert atmosphere with temperature values T = 1200K.It was shown that at this temperature level a chemical reaction can be initiated, turning into a self-sustaining mode. Wherein the reaction limiting factors can be mass transfer processes. Ignition temperatures were determined and plotted via the samples size. A physical ignition model was developed assuming the pre-ignition period limiting reaction Arrhenius law.The inverse combustion problem solution made it possible to calculate the low-temperature (T = 800 ÷ 1200K reaction kinetic constant values. Comparison thus obtained values  with the known data of other researchers showed their good agreement.Activation energy values for the Zn-S system were used to calculate the heat wave propagation speed. This value appeared to coincide with experimental values.Obtained results analysis leads to the conclusion about the availability and justification for the proposed method of express-analysis of presupposed, but previously not studied SHS systems. The results thus obtained allow us to estimate conditions for the SHS technology implementation, the reactor characteristic sizes and the thermal wave’s propagation speed.

  5. Kinetic Modeling of the Reaction Rate for Quartz and Carbon Pellet

    Science.gov (United States)

    Li, Fei; Tangstad, Merete

    2018-04-01

    Kinetic modeling of quartz and carbon pellet at temperatures of 1898 K, 1923 K, and 1948 K (1625 °C, 1650 °C, and 1675 °C) was investigated in this study. The carbon materials used were charcoal, coke, coal, and preheated coal. The overall SiC producing reaction can be described by the reaction SiO2 + 3C = SiC + 2CO. In the SiC-producing step, the reaction rate of quartz and carbon pellet can be expressed as {d{ pct}}/dt = ( {1 - 0.40 × X_{fix - C}^{ - 0.86} × FC × {pct}} ) × A × \\exp ( { - E/{{RT}}} ) The carbon factor F C was used to describe the influence of different carbon materials that effect the gas-solid interface reaction. For charcoal, coke, coal, and preheated coal, the F C values were 0.83, 0.80, 0.94, and 0.83, respectively. The pre-exponential factor A values for the preceding four carbon materials were 1.06 × 1016 min-1, 4.21 × 1015 min-1, 3.85 × 109 min-1, and 1.00 × 1025 min-1, respectively. The activation energies E for the SiC-producing step were 570, 563, 336, and 913 kJ/mole for charcoal, coke, coal, and preheated coal pellets, respectively.

  6. Kinetics of the reaction between H· and superheated water probed with muonium

    International Nuclear Information System (INIS)

    Alcorn, Chris D.; Brodovitch, Jean-Claude; Percival, Paul W.; Smith, Marisa; Ghandi, Khashayar

    2014-01-01

    Highlights: • Rate constants for reactions of H with water resolve a controversy. • H reacts with superheated water via two channels. • The findings have important implications for the safety of some nuclear power reactors. - Abstract: Safe operation of supercritical water-cooled reactors requires knowledge of the kinetics of transient species formed by the radiolysis of water in the range 300–650 °C. Using muonium, it is possible to study aqueous H · atom chemistry over this temperature range. An important reaction to study is that of the H · atom with water itself, because it is a potential source of molecular H 2 . The concentration of H 2 is important to plant coolant chemistry, as H 2 is currently added to suppress oxidative corrosion in CANDU reactors. The reaction of muonium with H 2 O and D 2 O was studied experimentally up to 450 °C, and also via quantum chemical computations to investigate possible isotope effects. Our results suggest that although the H · atom abstraction from H 2 O is important at temperatures above 300 °C, the electron-producing channel (H · + H 2 O ⇌ H 3 O + + e aq - ) is significant at temperatures up to 300 °C, and becomes the dominant reaction channel at lower temperatures

  7. Kinetics of the reaction between H{sup ·} and superheated water probed with muonium

    Energy Technology Data Exchange (ETDEWEB)

    Alcorn, Chris D. [Department of Chemistry and Biochemistry, Mount Allison University, Sackville, New Brunswick E4L 1G8 (Canada); Brodovitch, Jean-Claude [Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A 1S6 (Canada); Percival, Paul W. [Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A 1S6 (Canada); TRIUMF, 4004 Wesbrook Mall, Vancouver, British Columbia V6T 2A3 (Canada); Smith, Marisa [Department of Chemistry and Biochemistry, Mount Allison University, Sackville, New Brunswick E4L 1G8 (Canada); Ghandi, Khashayar, E-mail: kghandi@mta.ca [Department of Chemistry and Biochemistry, Mount Allison University, Sackville, New Brunswick E4L 1G8 (Canada)

    2014-05-19

    Highlights: • Rate constants for reactions of H with water resolve a controversy. • H reacts with superheated water via two channels. • The findings have important implications for the safety of some nuclear power reactors. - Abstract: Safe operation of supercritical water-cooled reactors requires knowledge of the kinetics of transient species formed by the radiolysis of water in the range 300–650 °C. Using muonium, it is possible to study aqueous H{sup ·} atom chemistry over this temperature range. An important reaction to study is that of the H{sup ·} atom with water itself, because it is a potential source of molecular H{sub 2}. The concentration of H{sub 2} is important to plant coolant chemistry, as H{sub 2} is currently added to suppress oxidative corrosion in CANDU reactors. The reaction of muonium with H{sub 2}O and D{sub 2}O was studied experimentally up to 450 °C, and also via quantum chemical computations to investigate possible isotope effects. Our results suggest that although the H{sup ·} atom abstraction from H{sub 2}O is important at temperatures above 300 °C, the electron-producing channel (H{sup ·} + H{sub 2}O ⇌ H{sub 3}O{sup +} + e{sub aq}{sup -}) is significant at temperatures up to 300 °C, and becomes the dominant reaction channel at lower temperatures.

  8. The kinetics of free radical metathetical and addition reactions in silane solutions

    International Nuclear Information System (INIS)

    Aloni, R.

    1976-12-01

    In this work radiolytic technique was employed for the initiation of free radical chainreactions in silane solution. The kinetic analysis of the chain mechanism in various solutions enabled the determination of the Arrhenius parameters for metathesis, addition and unimolecular decomposition reactions which make up the chainpropagation sequence in the systems studied. The following radical reactions were investigated: chlorine atom abstraction from chloromethanes by SiCl 3 and Et 3 Si radicals, and chlorine atom abstraction from chloroethanes by Et 3 Si radicals; unimolecular decomposition reactions and hydrogen atom abstraction, *from the solvent, of chloroethyl radicals in triethylsilane solutions; addition and abstraction reactions of Et 3 Si radicals with chloroolefins. Arrhenius parameters were determined for abstraction of chlorine atom from CH 3 Cl, CH 2 Cl 2 , CHCl 3 and CCl 4 , by SiCl 3 radicals and from CCl 4 , CHCl 3 , CH 2 Cl 2 , CCl 3 CN, C 2 Cl 5 H, sym-C 2 Cl 4 H 2 , asym-C 2 Cl 4 H 2 , 1.1.1-C 2 Cl 3 H 3 , 1.1.1-C 2 Dl 3 F 3 and 1.1-C 2 Cl 2 H 4 by Et 3 Si radicals. (author)

  9. Kinetics of the Reactions of IO Radicals with NO and NO2

    Science.gov (United States)

    Daykin, E. P.; Wine, P. H.

    1997-01-01

    A laser flash photolysis-long path absorption technique has been employed to study the kinetics of the reactions of IO radicals with NO and NO2 as a function of temperature and pressure. The IO and NO rate coefficient is independent of pressure over the range 40-200 Torr of N2, and its temperature dependence over the range 242-359 K is adequately described by the Arrhenius expression k(sub 1) = (6.9 +/- 1.7) x 10(exp -12) exp[(328 +/- 71)/T] cu cm/(molecule.s) (errors are 2 sigma, precision only). These Arrhenius parameters are similar to those determined previously for the ClO + NO and BrO + NO reactions. The IO and NO2 association reaction is found to be in the falloff regime over the temperature and pressure ranges investigated (254-354 K and 40-750 Torr of N2). Assuming F(sub c) = 0.4 independent of temperature, a physically reasonable set of falloff parameters which adequately describe the data are k(sub 0) = 7.7 x 10(exp -31)(T/300)(exp -5.0) cm(exp 6)/(molecule(exp 2).s) and k(sub infinity) = 1.55 x 10(exp -11)cu cm/(molecule.s) independent of temperature. The IO + NO2 rate coefficients determined in this study are about a factor of 2 faster than those reported in the only previous study of this reaction.

  10. The Effects of One-Dimensional Glide on the Reaction Kinetics of Interstitial Clusters

    International Nuclear Information System (INIS)

    Heinisch, Howard L.; Singh, B N.; Golubov, S I.

    2000-01-01

    Collision cascades in metals produce small interstitial clusters and perfect dislocation loops that glide in thermally activated one-dimensional (1D) random walks. These gliding defects can change their Burgers vectors by thermal activation or by interactions with other defects. Their migration is therefore''mixed 1D/3D migration'' along a 3D path consisting of 1D segments. The defect reaction kinetics under mixed 1D/3D diffusion are different from pure 1D diffusion and pure 3D diffusion, both of which can be formulated within analytical rate theory models of microstructure evolution under irradiation. Atomic-scale kinetic Monte Carlo (kMC) defect migration simulations are used to investigate the effects of mixed 1D/3D migration on defect reaction kinetics as a guide for implementing mixed 1D/3D migration into the analytical rate theory. The functional dependence of the sink strength on the sixe and concentration of sinks under mixed 1D/3D migration is shown to lie between that for pure 1D and pure 3D migration and varies with L, the average distance between direction changes of the gliding defects. It is shown that the sink strength in simulations for spherical sinks of radius R under mixed 1D/3D migration for values of L greater than R can be approximated by an expression that varies directly as R2. For small L, the form of the transition from mixed 1D/3D to pure 3D diffusion as L decreases is demonstrated in the simulations, the results of which can be used in the future development of an analytical expression describing this transition region

  11. Modelling and experimental evaluation of reaction kinetics in reactive extraction for chiral separation of amines, amino acids and amino-alcohols

    NARCIS (Netherlands)

    Steensma, M.; Kuipers, N.J.M.; de Haan, A.B.; Kwant, Gerard

    2007-01-01

    This paper reports on determination of the intrinsic reaction kinetics in reactive extraction of chiral compounds. It is important to know the mass transfer rates and reaction kinetics separately for a reliable scale-up. A kinetic model is developed to interpret the experimental data from the

  12. CuInSe2 nano-crystallite reaction kinetics using solid state reaction from Cu2Se and In2Se3 powders

    International Nuclear Information System (INIS)

    Hsiang, Hsing-I; Lu, Li-Hsin; Chang, Yu-Lun; Ray, Dahtong; Yen, Fu-Su

    2011-01-01

    Highlights: → CuInSe 2 phase increased gradually accompanied with a decrease in γ-In 2 Se 3 and no intermediate phase during calcination. → CuInSe 2 formation from Cu 2 Se and In 2 Se 3 powders follows a one-dimensional diffusion-controlled reaction with apparent activation energy of about 122.5 kJ/mol. → The solid reaction kinetics may be dominated by the diffusion of In 3+ ions. - Abstract: The reaction mechanism and CuInSe 2 formation kinetics using a solid state reaction from Cu 2 Se and In 2 Se 3 powders synthesized using a heating up process were investigated using X-ray diffractomy (XRD) and transmission electron microscopy (TEM). It was observed that the CuInSe 2 phase increased gradually, accompanied with a decrease in γ-In 2 Se 3 with no intermediate phase as the calcination temperature and soaking time were increased. The reaction kinetics was analyzed using the Avrami and polynomial kinetic model, suggesting that CuInSe 2 formation from Cu 2 Se and In 2 Se 3 powders follows a diffusion-controlled reaction with an apparent activation energy of about 122.5-182.3 kJ/mol. Cu 2 Se and In 2 Se 3 phases react and directly transform into CIS without the occurrence of any intermediate phase and the size of the newly formed CuInSe 2 crystallites was close to that of the Cu 2 Se reactant particle based on the TEM results, which indicated that the solid reaction kinetics may be dominated by the diffusion of In 3+ ions.

  13. Kinetics of reactions of the Actinomadura R39 DD-peptidase with specific substrates.

    Science.gov (United States)

    Adediran, S A; Kumar, Ish; Nagarajan, Rajesh; Sauvage, Eric; Pratt, R F

    2011-01-25

    The Actinomadura R39 DD-peptidase catalyzes the hydrolysis and aminolysis of a number of small peptides and depsipeptides. Details of its substrate specificity and the nature of its in vivo substrate are not, however, well understood. This paper describes the interactions of the R39 enzyme with two peptidoglycan-mimetic substrates 3-(D-cysteinyl)propanoyl-D-alanyl-D-alanine and 3-(D-cysteinyl)propanoyl-D-alanyl-D-thiolactate. A detailed study of the reactions of the former substrate, catalyzed by the enzyme, showed DD-carboxypeptidase, DD-transpeptidase, and DD-endopeptidase activities. These results confirm the specificity of the enzyme for a free D-amino acid at the N-terminus of good substrates and indicated a preference for extended D-amino acid leaving groups. The latter was supported by determination of the structural specificity of amine nucleophiles for the acyl-enzyme generated by reaction of the enzyme with the thiolactate substrate. It was concluded that a specific substrate for this enzyme, and possibly the in vivo substrate, may consist of a partly cross-linked peptidoglycan polymer where a free side chain N-terminal un-cross-linked amino acid serves as the specific acyl group in an endopeptidase reaction. The enzyme is most likely a DD-endopeptidase in vivo. pH-rate profiles for reactions of the enzyme with peptides, the thiolactate named above, and β-lactams indicated the presence of complex proton dissociation pathways with sticky substrates and/or protons. The local structure of the active site may differ significantly for reactions of peptides and β-lactams. Solvent kinetic deuterium isotope effects indicate the presence of classical general acid/base catalysis in both acylation and deacylation; there is no evidence of the low fractionation factor active site hydrogen found previously in class A and C β-lactamases.

  14. Kinetics on the reaction of substituted quinolines and p-substituted benzoylchlorides under various pressures

    International Nuclear Information System (INIS)

    Kim, Young Cheul; Lim, Jong Wan; Choi, Sung Yong; Kim, Se Kyong

    1999-01-01

    The reaction rates of substituted quinolines(6-CH 3 C 9 H 7 N, C 9 H 7 N) with p-substituted benzoylchlorides(p-CH 3 , p-H, p-NO 2 ) have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10,15, 20, 25 .deg. C) and pressures(1, 200, 500, 1000bar). From the values of rate constants, the activation parameters(Ea, ΔV ≠ , ΔS ≠ , and ΔG ≠ ) and the pressure dependence of Hammett ρ values were determined. The rate constants increase as a function of temperatures and pressures, and are further increase by introduction the electron donor substituents in nucleophile(p-CH 3 ) or electron acceptor(p-NO 2 ) substituents in substrate. The activation volume, and the activation entropy are all negative. Hammett ρ values are also negative for nucleophile (ρ X ) and positive for the substrate (ρ Y ) over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed in typical S N 2 reaction mechanism and 'associative S N 2' in which bond formation favored with increasing pressures

  15. Kinetics on the reaction of 6-chloroquinoline and p-substituted benzoylchlorides under high pressures

    International Nuclear Information System (INIS)

    Kim, Eung Ryul; Lim, Jong Wan; Kim, Se Kyong; Ko, Young Shin

    2002-01-01

    The reactions rates of substituted 6-chloroquinoline, with p-substituted benzoyichlorides (p-CH 3 , p-H, p-NO 2 ) have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10,15,20,25 .deg. C) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters (Ea, ΔV ≠ , ΔH ≠ , ΔS ≠ , and ΔG ≠ ) and the pressure dependence of Hammett ρ values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron donor substituents in substrate (p-NO 2 ) with 6-chloroquinoline. When, the activation volume and the activation entropy are all negative. And the Hammett ρ values are positive for the substrate over the pressure and temperature range studied. The results of kinetic studies for pressure and substituent show that thease reactions proceed in typical S N 2 reaction mechanism and 'associative S N 2' in bond formation favored with increasing pressures

  16. 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.

  17. Kinetics of the high-temperature combustion reactions of dibutylether using composite computational methods

    KAUST Repository

    Rachidi, Mariam El

    2015-01-01

    This paper investigates the high-temperature combustion kinetics of n-dibutyl ether (n-DBE), including unimolecular decomposition, H-abstraction by H, H-migration, and C{single bond}C/C{single bond}O β-scission reactions of the DBE radicals. The energetics of H-abstraction by OH radicals is also studied. All rates are determined computationally using the CBS-QB3 and G4 composite methods in conjunction with conventional transition state theory. The B3LYP/6-311++G(2df,2pd) method is used to optimize the geometries and calculate the frequencies of all reactive species and transition states for use in ChemRate. Some of the rates calculated in this study vary markedly from those obtained for similar reactions of alcohols or alkanes, particularly those pertaining to unimolecular decomposition and β-scission at the α-β C{single bond}C bond. These variations show that analogies to alkanes and alcohols are, in some cases, inappropriate means of estimating the reaction rates of ethers. This emphasizes the need to establish valid rates through computation or experimentation. Such studies are especially important given that ethers exhibit promising biofuel and fuel additive characteristics. © 2014.

  18. Kinetics of reaction of 1,10- decanedioland dimeric fatty acid C36

    International Nuclear Information System (INIS)

    Falah, A.

    2013-01-01

    Kinetic studies were carried out on the reaction between 1,10- Decanedioland dimeric fatty acid C 3 6 in melt phase. The reaction was performed at 140, 150, 160, 170, and 185 o C and followed by determining the acid value of the product. The polyesterfication reaction was found to be of overall second order with an activation energy of 39,91kj/mol up to (50, 44, 55,42, 63)% conversion at (140, 150, 160, 170, 185) o C and overall third order with an activation energy of 71.17 k j/ mol above (50, 44, 55, 42, 63)% conversion at (140, 150, 160, 170, 185) o C. The Degree of Polymerization, number average molecular weight and weight average molecular weight have been calculated during different times, the relationships between Degree of Polymerization, number average molecular weight, weight average molecular weight and the times is linear until, (50, 44, 55, 42, 63)%conversion at (140, 150, 160, 170, 185) o C. (author)

  19. Indistinguishability and identifiability of kinetic models for the MurC reaction in peptidoglycan biosynthesis.

    Science.gov (United States)

    Hattersley, J G; Pérez-Velázquez, J; Chappell, M J; Bearup, D; Roper, D; Dowson, C; Bugg, T; Evans, N D

    2011-11-01

    An important question in Systems Biology is the design of experiments that enable discrimination between two (or more) competing chemical pathway models or biological mechanisms. In this paper analysis is performed between two different models describing the kinetic mechanism of a three-substrate three-product reaction, namely the MurC reaction in the cytoplasmic phase of peptidoglycan biosynthesis. One model involves ordered substrate binding and ordered release of the three products; the competing model also assumes ordered substrate binding, but with fast release of the three products. The two versions are shown to be distinguishable; however, if standard quasi-steady-state assumptions are made distinguishability cannot be determined. Once model structure uniqueness is ensured the experimenter must determine if it is possible to successfully recover rate constant values given the experiment observations, a process known as structural identifiability. Structural identifiability analysis is carried out for both models to determine which of the unknown reaction parameters can be determined uniquely, or otherwise, from the ideal system outputs. This structural analysis forms an integrated step towards the modelling of the full pathway of the cytoplasmic phase of peptidoglycan biosynthesis. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

  20. Interactions of nitrite with catalase: Enzyme activity and reaction kinetics studies.

    Science.gov (United States)

    Krych-Madej, Justyna; Gebicka, Lidia

    2017-06-01

    Catalase, a heme enzyme, which catalyzes decomposition of hydrogen peroxide to water and molecular oxygen, is one of the main enzymes of the antioxidant defense system of the cell. Nitrite, used as a food preservative has long been regarded as a harmful compound due to its ability to form carcinogenic nitrosamines. Recently, much evidence has been presented that nitrite plays a protective role as a nitric oxide donor under hypoxic conditions. In this work the effect of nitrite on the catalytic reactions of catalase was studied. Catalase was inhibited by nitrite, and this process was pH-dependent. IC 50 values varied from about 1μM at pH5.0 to about 150μM of nitrite at pH7.4. The presence of chloride significantly enhanced nitrite-induced catalase inhibition, in agreement with earlier observations. The kinetics of the reactions of nitrite with ferric catalase, its redox intermediate, Compound I, and catalase inactive form, Compound II, was also studied. Possible mechanisms of nitrite-induced catalase inhibition are analyzed and the biological consequences of the reactions of catalase with nitrite are discussed. Copyright © 2017 Elsevier Inc. All rights reserved.

  1. Esterification with ethanol to produce biodiesel from high acidity raw materials. Kinetic studies and analysis of secondary reactions

    Energy Technology Data Exchange (ETDEWEB)

    Pisarello, M.L.; Dalla Costa, B.; Mendow, G.; Querini, C.A. [Instituto de Investigaciones en Catalisis y Petroquimica (INCAPE)-(FIQ-UNL, CONICET), Santiago del Estero 2654-Santa Fe, S3000AOJ (Argentina)

    2010-09-15

    In this work, the esterification reaction of free fatty acids (FFA) in sunflower oil, coconut oil and concentrated FFA, with ethanol, methanol and ethanol 96%, using homogeneous acid catalysts to produce biodiesel is studied. Kinetic parameters are estimated with a simplified model, and then used to predict the reaction behavior. Reactions other than the reversible esterification are considered to explain the behavior that this system displays. Such reactions are the triglycerides conversion by acid catalyzed transesterification and hydrolysis. In addition, we include kinetic studies of the reaction that occur between the sulphuric acid and methanol (or ethanol), forming mono and dialkylsulphates. This reaction produces water and consumes methanol (or ethanol), and consequently has a direct impact in the esterification reaction rate and equilibrium conversion. The concentration of sulphuric acid decreases to less than 50% of the initial value due to the reaction with the alcohol. A minimum in the acidity due to the free fatty acids as a function of time was clearly observed during the reaction, which has not been reported earlier. This behavior is related to the consecutive reactions that take place during the esterification of FFA in the presence of triglycerides. The phase separation due to the presence of water, which is generated during the reaction, is also studied. (author)

  2. Nitrous oxide production kinetics during nitrate reduction in river sediments.

    Science.gov (United States)

    Laverman, Anniet M; Garnier, Josette A; Mounier, Emmanuelle M; Roose-Amsaleg, Céline L

    2010-03-01

    A significant amount of nitrogen entering river basins is denitrified in riparian zones. The aim of this study was to evaluate the influence of nitrate and carbon concentrations on the kinetic parameters of nitrate reduction as well as nitrous oxide emissions in river sediments in a tributary of the Marne (the Seine basin, France). In order to determine these rates, we used flow-through reactors (FTRs) and slurry incubations; flow-through reactors allow determination of rates on intact sediment slices under controlled conditions compared to sediment homogenization in the often used slurry technique. Maximum nitrate reduction rates (R(m)) ranged between 3.0 and 7.1microg Ng(-1)h(-1), and affinity constant (K(m)) ranged from 7.4 to 30.7mg N-NO(3)(-)L(-1). These values were higher in slurry incubations with an R(m) of 37.9microg Ng(-1)h(-1) and a K(m) of 104mg N-NO(3)(-)L(-1). Nitrous oxide production rates did not follow Michaelis-Menten kinetics, and we deduced a rate constant with an average of 0.7 and 5.4ng Ng(-1)h(-1) for FTR and slurry experiments respectively. The addition of carbon (as acetate) showed that carbon was not limiting nitrate reduction rates in these sediments. Similar rates were obtained for FTR and slurries with carbon addition, confirming the hypothesis that homogenization increases rates due to release of and increasing access to carbon in slurries. Nitrous oxide production rates in FTR with carbon additions were low and represented less than 0.01% of the nitrate reduction rates and were even negligible in slurries. Maximum nitrate reduction rates revealed seasonality with high potential rates in fall and winter and low rates in late spring and summer. Under optimal conditions (anoxia, non-limiting nitrate and carbon), nitrous oxide emission rates were low, but significant (0.01% of the nitrate reduction rates). Copyright 2009 Elsevier Ltd. All rights reserved.

  3. Kinetics of solid-gas reactions characterized by scanning AC nano-calorimetry with application to Zr oxidation

    International Nuclear Information System (INIS)

    Xiao, Kechao; Lee, Dongwoo; Vlassak, Joost J.

    2014-01-01

    Scanning AC nano-calorimetry is a recently developed experimental technique capable of measuring the heat capacity of thin-film samples of a material over a wide range of temperatures and heating rates. Here, we describe how this technique can be used to study solid-gas phase reactions by measuring the change in heat capacity of a sample during reaction. We apply this approach to evaluate the oxidation kinetics of thin-film samples of zirconium in air. The results confirm parabolic oxidation kinetics with an activation energy of 0.59 ± 0.03 eV. The nano-calorimetry measurements were performed using a device that contains an array of micromachined nano-calorimeter sensors in an architecture designed for combinatorial studies. We demonstrate that the oxidation kinetics can be quantified using a single sample, thus enabling high-throughput mapping of the composition-dependence of the reaction rate.

  4. 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.

  5. Decolorization kinetics of Procion H-exl dyes from textile dyeing using Fenton-like reactions.

    Science.gov (United States)

    Ntampegliotis, K; Riga, A; Karayannis, V; Bontozoglou, V; Papapolymerou, G

    2006-08-10

    The decolorization kinetics of three commercially used Procion H-exl dyes was studied using a Fenton-like reagent. The effect of the major system parameters (pH, concentration of H(2)O(2) and Fe(3+) and initial dye concentration) on the kinetics was determined. For comparison, the effect of the use of UV irradiated Fenton-like reagent and of Fenton reagent on the kinetics was also examined. In addition, mineralization rates and the biodegradability improvement as well as the effect of the addition of Cl(-), CO(3)(2-) or HCO(3)(-) on the decolorization rates was studied. The reactions were carried out in a 300 ml stirred cylindrical reactor with the capability of UV irradiation. The dye half-life time goes through a minimum with respect to the solution pH between 3 and 4. It also exhibits a broad minimum with respect to Fe(3+) and H(2)O(2) at molar ratios of H(2)O(2)/Fe(3+) from about 100 to 10. The addition of CO(3)(2-) and HCO(3)(-) substantially reduces the decolorization rates, while this effect is significantly less pronounced with Cl(-). At an optimum range of parameters, the mineralization rate (TOC reduction) is very slow for the Fenton-like process (TOC decrease from an initial 49.5 to 41.1 mg/l after 30 min and to only 35.2 mg/l after 600 min), but it increases significantly for the photo-Fenton-like process (to TOC values of 39.7 and 11.4 mg/l, respectively). The biodegradability, as expressed by the BOD/COD ratio, increases significantly from an initial value of 0.11-0.55 for the Fenton-like and to 0.72 for the photo-Fenton-like processes.

  6. Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium-Tyrosine Complex.

    Science.gov (United States)

    Lennox, J Christian; Dempsey, Jillian L

    2017-11-22

    A polypyridyl ruthenium complex with fluorinated bipyridine ligands and a covalently bound tyrosine moiety was synthesized, and its photo-induced proton-coupled electron transfer (PCET) reactivity in acetonitrile was investigated with transient absorption spectroscopy. Using flash-quench methodology with methyl viologen as an oxidative quencher, a Ru 3+ species is generated that is capable of initiating the intramolecular PCET oxidation of the tyrosine moiety. Using a series of substituted pyridine bases, the reaction kinetics were found to vary as a function of proton acceptor concentration and identity, with no significant H/D kinetic isotope effect. Through analysis of the kinetics traces and comparison to a control complex without the tyrosine moiety, PCET reactivity was found to proceed through an equilibrium electron transfer followed by proton transfer (ET-PT) pathway in which irreversible deprotonation of the tyrosine radical cation shifts the ET equilibrium, conferring a base dependence on the reaction. Comprehensive kinetics modeling allowed for deconvolution of complex kinetics and determination of rate constants for each elementary step. Across the five pyridine bases explored, spanning a range of 4.2 pK a units, a linear free-energy relationship was found for the proton transfer rate constant with a slope of 0.32. These findings highlight the influence that proton transfer driving force exerts on PCET reaction kinetics.

  7. Kinetic Monte Carlo modeling of chemical reactions coupled with heat transfer.

    Science.gov (United States)

    Castonguay, Thomas C; Wang, Feng

    2008-03-28

    In this paper, we describe two types of effective events for describing heat transfer in a kinetic Monte Carlo (KMC) simulation that may involve stochastic chemical reactions. Simulations employing these events are referred to as KMC-TBT and KMC-PHE. In KMC-TBT, heat transfer is modeled as the stochastic transfer of "thermal bits" between adjacent grid points. In KMC-PHE, heat transfer is modeled by integrating the Poisson heat equation for a short time. Either approach is capable of capturing the time dependent system behavior exactly. Both KMC-PHE and KMC-TBT are validated by simulating pure heat transfer in a rod and a square and modeling a heated desorption problem where exact numerical results are available. KMC-PHE is much faster than KMC-TBT and is used to study the endothermic desorption of a lattice gas. Interesting findings from this study are reported.

  8. Numerical Model of Dephosphorization Reaction Kinetics in Top Blown Converter Coupled with Flow Field

    Science.gov (United States)

    Liu, Wei; Yang, Shufeng; Li, Jingshe; Wang, Minghui

    2017-07-01

    A 3D transient numerical model of dephosphorization kinetics coupled with flow field in a top blown converter was built. Through the model the dephosphorization reaction rate influenced by the oxygen jets and the steel flow were simulated. The results show that the dephosphorization rate at the droplet metal-slag interface is two orders of magnitude faster than that at bath metal-slag interface. When the lance oxygen pressure increases from 0.7 to 0.8 MPa, the dephosphorization rate increases notably and the end content of P has a decrease of 19 %. However, when the pressure continues rising to 0.9 MPa, the dephosphorization rate has no significant increase. In addition, the lance height shows a nearly linear relation to the end P content of steel, that the lower the height, the faster the dephosphorization rate.

  9. Kinetic and Reaction Pathway Analysis in the Application of Botulinum Toxin A for Wound Healing

    Directory of Open Access Journals (Sweden)

    Frank J. Lebeda

    2012-01-01

    Full Text Available A relatively new approach in the treatment of specific wounds in animal models and in patients with type A botulinum toxin is the focus of this paper. The indications or conditions include traumatic wounds (experimental and clinical, surgical (incision wounds, and wounds such as fissures and ulcers that are signs/symptoms of disease or other processes. An objective was to conduct systematic literature searches and take note of the reactions involved in the healing process and identify corresponding pharmacokinetic data. From several case reports, we developed a qualitative model of how botulinum toxin disrupts the vicious cycle of muscle spasm, pain, inflammation, decreased blood flow, and ischemia. We transformed this model into a minimal kinetic scheme for healing chronic wounds. The model helped us to estimate the rate of decline of this toxin's therapeutic effect by calculating the rate of recurrence of clinical symptoms after a wound-healing treatment with this neurotoxin.

  10. Biochemical toxicology studies of methomyl and its kinetic reaction with cholinesterase in rats

    International Nuclear Information System (INIS)

    Tawfik, S.M.; Abdel-Hamid, F.M.

    2001-01-01

    The effect of the pesticide methomyl on acetylcholinesterase activities in brain and blood of male rats in vivo and the kinetics involved in their reaction in vitro were studied. Also, its effect on peroxidase action of catalase in vivo was studied using 14C - formate. The results showed that methomyl is a competitive inhibitor for acetylcholinesterase and the concentration levels that caused 50% inhibition of the enzyme activity were 2.1 x 10-2 M and 1.9 x 10-4 for brain and blood- Ache, respectively. The inhibition of acetylcholinesterase activity decreased to 67.5 % at the time of appearance of toxicity symptoms. The radioactivity eliminated in both the expired air and in urine was reduced

  11. Programming chemical kinetics: engineering dynamic reaction networks with DNA strand displacement

    Science.gov (United States)

    Srinivas, Niranjan

    Over the last century, the silicon revolution has enabled us to build faster, smaller and more sophisticated computers. Today, these computers control phones, cars, satellites, assembly lines, and other electromechanical devices. Just as electrical wiring controls electromechanical devices, living organisms employ "chemical wiring" to make decisions about their environment and control physical processes. Currently, the big difference between these two substrates is that while we have the abstractions, design principles, verification and fabrication techniques in place for programming with silicon, we have no comparable understanding or expertise for programming chemistry. In this thesis we take a small step towards the goal of learning how to systematically engineer prescribed non-equilibrium dynamical behaviors in chemical systems. We use the formalism of chemical reaction networks (CRNs), combined with mass-action kinetics, as our programming language for specifying dynamical behaviors. Leveraging the tools of nucleic acid nanotechnology (introduced in Chapter 1), we employ synthetic DNA molecules as our molecular architecture and toehold-mediated DNA strand displacement as our reaction primitive. Abstraction, modular design and systematic fabrication can work only with well-understood and quantitatively characterized tools. Therefore, we embark on a detailed study of the "device physics" of DNA strand displacement (Chapter 2). We present a unified view of strand displacement biophysics and kinetics by studying the process at multiple levels of detail, using an intuitive model of a random walk on a 1-dimensional energy landscape, a secondary structure kinetics model with single base-pair steps, and a coarse-grained molecular model that incorporates three-dimensional geometric and steric effects. Further, we experimentally investigate the thermodynamics of three-way branch migration. Our findings are consistent with previously measured or inferred rates for

  12. 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

  13. Synchronous parallel kinetic Monte Carlo for continuum diffusion-reaction systems

    International Nuclear Information System (INIS)

    Martinez, E.; Marian, J.; Kalos, M.H.; Perlado, J.M.

    2008-01-01

    A novel parallel kinetic Monte Carlo (kMC) algorithm formulated on the basis of perfect time synchronicity is presented. The algorithm is intended as a generalization of the standard n-fold kMC method, and is trivially implemented in parallel architectures. In its present form, the algorithm is not rigorous in the sense that boundary conflicts are ignored. We demonstrate, however, that, in their absence, or if they were correctly accounted for, our algorithm solves the same master equation as the serial method. We test the validity and parallel performance of the method by solving several pure diffusion problems (i.e. with no particle interactions) with known analytical solution. We also study diffusion-reaction systems with known asymptotic behavior and find that, for large systems with interaction radii smaller than the typical diffusion length, boundary conflicts are negligible and do not affect the global kinetic evolution, which is seen to agree with the expected analytical behavior. Our method is a controlled approximation in the sense that the error incurred by ignoring boundary conflicts can be quantified intrinsically, during the course of a simulation, and decreased arbitrarily (controlled) by modifying a few problem-dependent simulation parameters

  14. Understanding the reaction kinetics to optimize graphene growth on Cu by chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Kraus, Juergen; Boebel, Lena; Zwaschka, Gregor; Guenther, Sebastian [Technische Universitaet Muenchen, Zentralinstitut fuer Katalyseforschung, Chemie Department, Physikalische Chemie mit Schwerpunkt Katalyse, Garching (Germany)

    2017-11-15

    Understanding and controlling the growth kinetics of graphene is a prerequisite to synthesize this highly wanted material by chemical vapor deposition on Cu, e.g. for the construction of ultra-stable electron transparent membranes. It is reviewed that Cu foils contain a considerable amount of carbon in the bulk which significantly exceeds the expected amount of thermally equilibrated dissolved carbon in Cu and that this carbon must be removed before any high quality graphene may be grown. Starting with such conditioned Cu foils, systematic studies of the graphene growth kinetics in a reactive CH{sub 4}/H{sub 2} atmosphere allow to extract the following meaningful data: prediction of the equilibrium constant of the graphene formation reaction within a precision of a factor of two, the confirmation that the graphene growth proceeds from a C(ad)-phase on Cu which is in thermal equilibrium with the reactive gas phase, its apparent activation barrier and finally the prediction of the achievable growth velocity of the growing graphene flakes during chemical vapor deposition. As a result of the performed study, growth parameters are identified for the synthesis of high quality monolayer graphene with single crystalline domains of 100-1000 μm in diameter within a reasonable growth time. (copyright 2017 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Kinetics of the tungsten hexafluoride-silane reaction for the chemical vapor deposition of tungsten

    International Nuclear Information System (INIS)

    Gokce, Huseyin.

    1991-01-01

    In this study, the kinetics of the low-pressure chemical vapor deposition (LPCVD) of tungsten by silane reduction of tungsten hexafluoride on Si(100) surfaces was studied. A single-wafer, cold-wall reactor was sued for the experiments. The SiH 4 /WF 6 ratio was 1.0. The pressure and temperature range were 1-10 torr and 137-385 degree C, respectively. Kinetic data were obtained in the absence of mass-transfer effects. The film thicknesses were measured by gravimetry. Scanning electron microscopy (SEM), Auger electron spectroscopy (AES), x-ray diffraction (XRD), and resistivity measurements were used to analyze the W films. For the horizontal substrate position and 4-minute reaction times, the apparent activation energies were determined to be 0.35 eV/atom for 10 torr, 0.17 eV/atom for 3 torr, and 0.08 eV/atom for 1 torr. Lower temperatures and higher pressures produced porous films, while higher temperatures and lower pressures resulted in continuous films with smoother surfaces. As the Si-W interface, a W(110) preferential orientation was observed. As the W films grew thicker, W orientation switched from (110) to (100). Apparent activation energy seems to change with thickness

  16. An experimental and theoretical kinetic study of the reaction of OH radicals with tetrahydrofuran

    KAUST Repository

    Giri, Binod

    2016-06-24

    Tetrahydrofuran (CHO, THF) and its alkylated derivatives of the cyclic ether family are considered to be promising future biofuels. They appear as important intermediates during the low-temperature oxidation of conventional hydrocarbon fuels and of heavy biofuels such as long-chain fatty acid methyl esters. The reaction of tetrahydrofuran with OH radicals was investigated in a shock tube, over a temperature range of 800-1340 K and at pressures near 1.5 bar. Hydroxyl radicals were generated by the rapid thermal decomposition of tert-butyl hydroperoxide, and a UV laser absorption technique was used to monitor the mole fraction of OH radicals. High-level CCSD(T)/cc-pV(D,T)Z//MP2/aug-cc-pVDZ quantum chemical calculations were performed to explore the chemistry of the THF+OH reaction system. Our calculations reveal that the THF+OH (R1) reaction proceeds via either direct or indirect H-abstraction from various sites, leading to the formation of tetrahydrofuran-2-yl (THF-R2) or tetrahydrofuran-3-yl (THF-R3) radicals and water. Theoretical kinetic analysis revealed that both channels are important under conditions relevant to combustion. To our knowledge, this is the first direct experimental and theoretical kinetic study of the reaction of tetrahydrofuran with OH radicals at high temperatures. The following theoretical rate expressions (in units of cmmols) are recommended for combustion modeling in the temperature range 800-1350 K: . k1(T)=4.11×1040.16em0ex(TK)2.69exp(1316.80.16em0exKT)2.em0ex0.16em0ex(THF+OH→Products) . k2(T)=6.930.16em0ex×10110.16em0ex(TK)0.41exp(-106.80.16em0exKT)2.em0ex0.16em0ex(THF+OH→THF-R20.16em0ex+H2O) . k3(T)=4.120.16em0ex×1030.16em0ex(TK)3.02exp(456.90.16em0exKT)2.em0ex0.16em0ex(THF+OH→THF-R30.16em0ex+H2O) . .

  17. Computational investigation of kinetics of cross-linking reactions in proteins: importance in structure prediction.

    Science.gov (United States)

    Bandyopadhyay, Pradipta; Kuntz, Irwin D

    2009-01-01

    The determination of protein structure using distance constraints is a new and promising field of study. One implementation involves attaching residues of a protein using a cross-linking agent, followed by protease digestion, analysis of the resulting peptides by mass spectroscopy, and finally sequence threading to detect the protein folds. In the present work, we carry out computational modeling of the kinetics of cross-linking reactions in proteins using the master equation approach. The rate constants of the cross-linking reactions are estimated using the pKas and the solvent-accessible surface areas of the residues involved. This model is tested with fibroblast growth factor (FGF) and cytochrome C. It is consistent with the initial experimental rate data for individual lysine residues for cytochrome C. Our model captures all observed cross-links for FGF and almost 90% of the observed cross-links for cytochrome C, although it also predicts cross-links that were not observed experimentally (false positives). However, the analysis of the false positive results is complicated by the fact that experimental detection of cross-links can be difficult and may depend on specific experimental conditions such as pH, ionic strength. Receiver operator characteristic plots showed that our model does a good job in predicting the observed cross-links. Molecular dynamics simulations showed that for cytochrome C, in general, the two lysines come closer for the observed cross-links as compared to the false positive ones. For FGF, no such clear pattern exists. The kinetic model and MD simulation can be used to study proposed cross-linking protocols.

  18. 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}.

  19. alfa-Deuterium kinetic isotope effects in reactions of methyllithium. Is better aggregation the cause of lower reactivity?

    DEFF Research Database (Denmark)

    Holm, Torkil

    1996-01-01

    The value of kH/kD for alfa deuterium kinetic isotope effects for the reaction of methyllithium and methylmagnesium iodid with a series of substrates are consistently ca. 10-15 % higher for the lithium reagent. This may indicate a pre-equilibrium......The value of kH/kD for alfa deuterium kinetic isotope effects for the reaction of methyllithium and methylmagnesium iodid with a series of substrates are consistently ca. 10-15 % higher for the lithium reagent. This may indicate a pre-equilibrium...

  20. The complex reaction kinetics of neptunium including redox and extraction process in 30% TBP-nitric acid system

    International Nuclear Information System (INIS)

    Hu Zhang; Zhan-yuan Liu; Xian-ming Zhou; Li Li

    2017-01-01

    In order to understand the complex and dynamic neptunium process chemistry in the TBP-HNO_3 system, the kinetics involved reversible redox reaction and extraction mass transfer was investigated. The results indicates that the mass transfer rate of Np(VI) is much faster than the redox reaction in aqueous solution. The concentrations of nitric acid and nitrous acid not only can change the Np(V) oxidation reaction and Np(VI) reduction reaction rate, but also can ultimately determine the distribution of neptunium extraction equilibrium. The variety of temperature can only influence the extraction equilibrium time, but cannot alter the equilibrium state of neptunium. (author)

  1. Synthesis Of Magnesium-Aluminum Layered Double Hydroxides By Mechanochemical Method And Its Solid State Reaction Kinetics

    Directory of Open Access Journals (Sweden)

    Hongbo Y.

    2015-06-01

    Full Text Available A mechanochemical method is developed in preparing magnesium-aluminum-layered double hydroxides (MgAl-LDHs. This approach includes activation process and diffusion process. In order to verify the LDHs structure and study the reaction kinetics, X-ray diffraction (XRD patterns, inductively coupled plasma(ICP and physical adsorption instrument were characterized. The results show that activation time can change the surface of particles and affect the reaction grade. During the diffusion process, reaction time is the most important factor. The reaction energy (ΔQ was calculated that is 6kJ/mol.

  2. 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.

  3. 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.

  4. The catalytic oxidation of 1-butene over bismuth molybdate catalysts : V. The kinetics of the oxidation: A. Pulse reaction kinetics; exploratory experiments for a kinetic investigation

    NARCIS (Netherlands)

    Keizer, K.; Batist, P.A.; Schuit, G.C.A.

    1969-01-01

    The kinetics of oxidn. of 1-butene with O on three types of bismuth molybdate catalysts were investigated in pulse expts. For all the catalysts mentioned the kinetics can be expressed by a first-order dependency on the butene pressure and a zero-order dependency on the O pressure. A slight deviation

  5. Two-scale large deviations for chemical reaction kinetics through second quantization path integral

    International Nuclear Information System (INIS)

    Li, Tiejun; Lin, Feng

    2016-01-01

    Motivated by the study of rare events for a typical genetic switching model in systems biology, in this paper we aim to establish the general two-scale large deviations for chemical reaction systems. We build a formal approach to explicitly obtain the large deviation rate functionals for the considered two-scale processes based upon the second quantization path integral technique. We get three important types of large deviation results when the underlying two timescales are in three different regimes. This is realized by singular perturbation analysis to the rate functionals obtained by the path integral. We find that the three regimes possess the same deterministic mean-field limit but completely different chemical Langevin approximations. The obtained results are natural extensions of the classical large volume limit for chemical reactions. We also discuss its implication on the single-molecule Michaelis–Menten kinetics. Our framework and results can be applied to understand general multi-scale systems including diffusion processes. (paper)

  6. Interplay between excitation kinetics and reaction-center dynamics in purple bacteria

    International Nuclear Information System (INIS)

    Caycedo-Soler, Felipe; RodrIguez, Ferney J; Quiroga, Luis; Johnson, Neil F

    2010-01-01

    Photosynthesis is arguably the fundamental process of life, since it enables energy from the Sun to enter the food chain on the Earth. It is a remarkable non-equilibrium process in which photons are converted to many-body excitations, which traverse a complex biomolecular membrane, where they are captured and fuel chemical reactions within a reaction center (RC) in order to produce nutrients. The precise nature of these dynamical processes-which lie at the interface between quantum and classical behavior and involve both noise and coordination-is still being explored. Here, we focus on a striking recent empirical finding concerning an illumination-driven transition in the biomolecular membrane architecture of the purple bacteria Rsp. photometricum. Using stochastic realizations to describe a hopping rate model for excitation transfer, we show numerically and analytically that this surprising shift in preferred architectures can be traced to the interplay between the excitation kinetics and the RC dynamics. The net effect is that the bacteria profit from efficient metabolism at low illumination intensities while using dissipation to avoid an oversupply of energy at high illumination intensities.

  7. New perspectives for organic chemistry and biochemistry in VUV: reaction kinetics, chirality and thermochemistry. Summaries

    International Nuclear Information System (INIS)

    Nahon, Laurent; Field, David; Gerber, Thomas; Knopp, Gregor; Beaud, Paul; Radi, Peter; Tulej, Marek; Dedonder-Lardeux, Claude; Jung, J.M.; Laprevote, Olivier; Thissen, Roland; Le Barbu, K.; Lahmani, F.; Zehnacker, A.; Maurizot, Jean Claude; Barbier, Bernard; Kagan, Henri B.

    2001-10-01

    The aim of this workshop was to examine the conditions of use of VUV for the study of complex molecular systems, and notably bio-molecules, a domain which is greatly expanding. The conclusions of this one-day workshop should allow to define new fields of utilization of the synchrotron radiation in VUV, to precise certain performances that are needed for the transferred line, to establish the complementarities with other VUV sources (lasers, free electron lasers, lamps) and to determine the eventual need for a second low energy light line at SOLEIL. The titles of the various abstract papers presented are (two papers are in English, the rest is in French): SU5, a high resolution and variable polarization VUV line that should be transferred at SOLEIL; Interstellar organic chemistry (in English); Application of spectroscopic techniques in the VUV to combustion relevant molecules (in English); Gaseous phase reaction kinetics (bi-molecular reactions in collision and in aggregates); Liquids of biological interest (excitation and relaxation close to the ionization threshold); Successes and impediments in protein mass spectrometry (the potential contribution of VUV synchrotron radiation); Stereo-specific effects; Complexes between chiral molecules; circular dichroism of biomolecules; Exobiology; asymmetric synthesis (principles and recent results)

  8. 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.

  9. Kinetic Modeling of the Reaction Rate for Quartz and Carbon Black Pellet

    Science.gov (United States)

    Li, Fei; Tangstad, Merete

    2018-06-01

    The kinetic modeling for the carbothermal reduction reaction rate in quartz and carbon black pellets is studied at different temperatures, under varying CO partial pressures in ambient atmosphere, varying carbon contents, different quartz particle sizes, and different crucible opening areas. Carbon black is produced by the cracking of natural gas. The activation energy of the SiC-producing step was determined to be 594 kJ/mol. The averaged pre-exponential factor A obtained from 1898 K, 1923 K, and 1948 K (1625 °C, 1650 °C, and 1675 °C) is 2.62E+16 min-1. The reaction rate of the gas-solid interface factor, fix-C content ( X fix-C), temperature ( T), and CO partial pressure ( X CO) can be expressed as follows: {{d/pct}}{{{d}t}} = (1 - 0.40 × X_{{{fix} - C}}^{ - 0.86} × {pct}) × 2.62 × 10^{16} × \\exp ( { - 594000/RT} ) × (2.6 - 0.015 × X_{co} ).

  10. HYDROBIOGEOCHEM: A coupled model of HYDROlogic transport and mixed BIOGEOCHEMical kinetic/equilibrium reactions in saturated-unsaturated media

    Energy Technology Data Exchange (ETDEWEB)

    Yeh, G.T.; Salvage, K.M. [Pennsylvania State Univ., University Park, PA (United States). Dept. of Civil and Environmental Engineering; Gwo, J.P. [Oak Ridge National Lab., TN (United States); Zachara, J.M.; Szecsody, J.E. [Pacific Northwest National Lab., Richland, WA (United States)

    1998-07-01

    The computer program HYDROBIOGEOCHEM is a coupled model of HYDROlogic transport and BIOGEOCHEMical kinetic and/or equilibrium reactions in saturated/unsaturated media. HYDROBIOGEOCHEM iteratively solves the two-dimensional transport equations and the ordinary differential and algebraic equations of mixed biogeochemical reactions. The transport equations are solved for all aqueous chemical components and kinetically controlled aqueous species. HYDROBIOGEOCHEM is designed for generic application to reactive transport problems affected by both microbiological and geochemical reactions in subsurface media. Input to the program includes the geometry of the system, the spatial distribution of finite elements and nodes, the properties of the media, the potential chemical and microbial reactions, and the initial and boundary conditions. Output includes the spatial distribution of chemical and microbial concentrations as a function of time and space, and the chemical speciation at user-specified nodes.

  11. Kinetics of the glucose/glycine Maillard reaction pathways: influences of pH and reactant initial concentrations

    NARCIS (Netherlands)

    Martins, S.I.F.S.; Boekel, van M.A.J.S.

    2005-01-01

    A previously proposed kinetic model for the glucose/glycine Maillard reaction pathways has been validated by changing the initial pH (4.8, 5.5, 6.0, 6.8 and 7.5) of the reaction and reactant initial concentrations (1:2 and 2:1 molar ratios were compared to the 1:1 ratio). The model consists of 10

  12. Reaction kinetics of free fatty acids esterification in palm fatty acid distillate using coconut shell biochar sulfonated catalyst

    Science.gov (United States)

    Hidayat, Arif; Rochmadi, Wijaya, Karna; Budiman, Arief

    2015-12-01

    Recently, a new strategy of preparing novel carbon-based solid acids has been developed. In this research, the esterification reactions of Palm Fatty Acid Distillate (PFAD) with methanol, using coconut shell biochar sulfonated catalyst from biomass wastes as catalyst, were studied. In this study, the coconut shell biochar sulfonated catalysts were synthesized by sulfonating the coconut shell biochar using concentrated H2SO4. The kinetics of free fatty acid (FFA) esterification in PFAD using a coconut shell biochar sulfonated catalyst was also studied. The effects of the mass ratio of catalyst to oil (1-10%), the molar ratio of methanol to oil (6:1-12:1), and the reaction temperature (40-60°C) were studied for the conversion of PFAD to optimize the reaction conditions. The results showed that the optimal conditions were an methanol to PFAD molar ratio of 12:1, the amount of catalyst of 10%w, and reaction temperature of 60°C. The proposed kinetic model shows a reversible second order reaction and represents all the experimental data satisfactorily, providing deeper insight into the kinetics of the reaction.

  13. Kinetics of transuranium element oxidation-reduction reactions in solution; Cinetique des reactions d'oxydo-reduction des elements transuraniens en solution

    Energy Technology Data Exchange (ETDEWEB)

    Gourisse, D. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1966-09-01

    A review of the kinetics of U, Np, Pu, Am oxidation-reduction reactions is proposed. The relations between the different activation thermodynamic functions (compensatory effect, formal entropy of the activated complex, magnitude of reactions velocities) are considered. The effects of acidity, ionic strength deuterium and mixed solvents polarity on reactions rates are described. The effect of different anions on reactions rates are explained by variations of the reaction standard free energy and variations of the activation free energy (coulombic interactions) resulting from the complexation of dissolved species by these anions. (author) [French] Une revue systematique de la cinetique des reactions d'oxydo-reduction des elements U, Np, Pu, Am, en solution perchlorique est proposee. Des considerations relatives aux grandeurs thermodynamiques d'activation associees aux actes elementaires (effet de compensation, entropie standard des complexes actives, rapidite des reactions) sont developpees. L'influence de l'acidite, de la force ionique, de l'eau lourde et de la polarite des solvants mixtes sur la vitesse des reactions est decrite. Enfin l'influence des differents anions sur la vitesse des reactions est expliquee par les variations de l'enthalpie libre standard de la reaction et de l'enthalpie libre d'activation (travail des forces electrostatiques) resultant de la complexation des especes dissoutes dans la solution. (auteur)

  14. Kinetics of transuranium element oxidation-reduction reactions in solution; Cinetique des reactions d'oxydo-reduction des elements transuraniens en solution

    Energy Technology Data Exchange (ETDEWEB)

    Gourisse, D [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1966-09-01

    A review of the kinetics of U, Np, Pu, Am oxidation-reduction reactions is proposed. The relations between the different activation thermodynamic functions (compensatory effect, formal entropy of the activated complex, magnitude of reactions velocities) are considered. The effects of acidity, ionic strength deuterium and mixed solvents polarity on reactions rates are described. The effect of different anions on reactions rates are explained by variations of the reaction standard free energy and variations of the activation free energy (coulombic interactions) resulting from the complexation of dissolved species by these anions. (author) [French] Une revue systematique de la cinetique des reactions d'oxydo-reduction des elements U, Np, Pu, Am, en solution perchlorique est proposee. Des considerations relatives aux grandeurs thermodynamiques d'activation associees aux actes elementaires (effet de compensation, entropie standard des complexes actives, rapidite des reactions) sont developpees. L'influence de l'acidite, de la force ionique, de l'eau lourde et de la polarite des solvants mixtes sur la vitesse des reactions est decrite. Enfin l'influence des differents anions sur la vitesse des reactions est expliquee par les variations de l'enthalpie libre standard de la reaction et de l'enthalpie libre d'activation (travail des forces electrostatiques) resultant de la complexation des especes dissoutes dans la solution. (auteur)

  15. Kinetics of adsorption and uptake of Cu2+ by Chlorella vulgaris: influence of pH, temperature, culture age, and cations.

    Science.gov (United States)

    Mehta, S K; Singh, Alpana; Gaur, J P

    2002-03-01

    Adsorption and uptake of Cu2+ by Chlorella vulgaris were distinguished by extracting the surface-bound Cu2+ with EDTA. The uptake of Cu2+ followed Michaelis Menten kinetics. The maximum rate of Cu2+ uptake (0.362fmolcell(-1) h(-1)) was obtained at pH 6.0. The rate of Cu2+ uptake was greater for cultures in the exponential phase of growth, and increased with a rise in temperature from 6 to 25 degrees C, thus pointing towards an active mechanism. The maximum number of Cu2+ binding sites was 3.245 fmol cell(-1) at pH 4.5. Adsorption of Cu2+ was strongly pH-dependent thereby indicating that the number and nature of metal binding sites on the cell surface change with changing chemistry of the solution. Unlike uptake, the adsorption remained unaffected by small changes in temperature. Older cultures displayed a higher Cu2+ adsorption capacity than the exponentially growing ones thus suggesting generation of new and/or additional Cu2+ binding sites on older cells of C. vulgaris. By pH titration, the cation-exchange capacity of Chlorella, measured in terms of H+/ Na+ exchange, was about 17 fmol cell(-1) at pH 10.5. Negligible cation exchange capacity at and below pH 5.0 indicated that ion exchange was not the sole mechanism of Cu2+ adsorption by Chlorella. The uptake and adsorption of Cu2+ were inhibited by 100 microM of various cations including other heavy metal ions. The general concept that cations competitively inhibit accumulation of metals in living organisms does not hold for C. vulgaris. Non-competitive, uncompetitive and mixed inhibition of Cu2+ uptake and adsorption by various cations were more common than competitive inhibition.

  16. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multi-zone Reaction Kinetics: Model Derivation and Validation

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoff; Rhamdhani, M. Akbar; Li, Zushu; Schrama, Frank N. H.; Sun, Jianjun

    2018-04-01

    A multi-zone kinetic model coupled with a dynamic slag generation model was developed for the simulation of hot metal and slag composition during the basic oxygen furnace (BOF) operation. The three reaction zones (i) jet impact zone, (ii) slag-bulk metal zone, (iii) slag-metal-gas emulsion zone were considered for the calculation of overall refining kinetics. In the rate equations, the transient rate parameters were mathematically described as a function of process variables. A micro and macroscopic rate calculation methodology (micro-kinetics and macro-kinetics) were developed to estimate the total refining contributed by the recirculating metal droplets through the slag-metal emulsion zone. The micro-kinetics involves developing the rate equation for individual droplets in the emulsion. The mathematical models for the size distribution of initial droplets, kinetics of simultaneous refining of elements, the residence time in the emulsion, and dynamic interfacial area change were established in the micro-kinetic model. In the macro-kinetics calculation, a droplet generation model was employed and the total amount of refining by emulsion was calculated by summing the refining from the entire population of returning droplets. A dynamic FetO generation model based on oxygen mass balance was developed and coupled with the multi-zone kinetic model. The effect of post-combustion on the evolution of slag and metal composition was investigated. The model was applied to a 200-ton top blowing converter and the simulated value of metal and slag was found to be in good agreement with the measured data. The post-combustion ratio was found to be an important factor in controlling FetO content in the slag and the kinetics of Mn and P in a BOF process.

  17. The influence of adsorbate interactions on elementary reaction kinetics : CO with NO, N, O, or H on Rh(100)

    NARCIS (Netherlands)

    Jansen, M.M.M.

    2010-01-01

    The kinetics of heterogeneously catalysed reactions is often described by highly simplified models. For example, the reacting adsorbates occupy one kind of site, surfaces do not reconstruct and lateral interactions between adsorbates are often neglected. Particularly the latter is only allowed for

  18. UV-visible spectrum of the phenyl radical and kinetics of its reaction with NO in the gas phase

    DEFF Research Database (Denmark)

    Wallington, T.J.; Egsgaard, H.; Nielsen, O.J.

    1998-01-01

    Pulse radiolysis transient UV-visible absorption spectroscopy was used to study the UV-visible absorption spectrum (225-575 nm) of the phenyl radical, C6H5(.), and kinetics of its reaction with NO. Phenyl radicals have a strong broad featureless absorption in the region of 225-340 nm...

  19. Kinetic study on bonding reaction of gelatin with CdS nanopaticles by UV-visible spectroscopy.

    Science.gov (United States)

    Tang, Shihua; Wang, Baiyang; Li, Youqun

    2015-04-15

    The chemical kinetics on gelatin-CdS direct conjugates has been systematically investigated as a function of different temperature and reactant concentration (i.e. Cd(2+), S(2-) and gelatin) by UV-visible spectroscopy, for the first time. The nonlinear fitting and the differential method were used to calculate the initial rate based on the absorbance-time data. A double logarithmic linear equation for calculating the rate constant (k) and the reaction order (n) was introduced. The reaction kinetic parameters (n, k, Ea, and Z) and activation thermodynamic parameters (ΔG(≠), ΔH(≠), and ΔS(≠)) were obtained from variable temperature kinetic studies. The overall rate equation allowing evaluation of conditions that provide required reaction rate could be expressed as: r = 1.11 × 10(8) exp(-4971/T)[Cd(2+)][gelatin](0.6)[S(2-)](0.6) (M/S) The calculated values of the reaction rate are well coincide with the experimental results. A suitable kinetic model is also proposed. This work will provide guidance for the rational design of gelatin-directed syntheses of metal sulfide materials, and help to understand the biological effects of nanoparticles at the molecular level. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Analyzing General Chemistry Texts' Treatment of Rates of Change Concepts in Reaction Kinetics Reveals Missing Conceptual Links

    Science.gov (United States)

    Seethaler, Sherry; Czworkowski, John; Wynn, Lynda

    2018-01-01

    Change over time is a crosscutting theme in the sciences that is pivotal to reaction kinetics, an anchoring concept in undergraduate chemistry, and students' struggles with rates of change are well-documented. Informed by the education scholarship in chemistry, physics, and mathematics, a research team with members from complementary disciplinary…

  1. In situ synchrotron powder diffraction study of the setting reaction kinetics of magnesium-potassium phosphate cements

    Czech Academy of Sciences Publication Activity Database

    Viani, Alberto; Pérez-Estébanez, Marta; Pollastri, S.; Gualtieri, A. F.

    2016-01-01

    Roč. 79, January (2016), s. 344-352 ISSN 0008-8846 R&D Projects: GA MŠk(CZ) LO1219 Keywords : kinetics * reaction * X-ray diffraction * MgO * chemically bonded ceramics Subject RIV: JN - Civil Engineering Impact factor: 4.762, year: 2016 http://www.sciencedirect.com/science/article/pii/S0008884615002690

  2. A cellular automata model for traffic flow based on kinetics theory, vehicles capabilities and driver reactions

    Science.gov (United States)

    Guzmán, H. A.; Lárraga, M. E.; Alvarez-Icaza, L.; Carvajal, J.

    2018-02-01

    In this paper, a reliable cellular automata model oriented to faithfully reproduce deceleration and acceleration according to realistic reactions of drivers, when vehicles with different deceleration capabilities are considered is presented. The model focuses on describing complex traffic phenomena by coding in its rules the basic mechanisms of drivers behavior, vehicles capabilities and kinetics, while preserving simplicity. In particular, vehiclés kinetics is based on uniform accelerated motion, rather than in impulsive accelerated motion as in most existing CA models. Thus, the proposed model calculates in an analytic way three safe preserving distances to determine the best action a follower vehicle can take under a worst case scenario. Besides, the prediction analysis guarantees that under the proper assumptions, collision between vehicles may not happen at any future time. Simulations results indicate that all interactions of heterogeneous vehicles (i.e., car-truck, truck-car, car-car and truck-truck) are properly reproduced by the model. In addition, the model overcomes one of the major limitations of CA models for traffic modeling: the inability to perform smooth approach to slower or stopped vehicles. Moreover, the model is also capable of reproducing most empirical findings including the backward speed of the downstream front of the traffic jam, and different congested traffic patterns induced by a system with open boundary conditions with an on-ramp. Like most CA models, integer values are used to make the model run faster, which makes the proposed model suitable for real time traffic simulation of large networks.

  3. Kinetic isotope effect studies of the S-adenosylmethionine synthetase reaction

    International Nuclear Information System (INIS)

    Markham, G.D.; Parkin, D.W.; Schramm, V.L.

    1986-01-01

    S-adenosylmethionine (AdoMet) synthetase catalyzes a unique substitution reaction at the 5' carbon of MgATP. Kinetic isotope effect (V/K) measurements have been used to investigate the mechanism of AdoMet synthetase from E. coli. Changes in 3 H/ 14 C ratios when AdoMet is formed from a mixture of either ([5'- 14 C]ATP and [5'- 12 C,1'- 3 H]ATP) or ([5'- 3 H]ATP and [5'- 1 H,1'- 14 C]ATP) were examined. The effects of varying the concentrations of the co-substrate methionine and the monovalent cation activator K + were investigated. Substitution of 14 C for 12 C at the 5' position of ATP yields a primary V/K kinetic isotope effect ( 12 C/ 14 C) of 1.128 +/- 0.004 at low K + and methionine concentrations. The observed isotope effect diminishes slightly to 1.107 +/- 0.003 when both K + and methionine are present at saturating concentrations, suggesting that MgATP has only a low commitment to catalysis from at conditions near Vmax. No secondary V/K 3 H isotope effect from [5'- 3 H]ATP was detected ( 1 H/ 3 H) = 0.997 +/- 0.003. The magnitude of the primary 14 C isotope effect and the small secondary 3 H effect demonstrate that AdoMet synthesis occurs with a S/sub N/ 2 transition state which is symmetric with respect to the sulfur nucleophile and the departing tripolyphosphate group

  4. Prediction and validation of burnout curves for Goettelborn char using reaction kinetics determined in shock tube experiments

    Energy Technology Data Exchange (ETDEWEB)

    Moors, J.H.J.; Banin, V.E.; Haas, J.H.P.; Weber, R.; Veefkind, A. [Eindhoven University of Technology, Eindhoven (Netherlands). Dept. of Applied Physics

    1999-01-01

    Using a shock tube facility the combustion characteristics of pulverised char ({lt} 10 {mu}m) were measured. A prediction was made for the burnout behaviour of a commercial sized char particle (75-90 {mu}m) in different ambient conditions using a `pseudo kinetic` approach. In this approach the kinetic rate of a surface containing micro pores is determined and these `pseudo kinetics` are then applied to the larger particle not taking into account the micro pores. Comparison of the predictions with measurements done with an isothermal plug flow reactor showed this approach to be valid within experimental error for low burnout. A linear decrease of the kinetic reaction rate with burnout is shown to predict the burnout behaviour in the complete range of burnout. A possible explanation for this linear decrease could be a growing fraction of non-combustible material in the char particles during burnout. 11 refs., 6 figs., 2 tabs.

  5. The browning kinetics of the non-enzymatic browning reaction in L-ascorbic acid/basic amino acid systems

    Directory of Open Access Journals (Sweden)

    Ai-Nong YU

    Full Text Available Abstract Under the conditions of weak basis and the reaction temperature range of 110-150 °C, lysine, arginine and histidine were reacted with L-ascorbic acid at equal amount for 30-150 min, respectively and the formation of browning products was monitored with UV–vis spectrometry. The kinetic characteristics of their non-enzymatic browning reaction were investigated. The study results indicated that the non-enzymatic browning reaction of these three amino acids with L-ascorbic acid to form browning products was zero-order reaction. The apparent activation energies for the formation of browning products from L-ascorbic acid/lysine, L-ascorbic acid/arginine and L-ascorbic acid/histidine systems were 54.94, 50.08 and 35.31kJ/mol. The activation energy data indicated the degree of effects of reaction temperature on non-enzymatic browning reaction. Within the temperature range of 110-150 °C, the reaction rate of L-ascorbic acid/lysine system was the fastest one, followed by that of the L-ascorbic acid/arginine system. The reaction rate of L-ascorbic acid/histidine system was the slowest one. Based on the observed kinetic data, the formation mechanisms of browning products were proposed.

  6. The influence of gas–solid reaction kinetics in models of thermochemical heat storage under monotonic and cyclic loading

    International Nuclear Information System (INIS)

    Nagel, T.; Shao, H.; Roßkopf, C.; Linder, M.; Wörner, A.; Kolditz, O.

    2014-01-01

    Highlights: • Detailed analysis of cyclic and monotonic loading of thermochemical heat stores. • Fully coupled reactive heat and mass transport. • Reaction kinetics can be simplified in systems limited by heat transport. • Operating lines valid during monotonic and cyclic loading. • Local integral degree of conversion to capture heterogeneous material usage. - Abstract: Thermochemical reactions can be employed in heat storage devices. The choice of suitable reactive material pairs involves a thorough kinetic characterisation by, e.g., extensive thermogravimetric measurements. Before testing a material on a reactor level, simulations with models based on the Theory of Porous Media can be used to establish its suitability. The extent to which the accuracy of the kinetic model influences the results of such simulations is unknown yet fundamental to the validity of simulations based on chemical models of differing complexity. In this article we therefore compared simulation results on the reactor level based on an advanced kinetic characterisation of a calcium oxide/hydroxide system to those obtained by a simplified kinetic model. Since energy storage is often used for short term load buffering, the internal reactor behaviour is analysed under cyclic partial loading and unloading in addition to full monotonic charge/discharge operation. It was found that the predictions by both models were very similar qualitatively and quantitatively in terms of thermal power characteristics, conversion profiles, temperature output, reaction duration and pumping powers. Major differences were, however, observed for the reaction rate profiles themselves. We conclude that for systems not limited by kinetics the simplified model seems sufficient to estimate the reactor behaviour. The degree of material usage within the reactor was further shown to strongly vary under cyclic loading conditions and should be considered when designing systems for certain operating regimes

  7. Decolorization kinetics of Procion H-exl dyes from textile dyeing using Fenton-like reactions

    Energy Technology Data Exchange (ETDEWEB)

    Ntampegliotis, K. [Department of Physical Sciences, Technological and Educational Institute of Larisa, T.K 411 10 Larisa (Greece); Riga, A. [Department of Physical Sciences, Technological and Educational Institute of Larisa, T.K 411 10 Larisa (Greece); Karayannis, V. [Department of Physical Sciences, Technological and Educational Institute of Larisa, T.K 411 10 Larisa (Greece); Bontozoglou, V. [Department of Mechanical and Industrial Engineering, University of Thessaly, Pedion Areos, T.K 383 34 Volos (Greece); Papapolymerou, G. [Department of Physical Sciences, Technological and Educational Institute of Larisa, T.K 411 10 Larisa (Greece)]. E-mail: papapoly@teilar.gr

    2006-08-10

    The decolorization kinetics of three commercially used Procion H-exl dyes was studied using a Fenton-like reagent. The effect of the major system parameters (pH, concentration of H{sub 2}O{sub 2} and Fe{sup 3+} and initial dye concentration) on the kinetics was determined. For comparison, the effect of the use of UV irradiated Fenton-like reagent and of Fenton reagent on the kinetics was also examined. In addition, mineralization rates and the biodegradability improvement as well as the effect of the addition of Cl{sup -}, CO{sub 3} {sup 2-} or HCO{sub 3} {sup -} on the decolorization rates was studied. The reactions were carried out in a 300 ml stirred cylindrical reactor with the capability of UV irradiation. The dye half-life time goes through a minimum with respect to the solution pH between 3 and 4. It also exhibits a broad minimum with respect to Fe{sup 3+} and H{sub 2}O{sub 2} at molar ratios of H{sub 2}O{sub 2}/Fe{sup 3+} from about 100 to 10. The addition of CO{sub 3} {sup 2-} and HCO{sub 3} {sup -} substantially reduces the decolorization rates, while this effect is significantly less pronounced with Cl{sup -}. At an optimum range of parameters, the mineralization rate (TOC reduction) is very slow for the Fenton-like process (TOC decrease from an initial 49.5 to 41.1 mg/l after 30 min and to only 35.2 mg/l after 600 min), but it increases significantly for the photo-Fenton-like process (to TOC values of 39.7 and 11.4 mg/l, respectively). The biodegradability, as expressed by the BOD/COD ratio, increases significantly from an initial value of 0.11-0.55 for the Fenton-like and to 0.72 for the photo-Fenton-like processes.

  8. 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.

  9. Arbuscular mycorrhiza and kinetic parameters of phosphorus absorption by bean plants Micorriza arbuscular e os parâmetros cinéticos de absorção de fósforo pelo feijoeiro

    Directory of Open Access Journals (Sweden)

    Adriana Parada Dias da Silveira

    2004-04-01

    Full Text Available The mechanisms that determine greater P absorption by mycorrhizal plants are still not completely clear, and are attributed, in part, to an increase in the number of absorption sites promoted by the hyphae, and/or to a greater affinity of the colonized hypha or root carriers to P. The effect of mycorrhizae formed by Glomus etunicatum on the kinetic parameters of P absorption by the roots and on P influx in bean plants of the IAC-Carioca cultivar was evaluated, in two distinct plant development periods: at the onset of flowering and at the pod-filling stage (35 and 50 days after sowing, respectively. A mixture of sand and silica (9:1 was utilized as substrate and irrigated with nutrient solution. The kinetics assay was performed by the method of 32P depletion from the solution (depletion curve, using intact plants. Mycorrhization promoted greater growth and P absorption by bean plants, which was more conspicuously observed at the pod-filling stage. Mycorrhizal plants showed higher values of maximum ion uptake rate (Vmax and net P influx at the flowering stage. Lower minimum ion concentration (Cmin and Michaelis-Menten constant (Km values were verified in mycorrhizal plants at the pod-filling stage. Mycorrhizal plants also presented higher net P influx per plant, in both stages. Cmin was the kinetic parameter more intimately related to P absorption, and a significant correlation was obtained between this parameter and shoot P content and accumulation in bean plants.Os mecanismos envolvidos na maior absorção de P pela planta micorrizada ainda não estão totalmente esclarecidos, atribuindo-se, em parte, ao aumento no número de sítios de absorção promovido pela hifa e/ou maior afinidade dos carregadores da hifa ou da raiz colonizada ao P. Avaliou-se o efeito da micorriza formada por Glomus etunicatum nos parâmetros cinéticos da absorção radicular de P e no influxo de P em feijoeiro, cultivar IAC-Carioca, em duas épocas do ciclo da planta

  10. Coupling of kinetic Monte Carlo simulations of surface reactions to transport in a fluid for heterogeneous catalytic reactor modeling

    International Nuclear Information System (INIS)

    Schaefer, C.; Jansen, A. P. J.

    2013-01-01

    We have developed a method to couple kinetic Monte Carlo simulations of surface reactions at a molecular scale to transport equations at a macroscopic scale. This method is applicable to steady state reactors. We use a finite difference upwinding scheme and a gap-tooth scheme to efficiently use a limited amount of kinetic Monte Carlo simulations. In general the stochastic kinetic Monte Carlo results do not obey mass conservation so that unphysical accumulation of mass could occur in the reactor. We have developed a method to perform mass balance corrections that is based on a stoichiometry matrix and a least-squares problem that is reduced to a non-singular set of linear equations that is applicable to any surface catalyzed reaction. The implementation of these methods is validated by comparing numerical results of a reactor simulation with a unimolecular reaction to an analytical solution. Furthermore, the method is applied to two reaction mechanisms. The first is the ZGB model for CO oxidation in which inevitable poisoning of the catalyst limits the performance of the reactor. The second is a model for the oxidation of NO on a Pt(111) surface, which becomes active due to lateral interaction at high coverages of oxygen. This reaction model is based on ab initio density functional theory calculations from literature.

  11. The role of high temperature heterogeneous reaction kinetics in the rate of radionuclide vaporisation during core-concrete interactions

    International Nuclear Information System (INIS)

    Raymond, D.P.; Clough, P.N.

    1989-09-01

    Heterogeneous reactions may cause enhanced release of radionuclides during the core-concrete interaction (CCl) stage of a PWR severe accident. The VANESA computer code models these CCI releases using chemical equilibrium assumptions; however, the possibility that chemical kinetics could prevent equilibrium from being achieved is considered in this report. Direct experimental evidence is lacking on these reactions. Therefore, some analogues studies are reviewed, including examples of Eyring's surface reaction rate theory; sequential vaporisation-oxidation processes; iron and steelmaking chemistry; radionuclide evaporation from solid UO 2 . This circumstantial evidence appeared to agree with the current assumptions, in VANESA and some UK modelling studies, that mass transfer, rather than chemical kinetics will limit the rate at which equilibrium is attained. (author)

  12. Aza Cope Rearrangement of Propargyl Enammonium Cations Catalyzed By a Self-Assembled `Nanozyme

    Energy Technology Data Exchange (ETDEWEB)

    Hastings, Courntey J.; Fiedler, Dorothea; Bergman, Robert G.; Raymond, Kenneth N.

    2008-02-27

    The tetrahedral [Ga{sub 4}L{sub 6}]{sup 12-} assembly (L = N,N-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene) encapsulates a variety of cations, including propargyl enammonium cations capable of undergoing the aza Cope rearrangement. For propargyl enammonium substrates that are encapsulated in the [Ga{sub 4}L{sub 6}]{sup 12-} assembly, rate accelerations of up to 184 are observed when compared to the background reaction. After rearrangement, the product iminium ion is released into solution and hydrolyzed allowing for catalytic turnover. The activation parameters for the catalyzed and uncatalyzed reaction were determined, revealing that a lowered entropy of activation is responsible for the observed rate enhancements. The catalyzed reaction exhibits saturation kinetics; the rate data obey the Michaelis-Menten model of enzyme kinetics, and competitive inhibition using a non-reactive guest has been demonstrated.

  13. Effect and Modeling of Glucose Inhibition and In Situ Glucose Removal During Enzymatic Hydrolysis of Pretreated Wheat Straw

    DEFF Research Database (Denmark)

    Andric, Pavle; Meyer, Anne S.; Jensen, Peter Arendt

    2010-01-01

    The enzymatic hydrolysis of lignocellulosic biomass is known to be product-inhibited by glucose. In this study, the effects on cellulolytic glucose yields of glucose inhibition and in situ glucose removal were examined and modeled during extended treatment of heat-pretreated wheat straw......, during 96 h of reaction. When glucose was removed by dialysis during the enzymatic hydrolysis, the cellulose conversion rates and glucose yields increased. In fact, with dialytic in situ glucose removal, the rate of enzyme-catalyzed glucose release during 48-72 h of reaction recovered from 20......-40% to become approximate to 70% of the rate recorded during 6-24 h of reaction. Although Michaelis-Menten kinetics do not suffice to model the kinetics of the complex multi-enzymatic degradation of cellulose, the data for the glucose inhibition were surprisingly well described by simple Michaelis...

  14. Analysis of insulation material deterioration under the LOCA simulated environment on the basis of reaction kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Okada, Sohei; Kusama, Yasuo; Ito, Masayuki; Yagi, Toshiaki; Yoshikawa, Masato (Japan Atomic Energy Research Inst., Takasaki, Gunma. Takasaki Radiation Chemistry Research Establishment)

    1982-12-01

    In the type test of the electric cables installed in reactor containment vessels, it is considerably difficult to perform the testing over a year once in a while to simulate the accidental environment containing radiation and high temperature steam. Two requirements which seem to be more realistic as compared with the above mentioned testing method are inconsistent with each other. To solve this problem, a general rule of deterioration or the expression by an equation is necessary, which enables the extrapolation to show that a short term testing stands on the safety side. The authors have tried to numerically analyze the change of mechanical characteristics of ethylene-propylene rubber (EPR) and Hypalon which are, important as the materials for PH cables (fire-retardant, EP rubber-insulated, chlorosulfonated polyethylene-sheathed cable), in a complex environment of radiation, steam and chemical spray simulating PWR LOCA conditions. In this report, a method is proposed to analyze and estimate the properties by the regression analysis technique on the basis of reaction kinetics, and the analyzed results are described in the order of experiment, analysis method and the results and consideration. The deterioration of the elongation P = e/esub(o) of EPR and Hypalon in the above described complex environment can be represented by the equation - dP/dt = KPsup(n). The exponent n varied in the cases when air is contained or not in that environment, suggesting that the different reactions are dominant in both conditions, respectively. For EPR, n was close to 2 if air was not contained and close to 1 if air was contained in the system.

  15. Electrodeposited ultrafine TaOx/CB catalysts for PEFC cathode application: Their oxygen reduction reaction kinetics

    KAUST Repository

    Seo, Jeongsuk

    2014-12-01

    Ultrafine TaOx nanoparticles were electrodeposited on carbon black (CB) powder in a nonaqueous Ta complex solution at room temperature, and the resultant TaOx/CB catalysts were assessed as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte fuel cell (PEFC) cathodes. The Ta electrodeposition process was scaled up using a newly designed working electrode containing a CB dense layer, without introducing any binder such as the ionomer Nafion in the electrode for electrodeposition. The electrodeposited TaOx/CB powders were removed from the deposition electrode and subsequent H2 treatment at varying temperatures between 523 and 1073 K was attempted to increase the ORR performance. The TaOx/CB samples were characterized by SEM, STEM, XPS, and EELS measurements. XPS and EELS results indicated the reduced nature of the Ta species caused by the high-temperature treatment in H2, while STEM images clearly revealed that the TaOx particles aggregated as the treatment temperature increased. When the TaOx/CB catalyst, which was treated at 873 K for 2 h, was deposited on a glassy carbon substrate with Nafion ionomer, it resulted in the highest activity among the samples investigated, giving an onset potential of 0.95 VRHE at -2 μA cm-2 in a 0.1 M H2SO4 solution. Moreover, the long-term stability test with 10,000 cycles of the voltammetry only led to a 6% loss in the ORR currents, demonstrating the high stability of the TaOx/CB catalysts. Kinetic analysis by R(R)DE indicated that the four-electron transfer pathway in the ORR process was dominant for this TaOx/CB catalyst, and Tafel plots showed a slope corresponding to a one-electron reaction for the rate-determining step.

  16. Modeling of reaction kinetics in bubbling fluidized bed biomass gasification reactor

    Energy Technology Data Exchange (ETDEWEB)

    Thapa, R.K.; Halvorsen, B.M. [Telemark University College, Kjolnes ring 56, P.O. Box 203, 3901 Porsgrunn (Norway); Pfeifer, C. [University of Natural Resources and Life Sciences, Vienna (Austria)

    2013-07-01

    Bubbling fluidized beds are widely used as biomass gasification reactors as at the biomass gasification plant in Gussing, Austria. The reactor in the plant is a dual circulating bubbling fluidized bed gasification reactor. The plant produces 2MW electricity and 4.5MW heat from the gasification of biomass. Wood chips as biomass and olivine particles as hot bed materials are fluidized with high temperature steam in the reactor. As a result, biomass undergoes endothermic chemical reaction to produce a mixture of combustible gases in addition to some carbon-dioxide (CO2). The combustible gases are mainly hydrogen (H2), carbon monoxide (CO) and methane (CH4). The gas is used to produce electricity and heat via utilization in a gas engine. Alternatively, the gas is further processed for gaseous or liquid fuels, but still on the process of development level. Composition and quality of the gas determine the efficiency of the reactor. A computational model has been developed for the study of reaction kinetics in the gasification rector. The simulation is performed using commercial software Barracuda virtual reactor, VR15. Eulerian-Lagrangian approach in coupling of gas-solid flow has been implemented. Fluid phase is treated with an Eulerian formulation. Discrete phase is treated with a Lagrangian formulation. Particle-particle and particle-wall interactions and inter-phase heat and mass transfer have been taken into account. Series of simulations have been performed to study model prediction of the gas composition. The composition is compared with data from the gasifier at the CHP plant in Güssing, Austria. The model prediction of the composition of gases has good agreements with the result of the operating plant.

  17. Electrodeposited ultrafine TaOx/CB catalysts for PEFC cathode application: Their oxygen reduction reaction kinetics

    KAUST Repository

    Seo, Jeongsuk; Anjum, Dalaver H.; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

    2014-01-01

    Ultrafine TaOx nanoparticles were electrodeposited on carbon black (CB) powder in a nonaqueous Ta complex solution at room temperature, and the resultant TaOx/CB catalysts were assessed as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte fuel cell (PEFC) cathodes. The Ta electrodeposition process was scaled up using a newly designed working electrode containing a CB dense layer, without introducing any binder such as the ionomer Nafion in the electrode for electrodeposition. The electrodeposited TaOx/CB powders were removed from the deposition electrode and subsequent H2 treatment at varying temperatures between 523 and 1073 K was attempted to increase the ORR performance. The TaOx/CB samples were characterized by SEM, STEM, XPS, and EELS measurements. XPS and EELS results indicated the reduced nature of the Ta species caused by the high-temperature treatment in H2, while STEM images clearly revealed that the TaOx particles aggregated as the treatment temperature increased. When the TaOx/CB catalyst, which was treated at 873 K for 2 h, was deposited on a glassy carbon substrate with Nafion ionomer, it resulted in the highest activity among the samples investigated, giving an onset potential of 0.95 VRHE at -2 μA cm-2 in a 0.1 M H2SO4 solution. Moreover, the long-term stability test with 10,000 cycles of the voltammetry only led to a 6% loss in the ORR currents, demonstrating the high stability of the TaOx/CB catalysts. Kinetic analysis by R(R)DE indicated that the four-electron transfer pathway in the ORR process was dominant for this TaOx/CB catalyst, and Tafel plots showed a slope corresponding to a one-electron reaction for the rate-determining step.

  18. Laccase-catalyzed removal of the antimicrobials chlorophene and dichlorophen from water: Reaction kinetics, pathway and toxicity evaluation.

    Science.gov (United States)

    Shi, Huanhuan; Peng, Jianbiao; Li, Jianhua; Mao, Liang; Wang, Zunyao; Gao, Shixiang

    2016-11-05

    As active agents in cleaning and disinfecting products, antimicrobials have been widely spread in the environment and have drawn extensive attention as potential threats to the ecological system and human health. In this study, the laccase-catalyzed removal of two emerging antimicrobials, chlorophene (CP) and dichlorophen (DCP), was investigated under simulated environmental conditions. Intrinsic reaction kinetics showed that the removal of CP and DCP followed second-order reaction kinetics, first-order with respect to both the enzyme and the substrate concentration. It was also found that fulvic acid could suppress the transformation of CP and DCP by reversing the oxidation reactions through its action as a scavenger of the free radical intermediates produced from reactions between laccase and the substrates. Several reaction products were identified by a quadrupole time-of-flight mass spectrometer, and detailed reaction pathways were proposed. For both CP and DCP, direct polymerization was the principal pathway, and the coupling patterns were further corroborated based on molecular modeling. The nucleophilic substitution of chlorine by the hydroxyl group was observed, and further oxidation products capable of coupling with each other were also found. Additionally, toxicity evaluation tests using Scenedesmus obliquus confirmed that the toxicity of CP and DCP was effectively eliminated during the reaction processes. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Pre-steady-state kinetics of Escherichia coli aspartate aminotransferase catalyzed reactions and thermodynamic aspects of its substrate specificity

    International Nuclear Information System (INIS)

    Kuramitsu, Seiki; Hiromi, Keitaro; Hayashi, Hideyuki; Morino, Yoshimasa; Kagamiyama, Hiroyuki

    1990-01-01

    The four half-transamination reactions [the pyridoxal form of Escherichia coli aspartate aminotransferase (AspAT) with aspartate or glutamate and the pyridoxamine form of the enzyme with oxalacetate or 2-oxoglutarate] were followed in a stopped-flow spectrometer by monitoring the absorbance change at either 333 or 358 nm. The reaction progress curves in all cases gave fits to a monophasic exponential process. Kinetic analyses of these reactions showed that each half-reaction is composed of the following three processes: (1) the rapid binding of an amino acid substrate to the pyridoxal form of the enzyme; (2) the rapid binding of the corresponding keto acid to the pyridoxamine form of the enzyme; (3) the rate-determining interconversion between the two complexes. This mechanism was supported by the findings that the equilibrium constants for half- and overall-transamination reactions and the steady-state kinetic constants agreed well with the predicted values on the basis of the above mechanism using pre-steady-state kinetic parameters. The significant primary kinetic isotope effect observed in the reaction with deuterated amino acid suggests that the withdrawal of the α-proton of the substrates is rate determining. The pyridoxal form of E. coli AspAT reacted with a variety of amino acids as substrates. The substrate specificity of the E. coli enzyme was much broader than that of pig isoenzymes, reflecting some subtle but distinct difference in microenvironment accommodating the side chain of the substrate between e. coli and mammalian AspATs

  20. Theoretical Study of the Kinetics of the Pyrolytic Elimination Reaction of Ethyl Chloride

    Directory of Open Access Journals (Sweden)

    Isaiah Ajibade Adejoro

    2010-01-01

    Full Text Available The products of the gas-phase elimination of ethyl chloride are hydrogen chloride and ethane. Using AM1, MNDO and PM3 Hamiltonians of quantum mechanical computer code called MOPAC, a procedure for the kinetics and computation of the Arrhenius parameters for the pyrolytic elimination reaction of ethyl chloride was devised in order to evaluate the predictive ability of the three Hamiltonians used. The first-order rate coefficient for the three Hamiltonians are 1.15x10-8s-1, 4.55x10-15s-1 and 5.36x10-4s-1 for AM1, MNDO and PM3 respectively. The results obtained showed that the rate constant for the computed Arrhenius parameters compare well with the experimental values in the literature, thus showing that the computational procedure adequately simulates experimental results; also the semi-empirical AMI calculation has the best predictive ability with experiment followed by PM3 while MNDO has the least.