WorldWideScience

Sample records for 18fflt kinetic parameters

  1. Determination of kinetic parameters for biomass combustion.

    Science.gov (United States)

    Álvarez, A; Pizarro, C; García, R; Bueno, J L; Lavín, A G

    2016-09-01

    The aim of this work is to provide a wide database of kinetic data for the most common biomass by thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). Due to the characteristic parameters of DTG curves, a two-stage reaction model is proposed and the kinetic parameters obtained from model-based methods with energy activation values for first and second stages in the range 1.75·10(4)-1.55·10(5)J/mol and 1.62·10(4)-2.37·10(5)J/mol, respectively. However, it has been found that Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose model-free methods are not suitable to determine the kinetic parameters of biomass combustion since the assumptions of these two methods were not accomplished in the full range of the combustion process.

  2. Kinetic Parameters of Thermal Degradation of Polymers

    Institute of Scientific and Technical Information of China (English)

    朱新生; 程嘉祺

    2003-01-01

    The derivative expressions between activation energy (E) and the temperature at the maximum mass loss rate(Tmax) and between activation energy (E) and exponent (N) were deduced in the light of Arrhenius theory. It was found that the increase of activation energy results in the decrease of exponent and the increase of Tmax. The kinetic parameters were involved in the analysis of the thermal degradation of several polymers. The degradation kinetics of these polymers well complied with the prediction of the derivative expressions for the polymer degradation with single mechanism dominated.

  3. Kinetic Parameter Measurements in the MINERVE Reactor

    Science.gov (United States)

    Perret, Grégory; Geslot, Benoit; Gruel, Adrien; Blaise, Patrick; Di-Salvo, Jacques; De Izarra, Grégoire; Jammes, Christian; Hursin, Mathieu; Pautz, Andréas

    2017-01-01

    In the framework of an international collaboration, teams of the PSI and CEA research institutes measure the critical decay constant (α0 = β/A), delayed neutron fraction (β) and generation time (A) of the Minerve reactor using the Feynman-α, Power Spectral Density and Rossi-α neutron noise measurement techniques. These measurements contribute to the experimental database of kinetic parameters used to improve nuclear data files and validate modern methods in Monte Carlo codes. Minerve is a zero-power pool reactor composed of a central experimental test lattice surrounded by a large aluminum buffer and four high-enriched driver regions. Measurements are performed in three slightly subcritical configurations (-2 cents to -30 cents) using two high-efficiency 235U fission chambers in the driver regions. Measurement of α0 and β obtained by the two institutes and with the different techniques are consistent for the configurations envisaged. Slight increases of the β values are observed with the subcriticality level. Best estimate values are obtained with the Cross-Power Spectral Density technique at -2 cents, and are worth: β = 716.9±9.0 pcm, α0 = 79.0±0.6 s-1 and A = 90.7±1.4 μs. The kinetic parameters are predicted with MCNP5-v1.6 and TRIPOLI4.9 and the JEFF-3.1/3.1.1 and ENDF/B-VII.1 nuclear data libraries. The predictions for β and α0 overestimate the experimental results by 3-5% and 10-12%, respectively; that for A underestimate the experimental result by 6-7%. The discrepancies are suspected to come from the driven system nature of Minerve and the location of the detectors in the driver regions, which prevent accounting for the full reactor.

  4. Estimation of Kinetic Parameters in an Automotive SCR Catalyst Model

    DEFF Research Database (Denmark)

    Åberg, Andreas; Widd, Anders; Abildskov, Jens;

    2016-01-01

    A challenge during the development of models for simulation of the automotive Selective Catalytic Reduction catalyst is the parameter estimation of the kinetic parameters, which can be time consuming and problematic. The parameter estimation is often carried out on small-scale reactor tests, or p...

  5. Kinetic and Thermodynamic Parameters for Uncatalyzed Esterification of Carboxylic Acid

    Directory of Open Access Journals (Sweden)

    Kehinde S. Bankole

    2014-06-01

    Full Text Available A fundamental study on uncatalyzed esterification of various biomass-derived aliphatic carboxylic acids with stoichiometric amount of ethanol has been investigated in an isothermal batch reactor, with the objective to convert carboxylic acids to corresponding ethyl esters and to determine both the kinetic and thermodynamic parameters. The effects of temperature on the conversion of carboxylic acid, kinetic and thermodynamic parameters have been investigated. Temperature was found to have significant effect on the rate of reaction and conversion of carboxylic acid. A simple second order reversible kinetic model was developed to determine the kinetic and thermodynamic parameters. The thermodynamic and kinetic parameters varied for uncatalyzed esterification reaction of both short-chain and long-chain carboxylic acids considered. The predicted data from the kinetic model were correlated with experimental data and the two sets of data agreed reasonably well for the uncatalyzed esterification systems. It was observed that the Van’t Hoff plot for uncatalyzed esterification of linoleic acid was non-linear curve, whereas for the Arrhenius and Eyring plots, they were linear. Additional experiments to assess the catalytic and corrosion effects of several metallic substances revealed Inconel 625 alloy, nickel wire and stainless steel materials were susceptible to corrosion problem with uncatalyzed esterification reaction at elevated reaction temperatures. However, tantalum and grade-5 titanium materials were corrosion resistance metals, suitable for similar reaction conditions and this can encourage the design of a flow reactor system. Although, uncatalyzed esterification of carboxylic acids at elevated reaction temperature is still at laboratory scale. It is our hope that the estimated kinetic and thermodynamic parameters would be the guiding tools for reactor scale-up, thus providing a new perspective into the conversion of biomass-derived carboxylic

  6. Simultaneous Thermodynamic and Kinetic Parameters Determination Using Differential Scanning Calorimetry

    Directory of Open Access Journals (Sweden)

    Nader Frikha

    2011-01-01

    Full Text Available Problem statement: The determination of reaction kinetics is of major importance, as for industrial reactors optimization as for environmental reasons or energy limitations. Although calorimetry is often used for the determination of thermodynamic parameters alone, the question that arises is: how can we apply the Differential Scanning Calorimetry for the determination of kinetic parameters. The objective of this study consists to proposing an original methodology for the simultaneous determination of thermodynamic and kinetic parameters, using a laboratory scale Differential Scanning Calorimeter (DSC. The method is applied to the dichromate-catalysed hydrogen peroxide decomposition. Approach: The methodology is based on operating of experiments carried out with a Differential Scanning Calorimeter. The interest of this approach proposed is that it requires very small quantities of reactants (about a few grams to be implemented. The difficulty lies in the fact that, using such microcalorimeters, the reactants temperature cannot directly be measured and a particular calibration procedure has thus to be developed, to determine the media temperature in an indirect way. The proposed methodology for determination of kinetics parameters is based on resolution of the coupled heat and mass balances. Results: A complete kinetic law is proposed. The Arrhenius parameters are determined as frequency factor k0 = 1.39×109 s−1 and activation energy E = 54.9 kJ mol−1. The measured enthalpy of reaction is ΔrH=−94 kJ mol−1. Conclusion: The comparison of the results obtained by such an original methodology with those obtained using a conventional laboratory scale reactor calorimetry, for the kinetics determination of, shows that this new approach is very relevant.

  7. Unscented Kalman filter with parameter identifiability analysis for the estimation of multiple parameters in kinetic models

    OpenAIRE

    Baker Syed; Poskar C; Junker Björn

    2011-01-01

    Abstract In systems biology, experimentally measured parameters are not always available, necessitating the use of computationally based parameter estimation. In order to rely on estimated parameters, it is critical to first determine which parameters can be estimated for a given model and measurement set. This is done with parameter identifiability analysis. A kinetic model of the sucrose accumulation in the sugar cane culm tissue developed by Rohwer et al. was taken as a test case model. Wh...

  8. Breakdown parameter for kinetic modeling of multiscale gas flows.

    Science.gov (United States)

    Meng, Jianping; Dongari, Nishanth; Reese, Jason M; Zhang, Yonghao

    2014-06-01

    Multiscale methods built purely on the kinetic theory of gases provide information about the molecular velocity distribution function. It is therefore both important and feasible to establish new breakdown parameters for assessing the appropriateness of a fluid description at the continuum level by utilizing kinetic information rather than macroscopic flow quantities alone. We propose a new kinetic criterion to indirectly assess the errors introduced by a continuum-level description of the gas flow. The analysis, which includes numerical demonstrations, focuses on the validity of the Navier-Stokes-Fourier equations and corresponding kinetic models and reveals that the new criterion can consistently indicate the validity of continuum-level modeling in both low-speed and high-speed flows at different Knudsen numbers.

  9. Robust Nonlinear Regression in Enzyme Kinetic Parameters Estimation

    Directory of Open Access Journals (Sweden)

    Maja Marasović

    2017-01-01

    Full Text Available Accurate estimation of essential enzyme kinetic parameters, such as Km and Vmax, is very important in modern biology. To this date, linearization of kinetic equations is still widely established practice for determining these parameters in chemical and enzyme catalysis. Although simplicity of linear optimization is alluring, these methods have certain pitfalls due to which they more often then not result in misleading estimation of enzyme parameters. In order to obtain more accurate predictions of parameter values, the use of nonlinear least-squares fitting techniques is recommended. However, when there are outliers present in the data, these techniques become unreliable. This paper proposes the use of a robust nonlinear regression estimator based on modified Tukey’s biweight function that can provide more resilient results in the presence of outliers and/or influential observations. Real and synthetic kinetic data have been used to test our approach. Monte Carlo simulations are performed to illustrate the efficacy and the robustness of the biweight estimator in comparison with the standard linearization methods and the ordinary least-squares nonlinear regression. We then apply this method to experimental data for the tyrosinase enzyme (EC 1.14.18.1 extracted from Solanum tuberosum, Agaricus bisporus, and Pleurotus ostreatus. The results on both artificial and experimental data clearly show that the proposed robust estimator can be successfully employed to determine accurate values of Km and Vmax.

  10. Evaluation of true kinetic parameters for reversible immobilized enzyme reactions

    Energy Technology Data Exchange (ETDEWEB)

    Ishikawa, H.; Tanaka, T.; Kurose, K.; Hikita, H.

    1987-06-01

    For a reversible one-substrate reaction system that follows the Haldane reaction mechanism, a new and effective method has been proposed to extract true or intrinsic kinetic parameters of immobilized enzymes from diffusion limited rate data. The method utilizes the effectiveness factors correlated in terms of the general modulus defined by Aris and Bischoff, and a new modulus defined in the present study. It requires a trial-and-error calculation, but only a few data points. Furthermore, it provides a saving of materials such as substrates and enzymes, and takes less time for experiments compared to the initial rate methods. The usefulness of the method is demonstrated by determining the kinetic parameters for membrane bound fumarase which catalyzes the reaction of the conversion of fumarate to L-malate, for which the equilibrium constant is circa 4. (Refs. 20).

  11. Thermoluminescent kinetics parameters of inorganic dust from camomile

    Energy Technology Data Exchange (ETDEWEB)

    Furetta, C.; Cruz Z, E. [ICN-UNAM, A.P. 70-543, 04510 Mexico D.F. (Mexico); Favalli, A. [European Commission, Joint Research Centre, Institute for the Protection and Security of Citizen, TP800, Via E. Fermi 21020, Ispra VA (Italy); Gomez R, J.M. [CIEMAT, Av. Complutense 22, 28040 Madrid (Spain); Kitis, G. [Nuclear Physics Laboratory, University of Thessaloniky (Greece)

    2006-07-01

    The poly mineral dust extracted from camomile herb was exposed to gamma radiation. The glow curves from these poly minerals show a large, single TL peak, centred at about 440 K. Because the large structure of the glow curves, it seems that the TL signal could be produced by a trap distribution instead of a single level. The thermoluminescent kinetic parameters of the glow curves have been accurately analysed using the Computerized Glow Curve Deconvolution (CGCD) applied at different steps during fading experiment at room temperature (RT). Deconvolution has been performed using a continuous distribution of trapping levels, uniformly distributed, including one additional peak in the high temperature region. This peak has been modelled with second-order kinetics. (Author)

  12. 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.

  13. Correlating thermodynamic and kinetic parameters with amorphous stability

    DEFF Research Database (Denmark)

    Graeser, Kirsten A; Patterson, James E; Zeitler, J Axel

    2009-01-01

    Poor physical stability is one of the single most important factors limiting the widespread use of the amorphous state in pharmaceutics. The purpose of this study is to move away from the case study approach by investigating thermodynamic and kinetic parameters as potential predictors of physical...... stability of amorphous drugs for a larger sample set (12 drugs). The relaxation time, fragility index and configurational thermodynamic properties (enthalpy, entropy and Gibbs free energy) were calculated and correlated to the actual stability behaviour, obtained for 12 drugs. Below the glass transition...

  14. Parameter estimation for models of ligninolytic and cellulolytic enzyme kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Gangsheng [ORNL; Post, Wilfred M [ORNL; Mayes, Melanie [ORNL; Frerichs, Joshua T [ORNL; Jagadamma, Sindhu [ORNL

    2012-01-01

    While soil enzymes have been explicitly included in the soil organic carbon (SOC) decomposition models, there is a serious lack of suitable data for model parameterization. This study provides well-documented enzymatic parameters for application in enzyme-driven SOC decomposition models from a compilation and analysis of published measurements. In particular, we developed appropriate kinetic parameters for five typical ligninolytic and cellulolytic enzymes ( -glucosidase, cellobiohydrolase, endo-glucanase, peroxidase, and phenol oxidase). The kinetic parameters included the maximum specific enzyme activity (Vmax) and half-saturation constant (Km) in the Michaelis-Menten equation. The activation energy (Ea) and the pH optimum and sensitivity (pHopt and pHsen) were also analyzed. pHsen was estimated by fitting an exponential-quadratic function. The Vmax values, often presented in different units under various measurement conditions, were converted into the same units at a reference temperature (20 C) and pHopt. Major conclusions are: (i) Both Vmax and Km were log-normal distributed, with no significant difference in Vmax exhibited between enzymes originating from bacteria or fungi. (ii) No significant difference in Vmax was found between cellulases and ligninases; however, there was significant difference in Km between them. (iii) Ligninases had higher Ea values and lower pHopt than cellulases; average ratio of pHsen to pHopt ranged 0.3 0.4 for the five enzymes, which means that an increase or decrease of 1.1 1.7 pH units from pHopt would reduce Vmax by 50%. (iv) Our analysis indicated that the Vmax values from lab measurements with purified enzymes were 1 2 orders of magnitude higher than those for use in SOC decomposition models under field conditions.

  15. The kinetic parameters of carbonaceous materials activated with potassium hydroxide

    Energy Technology Data Exchange (ETDEWEB)

    Yong, Z.; Han, B.X.

    2000-07-01

    On the basis of microspore formation in carbonaceous materials, the activation energy for the potassium hydroxide activation of Chinese petroleum coke and coal has been deduced theoretically as dB(O)/dt = A exp(-E(a)) is an element of/RT), where is an element of is the formation energy for the metastable solid formed at the activation temperature. The kinetic parameters (frequency factor, A, and apparent activation energy, E(a) were calculated from this equation as being 5.319 mg/(g min), 36.51 kJ/mol and 6.64 mg/(g min), 49.46 kJ/mol, respectively, for the two carbonaceous materials studied.

  16. 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

    Effective estimation of parameters in biocatalytic reaction kinetic expressions are very important when building process models to enable evaluation of process technology options and alternative biocatalysts. The kinetic models used to describe enzyme-catalyzed reactions generally include several...

  17. Unscented Kalman filter with parameter identifiability analysis for the estimation of multiple parameters in kinetic models

    Directory of Open Access Journals (Sweden)

    Baker Syed

    2011-01-01

    Full Text Available Abstract In systems biology, experimentally measured parameters are not always available, necessitating the use of computationally based parameter estimation. In order to rely on estimated parameters, it is critical to first determine which parameters can be estimated for a given model and measurement set. This is done with parameter identifiability analysis. A kinetic model of the sucrose accumulation in the sugar cane culm tissue developed by Rohwer et al. was taken as a test case model. What differentiates this approach is the integration of an orthogonal-based local identifiability method into the unscented Kalman filter (UKF, rather than using the more common observability-based method which has inherent limitations. It also introduces a variable step size based on the system uncertainty of the UKF during the sensitivity calculation. This method identified 10 out of 12 parameters as identifiable. These ten parameters were estimated using the UKF, which was run 97 times. Throughout the repetitions the UKF proved to be more consistent than the estimation algorithms used for comparison.

  18. Unscented Kalman filter with parameter identifiability analysis for the estimation of multiple parameters in kinetic models.

    Science.gov (United States)

    Baker, Syed Murtuza; Poskar, C Hart; Junker, Björn H

    2011-10-11

    In systems biology, experimentally measured parameters are not always available, necessitating the use of computationally based parameter estimation. In order to rely on estimated parameters, it is critical to first determine which parameters can be estimated for a given model and measurement set. This is done with parameter identifiability analysis. A kinetic model of the sucrose accumulation in the sugar cane culm tissue developed by Rohwer et al. was taken as a test case model. What differentiates this approach is the integration of an orthogonal-based local identifiability method into the unscented Kalman filter (UKF), rather than using the more common observability-based method which has inherent limitations. It also introduces a variable step size based on the system uncertainty of the UKF during the sensitivity calculation. This method identified 10 out of 12 parameters as identifiable. These ten parameters were estimated using the UKF, which was run 97 times. Throughout the repetitions the UKF proved to be more consistent than the estimation algorithms used for comparison.

  19. Electrochemical evaluation of glutathione S-transferase kinetic parameters.

    Science.gov (United States)

    Enache, Teodor Adrian; Oliveira-Brett, Ana Maria

    2015-02-01

    Glutathione S-transferases (GSTs), are a family of enzymes belonging to the phase II metabolism that catalyse the formation of thioether conjugates between the endogenous tripeptide glutathione and xenobiotic compounds. The voltammetric behaviour of glutathione (GSH), 1-chloro-2,4-dinitrobenzene (CDNB) and glutathione S-transferase (GST), as well as the catalytic conjugation reaction of GSH to CDNB by GST was investigated at room temperature, T=298.15K (25°C), at pH6.5, for low concentration of substrates and enzyme, using differential pulse (DP) voltammetry at a glassy carbon electrode. Only GSH can be oxidized; a sensitivity of 0.14nA/μM and a LOD of 6.4μM were obtained. The GST kinetic parameter electrochemical evaluation, in relation to its substrates, GSH and CDNB, using reciprocal Michaelis-Menten and Lineweaver-Burk double reciprocal plots, was determined. A value of KM~100μM was obtained for either GSH or CDNB, and Vmax varied between 40 and 60μmol/min per mg of GST.

  20. Comparison of Seven Kinetic Equations for K Release and Application of Kinetic Parameters

    Institute of Scientific and Technical Information of China (English)

    L(U) Xiao-Nan; XU Jian-Ming; MA Wan-Zhu; LU Yun-Fu

    2007-01-01

    Corn field experiments with two treatments, NP and NPK, where N in the form of urea, P in the form of calcium phosphate, and K in the form of KC1 were applied at rates of 187.5, 33.3, and 125 kg ha-1, respectively, on soils derived from Quaternary red clay were conducted in the hilly red soil region of Zhejiang Province, China. Plant grains and stalks were collected for determination of K content. Seven equations were used to describe the kinetics of K release from surface soil samples taken before the corn experiments under electric field strengths of 44.4 and 88.8 V cm-1 by means of electro-ultrafiltration (EUF) and to determine if their parameters had a practical application. The second-order and Elovich equations excellently described K release; the first-order, power function, and parabolic diffusion equations also described K release well; but the zero-order and exponential equations were not so good at reflecting K release. Five reference standards from the field experiments, including relative grain yield (yield of the NP treatment/yield of the NPK treatment), relative dry matter yield (dry matter of the NP treatment/dry matter of the NPK treatment), quantity of K uptake in the NP treatment (no K application), soil exchangeable K, and soil HNO3-soluble K, were used to test the effectiveness of equation parameters obtained from the slope or intercept of these equations. Correlations of the ymax (the maximum desorbable quantity of K) in the second-order equation and the constant b in the first-order and E lovich equations to all five reference standards were highly significant (P ≤ 0.01). The constant a in the power function equation was highly significant (P ≤ 0.01) for four of the five reference standards with the fifth being significant (P ≤ 0.05). The constant b in the parabolic equation was also significantly correlated (P ≤ 0.05) to the relative grain yield and soil HNO3-solublc K. These suggested that all of these parameters could be used to

  1. Determination of kinetic parameters for complex transesterification reaction by standard optimisation methods

    Directory of Open Access Journals (Sweden)

    Almagrbi Abdualnaser Muftah

    2014-01-01

    Full Text Available This article presents a methodology for kinetic parameter estimation which is based on standard optimization methods. The parameter estimation procedure is applied to the example of modelling of non-catalytic transesterification reaction, based on laboratory experiments performed under elevated pressure. The kinetic model employed in this study consists of three consecutive and parallel reversible reactions of the second order, with six kinetic constants. The influence of the mass transfer effects was considered as well. The best results were obtained by Genetic Algorithm method. The application of this method resulted in kinetic parameters with improved accuracy in predicting concentrations of important reaction intermediates, i.e. diglycerides and monoglycerides. Activation energies of kinetic parameters obtained by the Genetic Algorithm method are in very good agreement with theoretical values determined by molecular orbital calculations. [Projekat Ministarstva nauke Republike Srbije, br. III-45019

  2. Non-linear relationship between combustion kinetic parameters and coal quality

    Institute of Scientific and Technical Information of China (English)

    Jian-guo YANG; Xiao-long ZHANG; Hong ZHAO; Li SHEN

    2012-01-01

    Combustion kinetic parameters (i.e.,activation energy and frequency factor) of coal have been proven to relate closely to coal properties; however,the quantitative relationship between them still requires further study.This paper adopts a support vector regression machine (SVR) to generate the models of the non-linear relationship between combustion kinetic parameters and coal quality.Kinetic analyses on the thermo-gravimetry (TG) data of 80 coal samples were performed to prepare training data and testing data for the SVR.The models developed were used in the estimation of the combustion kinetic parameters of ten testing samples.The predicted results showed that the root mean square errors (RMSEs) were 2.571 for the activation energy and 0.565for the frequency factor in logarithmic form,respectively.TG curves defined by predicted kinetic parameters were fitted to the experimental data with a high degree of precision.

  3. Determination of Kinetic Parameters of Molecular Beam Epitaxy,

    Science.gov (United States)

    1985-04-17

    A kinetic growth model for molecular beam epitaxy (MBE) was discussed. Furthermore, high energy electron diffraction (HEED) was used as a surface...characterization method to provide evidence for this model. GaAs was used as an example to study the growth rate of molecular beam epitaxy . The relation

  4. Development of simple kinetic models and parameter estimation for ...

    African Journals Online (AJOL)

    PANCHIGA

    Key words: Exponential feed, growth modeling, Monod kinetic equation, Pichia pastoris, recombinant human ... Author(s) agree that this article remains permanently open access under the terms of the Creative Commons .... Methanol was the only energy and carbon source ..... A potential explanation for the decline in cell.

  5. Mechanism and Kinetic Parameters of Thermal Decomposition of Cobalt Dichloride Hexahydrate

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The thermal decomposition of the cobalt dichloride hexahydrate and its kinetics were studied by TG and DTG technique under the non-isothermal condition with nitrogen atnosphere.The non-isothermal kinetic data and kinetic parameters were evaluated by means of integral and differential methods.The most probable mechanism functions of the thermal decomposition reaction for the first stage are:f(α)=(1-α)2 and g(α)=(1-α)-1-1.

  6. Estimation of Kinetic Parameters for Autocatalytic Oxidation of Cyclohexane Based on a Modified Adaptive Genetic Algorithm

    Institute of Scientific and Technical Information of China (English)

    刘平乐; 邹丽珊; 罗和安; 王良芥; 郑金华

    2004-01-01

    A modified genetic algorithm of multiple selection strategies, crossover strategies and adaptive operator is constructed, and it is used to estimate the kinetic parameters in autocatalytic oxidation of cyclohexane. The influences of selection strategy, crossover strategy and mutation strategy on algorithm performance are discussed. This algorithm with a specially designed adaptive operator avoids the problem of local optimum usually associated with using standard genetic algorithm and simplex method. The kinetic parameters obtained from the modified genetic algorithm are credible and the calculation results using these parameters agree well with experimental data. Furthermore, a new kinetic model of cyclohexane autocatalytic oxidation is established and the kinetic parameters are estimated by using the modified genetic algorithm.

  7. Effect of kinetic parameters on heterologous protein production: a sysbio approach

    DEFF Research Database (Denmark)

    Nandy, Subir Kumar; Rattleff, Stig; Thykær, Jette

    To improve the expression and secretion of heterologous proteins in the filamentous grampositive bacteria, Streptomyces lividans, bioprocessing strategies were developed. A mathematical model was constructed to study the effects of the process kinetic parameters on the production of the model...

  8. Parameter Optimization of Nitriding Process Using Chemical Kinetics

    Science.gov (United States)

    Özdemir, İ. Bedii; Akar, Firat; Lippmann, Nils

    2016-09-01

    Using the dynamics of chemical kinetics, an investigation to search for an optimum condition for a gas nitriding process is performed over the solution space spanned by the initial temperature and gas composition of the furnace. For a two-component furnace atmosphere, the results are presented in temporal variations of gas concentrations and the nitrogen coverage on the surface. It seems that the exploitation of the nitriding kinetics can provide important feedback for setting the model-based control algorithms. The present work shows that when the nitrogen gas concentration is not allowed to exceed 6 pct, the Nad coverage can attain maximum values as high as 0.97. The time evolution of the Nad coverage also reveals that, as long as the temperature is above the value where nitrogen poisoning of the surface due to the low-temperature adsorption of excess nitrogen occurs, the initial ammonia content in the furnace atmosphere is much more important in the nitriding process than is the initial temperature.

  9. Estimation of kinetic parameters related to biochemical interactions between hydrogen peroxide and signal transduction proteins

    Directory of Open Access Journals (Sweden)

    Paula Matos de Brito

    2014-10-01

    Full Text Available The lack of kinetic data concerning the biological effects of reactive oxygen species is slowing down the development of the field of redox signaling. Herein, we deduced and applied equations to estimate kinetic parameters from typical redox signaling experiments. H2O2-sensing mediated by the oxidation of a protein target and the switch-off of this sensor, by being converted back to its reduced form, are the two processes for which kinetic parameters are determined. The experimental data required to apply the equations deduced is the fraction of the H2O2 sensor protein in the reduced or in the oxidized state measured in intact cells or living tissues after exposure to either endogenous or added H2O2. Either non-linear fittings that do not need transformation of the experimental data or linearized plots in which deviations from the equations are easily observed can be used. The equations were shown to be valid by fitting to them virtual time courses simulated with a kinetic model. The good agreement between the kinetic parameters estimated in these fittings and those used to simulate the virtual time courses supported the accuracy of the kinetic equations deduced. Finally, equations were successfully tested with real data taken from published experiments that describe redox signaling mediated by the oxidation of two protein tyrosine phosphatases, PTP1B and SHP-2, which are two of the few H2O2-sensing proteins with known kinetic parameters. Whereas for PTP1B estimated kinetic parameters fitted in general the present knowledge, for SHP-2 results obtained suggest that reactivity towards H2O2 as well as the rate of SHP-2 regeneration back to its reduced form are higher than previously thought. In conclusion, valuable quantitative kinetic data can be estimated from typical redox signaling experiments, thus improving our understanding about the complex processes that underline the interplay between oxidative stress and redox signaling responses.

  10. Estimation of kinetic parameters related to biochemical interactions between hydrogen peroxide and signal transduction proteins

    Science.gov (United States)

    Brito, Paula; Antunes, Fernando

    2014-10-01

    The lack of kinetic data concerning the biological effects of reactive oxygen species is slowing down the development of the field of redox signaling. Herein, we deduced and applied equations to estimate kinetic parameters from typical redox signaling experiments. H2O2-sensing mediated by the oxidation of a protein target and the switch-off of this sensor, by being converted back to its reduced form, are the two processes for which kinetic parameters are determined. The experimental data required to apply the equations deduced is the fraction of the H2O2 sensor protein in the reduced or in the oxidized state measured in intact cells or living tissues after exposure to either endogenous or added H2O2. Either non-linear fittings that do not need transformation of the experimental data or linearized plots in which deviations from the equations are easily observed can be used. The equations were shown to be valid by fitting to them virtual time courses simulated with a kinetic model. The good agreement between the kinetic parameters estimated in these fittings and those used to simulate the virtual time courses supported the accuracy of the kinetic equations deduced. Finally, equations were successfully tested with real data taken from published experiments that describe redox signaling mediated by the oxidation of two protein tyrosine phosphatases, PTP1B and SHP-2, which are two of the few H2O2-sensing proteins with known kinetic parameters. Whereas for PTP1B estimated kinetic parameters fitted in general the present knowledge, for SHP-2 results obtained suggest that reactivity towards H2O2 as well as the rate of SHP-2 regeneration back to its reduced form are higher than previously thought. In conclusion, valuable quantitative kinetic data can be estimated from typical redox signaling experiments, thus improving our understanding about the complex processes that underline the interplay between oxidative stress and redox signaling responses.

  11. Calculation of statistic estimates of kinetic parameters from substrate uncompetitive inhibition equation using the median method

    Directory of Open Access Journals (Sweden)

    Pedro L. Valencia

    2017-04-01

    Full Text Available We provide initial rate data from enzymatic reaction experiments and tis processing to estimate the kinetic parameters from the substrate uncompetitive inhibition equation using the median method published by Eisenthal and Cornish-Bowden (Cornish-Bowden and Eisenthal, 1974; Eisenthal and Cornish-Bowden, 1974. The method was denominated the direct linear plot and consists in the calculation of the median from a dataset of kinetic parameters Vmax and Km from the Michaelis–Menten equation. In this opportunity we present the procedure to applicate the direct linear plot to the substrate uncompetitive inhibition equation; a three-parameter equation. The median method is characterized for its robustness and its insensibility to outlier. The calculations are presented in an Excel datasheet and a computational algorithm was developed in the free software Python. The kinetic parameters of the substrate uncompetitive inhibition equation Vmax, Km and Ks were calculated using three experimental points from the dataset formed by 13 experimental points. All the 286 combinations were calculated. The dataset of kinetic parameters resulting from this combinatorial was used to calculate the median which corresponds to the statistic estimator of the real kinetic parameters. A comparative statistical analyses between the median method and the least squares was published in Valencia et al. [3].

  12. Calculation of statistic estimates of kinetic parameters from substrate uncompetitive inhibition equation using the median method.

    Science.gov (United States)

    Valencia, Pedro L; Astudillo-Castro, Carolina; Gajardo, Diego; Flores, Sebastián

    2017-04-01

    We provide initial rate data from enzymatic reaction experiments and tis processing to estimate the kinetic parameters from the substrate uncompetitive inhibition equation using the median method published by Eisenthal and Cornish-Bowden (Cornish-Bowden and Eisenthal, 1974; Eisenthal and Cornish-Bowden, 1974). The method was denominated the direct linear plot and consists in the calculation of the median from a dataset of kinetic parameters Vmax and Km from the Michaelis-Menten equation. In this opportunity we present the procedure to applicate the direct linear plot to the substrate uncompetitive inhibition equation; a three-parameter equation. The median method is characterized for its robustness and its insensibility to outlier. The calculations are presented in an Excel datasheet and a computational algorithm was developed in the free software Python. The kinetic parameters of the substrate uncompetitive inhibition equation Vmax , Km and Ks were calculated using three experimental points from the dataset formed by 13 experimental points. All the 286 combinations were calculated. The dataset of kinetic parameters resulting from this combinatorial was used to calculate the median which corresponds to the statistic estimator of the real kinetic parameters. A comparative statistical analyses between the median method and the least squares was published in Valencia et al. [3].

  13. Comparison Of A Neutron Kinetics Parameter For A Polyethylene Moderated Highly Enriched Uranium System

    Energy Technology Data Exchange (ETDEWEB)

    McKenzie, IV, George Espy [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Goda, Joetta Marie [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Grove, Travis Justin [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Sanchez, Rene Gerardo [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-04-17

    This paper examines the comparison of MCNP® code’s capability to calculate kinetics parameters effectively for a thermal system containing highly enriched uranium (HEU). The Rossi-α parameter was chosen for this examination because it is relatively easy to measure as well as easy to calculate using MCNP®’s kopts card. The Rossi-α also incorporates many other parameters of interest in nuclear kinetics most of which are more difficult to precisely measure. The comparison looks at two different nuclear data libraries for comparison to the experimental data. These libraries are ENDF/BVI (.66c) and ENDF/BVII (.80c).

  14. Kinetics of nitrite reduction by zinc metal: influence of metal shape on the determination of kinetic parameters.

    Science.gov (United States)

    Limousy, L; Dutournie, P; Hadjiev, D

    2010-07-01

    Heterogeneous chemical reactions are complicated, especially in the case of competitive reactions. The aim of this study was to investigate the elimination of nitrite (NO2(-)) by applying a metallic reduction using zero-valent zinc (Zn0). The effect of pH, stirring, and metal shape (powder and chips) on the rate and products of nitrite reduction were studied in a batch-stirred reactor. The obtained data have been used to optimize the conditions for metallic reduction of NO2(-) and for kinetic parameters identification. It was found that the dissolution of zinc involves a pseudo-first-order reaction independent of the shape of the metal. Further, the influence of operating conditions on nitrogen (N2) and ammonium (NH4(+)) formation has been determined. It was found that a decrease in pH and in the Zn0 content enhances NH4(+) production. If kinetic parameters can be approximated easily for constant surface area, it was demonstrated that surface evolution had to be integrated for metal powder. Finally, a numerical simulation has been used to determine the kinetic parameters for NO2(-) reduction with zinc powder.

  15. Kinetic parameters calculation and measurements during the OPAL commissioning

    Energy Technology Data Exchange (ETDEWEB)

    Hergenreder, D.F.; Lecot, C.A.; Villarino, E.A. [INVAP S.E., Nuclear Projects Dept., Nuclear Engineering Div., Rio Negro (Argentina)

    2007-07-01

    During the Commissioning Stage of the OPAL Research Reactor (Australia) the Prompt Neutron Decay constant ({alpha}) was measured by analysing the inherent fluctuations that occur in the neutron population. The ratio of the variance to the mean number of counts as a function of counting time is used to determine experimentally the {alpha} parameter. This technique is also called Feynman-{alpha} Method. The CITVAP and MCNP codes were used to calculate the prompt neutron decay constant for the first core configuration. By means of two different MCNP calculations, one considering prompt fission neutrons only and another with total fission neutrons; the effective delayed neutron fraction is estimated. The experimental method, the measured value as well as the numerical assessment are presented in this paper. A good agreement was obtained between measurements and calculations, particularly it is worth noticing that the measured value for the {alpha} parameter, when {rho} = 0, is 38.1 s{sup -1} while the calculated value is 37.2 s{sup -1}.

  16. Inverse modeling approach for evaluation of kinetic parameters of a biofilm reactor using tabu search.

    Science.gov (United States)

    Kumar, B Shiva; Venkateswarlu, Ch

    2014-08-01

    The complex nature of biological reactions in biofilm reactors often poses difficulties in analyzing such reactors experimentally. Mathematical models could be very useful for their design and analysis. However, application of biofilm reactor models to practical problems proves somewhat ineffective due to the lack of knowledge of accurate kinetic models and uncertainty in model parameters. In this work, we propose an inverse modeling approach based on tabu search (TS) to estimate the parameters of kinetic and film thickness models. TS is used to estimate these parameters as a consequence of the validation of the mathematical models of the process with the aid of measured data obtained from an experimental fixed-bed anaerobic biofilm reactor involving the treatment of pharmaceutical industry wastewater. The results evaluated for different modeling configurations of varying degrees of complexity illustrate the effectiveness of TS for accurate estimation of kinetic and film thickness model parameters of the biofilm process. The results show that the two-dimensional mathematical model with Edward kinetics (with its optimum parameters as mu(max)rho(s)/Y = 24.57, Ks = 1.352 and Ki = 102.36) and three-parameter film thickness expression (with its estimated parameters as a = 0.289 x 10(-5), b = 1.55 x 10(-4) and c = 15.2 x 10(-6)) better describes the biofilm reactor treating the industry wastewater.

  17. Reaction Kinetic Parameters and Surface Thermodynamic Properties of Cu2O Nanocubes

    Directory of Open Access Journals (Sweden)

    Xingxing Li

    2015-07-01

    Full Text Available Cuprous oxide (Cu2O nanocubes were synthesized by reducing Cu(OH2 in the presence of sodium citrate at room temperature. The samples were characterized in detail by field-emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray powder diffraction, and N2 absorption (BET specific surface area. The equations for acquiring reaction kinetic parameters and surface thermodynamic properties of Cu2O nanocubes were deduced by establishment of the relations between thermodynamic functions of Cu2O nanocubes and these of the bulk Cu2O. Combined with thermochemical cycle, transition state theory, basic theory of chemical thermodynamics, and in situ microcalorimetry, reaction kinetic parameters, specific surface enthalpy, specific surface Gibbs free energy, and specific surface entropy of Cu2O nanocubes were successfully determined. We also introduced a universal route for gaining reaction kinetic parameters and surface thermodynamic properties of nanomaterials.

  18. Fuzzy Stochastic Petri Nets for Modeling Biological Systems with Uncertain Kinetic Parameters.

    Science.gov (United States)

    Liu, Fei; Heiner, Monika; Yang, Ming

    2016-01-01

    Stochastic Petri nets (SPNs) have been widely used to model randomness which is an inherent feature of biological systems. However, for many biological systems, some kinetic parameters may be uncertain due to incomplete, vague or missing kinetic data (often called fuzzy uncertainty), or naturally vary, e.g., between different individuals, experimental conditions, etc. (often called variability), which has prevented a wider application of SPNs that require accurate parameters. Considering the strength of fuzzy sets to deal with uncertain information, we apply a specific type of stochastic Petri nets, fuzzy stochastic Petri nets (FSPNs), to model and analyze biological systems with uncertain kinetic parameters. FSPNs combine SPNs and fuzzy sets, thereby taking into account both randomness and fuzziness of biological systems. For a biological system, SPNs model the randomness, while fuzzy sets model kinetic parameters with fuzzy uncertainty or variability by associating each parameter with a fuzzy number instead of a crisp real value. We introduce a simulation-based analysis method for FSPNs to explore the uncertainties of outputs resulting from the uncertainties associated with input parameters, which works equally well for bounded and unbounded models. We illustrate our approach using a yeast polarization model having an infinite state space, which shows the appropriateness of FSPNs in combination with simulation-based analysis for modeling and analyzing biological systems with uncertain information.

  19. EQUILIBRIUM AND KINETIC PARAMETERS FOR THE SEDIMENTATION OF TARTARIC SALTS IN YOUNG WINES

    Directory of Open Access Journals (Sweden)

    Ecaterina Covaci

    2015-06-01

    Full Text Available In young wines potassium hydrogen tartrate is always present in supersaturating concentration and crystallizes spontaneously. The aim of this study is to obtain kinetic parameters, which explain the stability of young wines during the stabilization treatments. The kinetic and equilibrium parameters were evaluated and discussed. The heating factor has a decisive influence on the reaction rate of potassium hydrogen tartrate precipitation in young wines. An increase of temperature leads to a decrease in efficiency of stabilization process and to an enhancement of the activation energy of the system. According to the obtained experimental results, the optimal regime for production and stabilization of young wines has been established.

  20. A novel method for measuring the concentration of chloroform based on kinetic parameters at atmosphere

    Science.gov (United States)

    Wang, Yuguo; Han, Haiyan; Chang, Tao; Liu, Xiuhong; Zhu, Qiaofen; Liu, Feng; Yan, Yongliang; Shen, Chengyin; Chu, Yannan

    2016-06-01

    A novel method is proposed to detect chloroform concentrations based on the kinetic parameters using ion mobility spectrometer with a negative corona discharge ion source operating at atmospheric pressure. Unlike conventional sample introduction mode, in this technique, CHCl3 enters into the drift tube from the end of drift region carried by the drift gas. There are two tails before Cl- and (CHCl3)·Cl- ion peaks, which fit to the ions formed in the drift region. Utilizing the kinetic parameters, concentration for CHCl3 can be calculated. This method not only offers a new way to get concentrations of CHCl3 under atmospheric pressure.

  1. Kinetics parameters of a slurry remediation process in rotating drum bioreactors

    Energy Technology Data Exchange (ETDEWEB)

    Esquivel-Rios, I.; Rodriguez-Meza, M. A.; Barrera-Cortes, J.

    2009-07-01

    The knowledge of biotransformation pollution dynamics in any systems is important for design and optimization purposes of biochemical processes involved. this is focus to the determination of kinetics parameters such as the maximum specific growth rate ({mu}MAX), saturation constant (Ks), biomass yield (YX/S; X: biomass, S: substrate) and oxygen consumption (YO{sub 2}/S; O{sub 2}: oxygen). Several approximations, based on Monod equation, have been developed for estimating kinetics parameters in terms of concentration and type of substrate, bioprocess type and microflora available. (Author)

  2. Application of micro-genetic algorithm for calibration of kinetic parameters in HCCI engine combustion model

    Institute of Scientific and Technical Information of China (English)

    Haozhong HUANG; Wanhua SU

    2008-01-01

    The micro-genetic algorithm (μGA) as a highly effective optimization method, is applied to calibrate to a newly developed reduced chemical kinetic model (40 species and 62 reactions) for the homogeneous charge compression ignition (HCCI) combustion of n-heptane to improve its autoignition predictions for different engine operating conditions. The seven kinetic parameters of the calibrated model are determined using a combination of the Micro-Genetic Algorithm and the SENKIN program of CHEMKIN chemical kinetics software package. Simulation results show that the autoignition predictions of the calibrated model agree better with those of the detailed chemical kinetic model (544 species and 2 446 reactions) than the original model over the range of equivalence ratios from 0.1-1.3 and temperature from 300-3 000 K. The results of this study have demonstrated that the μGA is an effective tool to facilitate the calibration of a large number of kinetic parameters in a reduced kinetic model.

  3. Evaluation of Anaerobic Biofilm Reactor Kinetic Parameters Using Ant Colony Optimization.

    Science.gov (United States)

    Satya, Eswari Jujjavarapu; Venkateswarlu, Chimmiri

    2013-09-01

    Fixed bed reactors with naturally attached biofilms are increasingly used for anaerobic treatment of industry wastewaters due their effective treatment performance. The complex nature of biological reactions in biofilm processes often poses difficulty in analyzing them experimentally, and mathematical models could be very useful for their design and analysis. However, effective application of biofilm reactor models to practical problems suffers due to the lack of knowledge of accurate kinetic models and uncertainty in model parameters. In this work, an inverse modeling approach based on ant colony optimization is proposed and applied to estimate the kinetic and film thickness model parameters of wastewater treatment process in an anaerobic fixed bed biofilm reactor. Experimental data of pharmaceutical industry wastewater treatment process are used to determine the model parameters as a consequence of the solution of the rigorous mathematical models of the process. Results were evaluated for different modeling configurations derived from the combination of mathematical models, kinetic expressions, and optimization algorithms. Analysis of results showed that the two-dimensional mathematical model with Haldane kinetics better represents the pharmaceutical wastewater treatment in the biofilm reactor. The mathematical and kinetic modeling of this work forms a useful basis for the design and optimization of industry wastewater treating biofilm reactors.

  4. MCNP5 study on kinetics parameters of coupled fast-thermal system HERBE

    Directory of Open Access Journals (Sweden)

    Pešić Milan P.

    2011-01-01

    Full Text Available New validation of the well-known Monte Carlo code MCNP5 against measured criticality and kinetics data for the coupled fast-thermal HERBE System at the Reactor B critical assembly is shown in this paper. Results of earlier calculations of these criticality and kinetics parameters, done by combination of transport and diffusion codes using two-dimension geometry model are compared to results of new calculations carried out by the MCNP5 code in three-dimension geometry. Satisfactory agreements in comparison of new results with experimental data, in spite complex heterogeneous composition of the HERBE core, are achieved confirming that MCNP5 code could apply successfully to study on HERBE kinetics parameters after uncertainties in impurities in material compositions and positions of fuel elements in fast zone were removed.

  5. Kinetic exchange opinion model: solution in the single parameter map limit

    CERN Document Server

    Chowdhury, Krishanu Roy; Biswas, Soumyajyoti; Chakrabarti, Bikas K

    2011-01-01

    We study a recently proposed kinetic exchange opinion model (Lallouache et. al., Phys. Rev E 82, 056112 (2010)) in the limit of a single parameter map. Although it does not include the essentially complex behavior of the multiagent version, it provides us with the insight regarding the choice of order parameter for the system as well as some of its other dynamical properties. We also study the generalized two-parameter version of the model, and provide the exact phase diagram. The universal behavior along this phase boundary in terms of the suitably defined order parameter is seen.

  6. Estimation of the overall kinetic parameters of enzyme inactivation using an isoconversional method

    OpenAIRE

    2008-01-01

    Estimation of the overall kinetic parameters of enzyme inactivation using an isoconversional method correspondance: Corresponding author. Tel./fax: +40 213275116, +40 722624585 (Mobile). (Raducan, Adina) (Raducan, Adina) Department of Physical Chemistry--> , Faculty of Chemistry--> , University of Bucharest--> , Bd. Elisabeta 4-12--> , 030018--> , Bucharest--> - RO...

  7. Estimating kinetic parameters of complex catalytic reactions using a curve resolution based method

    NARCIS (Netherlands)

    Cruz, S.C.; Rothenberg, G.; Westerhuis, J.A.; Smilde, A.K.

    2008-01-01

    A Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) based algorithm is used to extract kinetic parameters from on-line FT - NIR data of a series of Heck reactions between iodobenzene and n-butyl acrylate (NBA), measured at different temperatures with different catalysts. Four

  8. Dynamic identification of growth and survival kinetic parameters of microorganisms in foods

    Science.gov (United States)

    Inverse analysis is a mathematical method used in predictive microbiology to determine the kinetic parameters of microbial growth and survival in foods. The traditional approach in inverse analysis relies on isothermal experiments that are time-consuming and labor-intensive, and errors are accumula...

  9. Curcumin and kaempferol prevent lysozyme fibril formation by modulating aggregation kinetic parameters.

    Science.gov (United States)

    Borana, Mohanish S; Mishra, Pushpa; Pissurlenkar, Raghuvir R S; Hosur, Ramakrishna V; Ahmad, Basir

    2014-03-01

    Interaction of small molecule inhibitors with protein aggregates has been studied extensively, but how these inhibitors modulate aggregation kinetic parameters is little understood. In this work, we investigated the ability of two potential aggregation inhibiting drugs, curcumin and kaempferol, to control the kinetic parameters of aggregation reaction. Using thioflavin T fluorescence and static light scattering, the kinetic parameters such as amplitude, elongation rate constant and lag time of guanidine hydrochloride-induced aggregation reactions of hen egg white lysozyme were studied. We observed a contrasting effect of inhibitors on the kinetic parameters when aggregation reactions were measured by these two probes. The interactions of these inhibitors with hen egg white lysozyme were investigated using fluorescence quench titration method and molecular dynamics simulations coupled with binding free energy calculations. We conclude that both the inhibitors prolong nucleation of amyloid aggregation through binding to region of the protein which is known to form the core of the protein fibril, but once the nucleus is formed the rate of elongation is not affected by the inhibitors. This work would provide insight into the mechanism of aggregation inhibition by these potential drug molecules. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Accurate kinetic parameter estimation during progress curve analysis of systems with endogenous substrate production.

    Science.gov (United States)

    Goudar, Chetan T

    2011-10-01

    We have identified an error in the published integral form of the modified Michaelis-Menten equation that accounts for endogenous substrate production. The correct solution is presented and the error in both the substrate concentration, S, and the kinetic parameters Vm , Km , and R resulting from the incorrect solution was characterized. The incorrect integral form resulted in substrate concentration errors as high as 50% resulting in 7-50% error in kinetic parameter estimates. To better reflect experimental scenarios, noise containing substrate depletion data were analyzed by both the incorrect and correct integral equations. While both equations resulted in identical fits to substrate depletion data, the final estimates of Vm , Km , and R were different and Km and R estimates from the incorrect integral equation deviated substantially from the actual values. Another observation was that at R = 0, the incorrect integral equation reduced to the correct form of the Michaelis-Menten equation. We believe this combination of excellent fits to experimental data, albeit with incorrect kinetic parameter estimates, and the reduction to the Michaelis-Menten equation at R = 0 is primarily responsible for the incorrectness to go unnoticed. However, the resulting error in kinetic parameter estimates will lead to incorrect biological interpretation and we urge the use of the correct integral form presented in this study.

  11. A novel optimization approach to estimating kinetic parameters of the enzymatic hydrolysis of corn stover

    Directory of Open Access Journals (Sweden)

    Fenglei Qi

    2016-01-01

    Full Text Available Enzymatic hydrolysis is an integral step in the conversion of lignocellulosic biomass to ethanol. The conversion of cellulose to fermentable sugars in the presence of inhibitors is a complex kinetic problem. In this study, we describe a novel approach to estimating the kinetic parameters underlying this process. This study employs experimental data measuring substrate and enzyme loadings, sugar and acid inhibitions for the production of glucose. Multiple objectives to minimize the difference between model predictions and experimental observations are developed and optimized by adopting multi-objective particle swarm optimization method. Model reliability is assessed by exploring likelihood profile in each parameter space. Compared to previous studies, this approach improved the prediction of sugar yields by reducing the mean squared errors by 34% for glucose and 2.7% for cellobiose, suggesting improved agreement between model predictions and the experimental data. Furthermore, kinetic parameters such as K2IG2, K1IG, K2IG, K1IA, and K3IA are identified as contributors to the model non-identifiability and wide parameter confidence intervals. Model reliability analysis indicates possible ways to reduce model non-identifiability and tighten parameter confidence intervals. These results could help improve the design of lignocellulosic biorefineries by providing higher fidelity predictions of fermentable sugars under inhibitory conditions.

  12. Thermal kinetic and dielectric parameters of acenaphthene crystal grown by vertical Bridgman technique

    Science.gov (United States)

    Karuppusamy, S.; Dinesh Babu, K.; Nirmal Kumar, V.; Gopalakrishnan, R.

    2016-05-01

    The bulk acenaphthene crystal was grown in a single-wall ampoule by vertical Bridgman technique. X-ray diffraction analysis confirmed the orthorhombic crystal system of title compound with space group Pcm21. Thermal behavior of compound was studied using thermogravimetry—differential scanning calorimetry analysis. Thermal kinetic parameters like activation energy, frequency factor, Avrami exponent, reaction rate and degree of conversion were calculated using Kissingers and Ozawa methods under non-isothermal condition for acenaphthene crystal and reported for the first time. The calculated thermal kinetic parameters are presented. Dielectric studies were performed to calculate the dielectric parameters such as dielectric constant, dielectric loss, AC conductivity, and activation energy from Arrhenius plot.

  13. Inverse and direct modeling applied in the estimation of kinetic parameters of BSA adsorption

    Directory of Open Access Journals (Sweden)

    David Curbelo Rodríguez

    2010-11-01

    Full Text Available Normal 0 21 false false false MicrosoftInternetExplorer4 /* Style Definitions */ table.MsoNormalTable {mso-style-name:"Tabla normal"; mso-tstyle-rowband-size:0; mso-tstyle-colband-size:0; mso-style-noshow:yes; mso-style-parent:""; mso-padding-alt:0cm 5.4pt 0cm 5.4pt; mso-para-margin:0cm; mso-para-margin-bottom:.0001pt; mso-pagination:widow-orphan; font-size:10.0pt; font-family:"Times New Roman"; mso-ansi-language:#0400; mso-fareast-language:#0400; mso-bidi-language:#0400;} The kinetic modeling applied in the parameters estimation of chromatographic adsorption processes is an important tool in the understanding and improvement of these separation systems. In this work, two kinetic models were utilized in the parameters estimation of BSA adsorption. The correlations between the irreversible kinetic model and the reversible kinetic model with the experimental data were carried out using the Linear Driving Force and the Random Restricted Window (R2W method, respectively. From both models was possible to achieve a good fit with the experimental data, obtaining parameters with higher accuracy due to the low residues of the cost function.

  14. Kinetics of 12-Hydroxyoctadecanoic Acid SAFiN Crystallization Rationalized Using Hansen Solubility Parameters.

    Science.gov (United States)

    Rogers, Michael A; Marangoni, Alejandro G

    2016-12-06

    Changes in solvent chemistry influenced kinetics of both nucleation and crystallization of 12-hydroxyoctadecenoic, as determined using differential scanning calorimetry and applying a modified Avrami model to the calorimetric data. Altering solvent properties influenced solvent-gelator compatibility, which in turn altered the chemical potential of the system at the onset of crystallization, the kinetics of gelation, and the resulting 12HOA crystal fiber length. The chemical potential at the onset of crystallization was linearly correlated to both the hydrogen-bonding Hansen solubility parameter and the solvent-gelator vectorial distance in Hansen space, Ra. Our work suggests that solvent properties can be modulated to affect the solubility of 12HOA, which in turn influences the kinetics of crystallization and the self-assembly of this organogelator into supramolecular crystalline structures. Therefore, modulation of solvent properties during organogelation can be used to control fiber length and thus engineer the physical properties of the gel.

  15. Parameter estimation for whole-body kinetic model of FDG metabolism

    Institute of Scientific and Technical Information of China (English)

    CUI Yunfeng; BAI Jing; CHEN Yingmao; TIAN Jiahe

    2006-01-01

    Based on the radioactive tracer [18F]2-fluoro-2-deoxy-D-glucose (FDG), positron emission tomography (PET), and compartment model, the tracer kinetic study has become an important method to investigate the glucose metabolic kinetics in human body.In this work, the kinetic parameters of three-compartment and four-parameter model for the FDG metabolism in the tissues of myocardium, lung, liver, stomach, spleen, pancreas, and marrow were estimated through some dynamic FDG-PET experiments. Together with published brain and skeletal muscle parameters, a relatively complete whole-body model was presented. In the liver model, the dual blood supply from the hepatic artery and the portal vein to the liver was considered for parameter estimation, and the more accurate results were obtained using the dual-input rather than the single arterial-input. The established whole-body model provides the functional information of FDG metabolism in human body. It can be used to further investigate the glucose metabolism, and also be used for the simulation and visualization of FDG metabolic process in human body.

  16. Absorption and desorption mass transfer rates in chemically enhanced reactive systems. Part II : Reverse kinetic rate parameters

    NARCIS (Netherlands)

    Hamborg, Espen S.; Versteeg, Geert F.

    2012-01-01

    The forward and reverse kinetic rate parameters have been determined for CO2 absorption and desorption mass transfer processes in aqueous 2.0 M MDEA solutions at temperatures of 298.15, 313.15, and 333.15 K and the loading of CO2 ranging from 0 to 0.8. The derived kinetic rate parameters have been b

  17. An investigation on the catalytic capacity of dolomite in transesterification and the calculation of kinetic parameters.

    Science.gov (United States)

    Niu, Sheng-Li; Huo, Meng-Jia; Lu, Chun-Mei; Liu, Meng-Qi; Li, Hui

    2014-04-01

    The catalytic capacity of dolomite in transesterification was investigated and the kinetic parameters were calculated. The activated dolomites as transesterification catalyst were characterized by X-ray diffraction, nitrogen adsorption and desorption and Hammett indicator method, where the original dolomite was analyzed by thermogravimetric and X-ray fluorescence in advance. Its potential catalytic capacity was validated from aspects of the activated temperature and the reused property, where the reliability of the experimental system was also examined. Then, influences of the catalyst added amount, the mole ratio of methanol to oil, the transesterification temperature and the transesterification time on the catalytic capacity were investigated. Finally, kinetic parameters of the transesterification catalyzed by the activated dolomite were calculated.

  18. Investigation of the effect of organic solvents on kinetic parameters in metal catalyzed reactions

    Directory of Open Access Journals (Sweden)

    GORDANA A. MILOVANOVIC

    2000-03-01

    Full Text Available The effects of acetone and acetonitrile on the kinetic parameters of azorubin S oxidation by hydrogen peroxide catalyzed by manganese(II, pyrocatechol violet oxidation by hydrogen peroxide catalyzed by copper(II, and carminic acid oxidation by hydrogen peroxide catalyzed by copper(II and activated by bifenox, were examined. It was established that the examined solvents exhibit various effects on the kinetic parameters of the above said reactions. In a11 instances a change in the solvent concentration effects both the anthalpy and the entropy contributions to the free activation energy during the transition of the system into the active state, as well as the constant of the active complex formed at this point.

  19. Optimization of Process Parameters and Kinetic Model of Enzymatic Extraction of Polyphenols from Lonicerae Flos

    OpenAIRE

    Kong,Fansheng; Yu, Shujuan; Bi, Yongguang; Huang, Xiaojun; Huang, Mengqian

    2016-01-01

    Objective: To optimize and verify the cellulase extraction of polyphenols from honeysuckle and provide a reference for enzymatic extracting polyphenols from honeysuckle. Materials and Methods: The uniform design was used According to Fick's first law and kinetic model, fitting analysis of the dynamic process of enzymatic extracting polyphenols was conducted. Results: The optimum enzymatic extraction parameters for polyphenols from honeysuckle are found to be 80% (v/v) of alcohol, 35:1 (mL/g) ...

  20. Classical nucleation theory of immersion freezing: sensitivity of contact angle schemes to thermodynamic and kinetic parameters

    Science.gov (United States)

    Ickes, Luisa; Welti, André; Lohmann, Ulrike

    2017-02-01

    Heterogeneous ice formation by immersion freezing in mixed-phase clouds can be parameterized in general circulation models (GCMs) by classical nucleation theory (CNT). CNT parameterization schemes describe immersion freezing as a stochastic process, including the properties of insoluble aerosol particles in the droplets. There are different ways to parameterize the properties of aerosol particles (i.e., contact angle schemes), which are compiled and tested in this paper. The goal of this study is to find a parameterization scheme for GCMs to describe immersion freezing with the ability to shift and adjust the slope of the freezing curve compared to homogeneous freezing to match experimental data. We showed in a previous publication that the resulting freezing curves from CNT are very sensitive to unconstrained kinetic and thermodynamic parameters in the case of homogeneous freezing. Here we investigate how sensitive the outcome of a parameter estimation for contact angle schemes from experimental data is to unconstrained kinetic and thermodynamic parameters. We demonstrate that the parameters describing the contact angle schemes can mask the uncertainty in thermodynamic and kinetic parameters. Different CNT formulations are fitted to an extensive immersion freezing dataset consisting of size-selected measurements as a function of temperature and time for different mineral dust types, namely kaolinite, illite, montmorillonite, microcline (K-feldspar), and Arizona test dust. We investigated how accurate different CNT formulations (with estimated fit parameters for different contact angle schemes) reproduce the measured freezing data, especially the time and particle size dependence of the freezing process. The results are compared to a simplified deterministic freezing scheme. In this context, we evaluated which CNT-based parameterization scheme able to represent particle properties is the best choice to describe immersion freezing in a GCM.

  1. Reliability of spatiotemporal and kinetic gait parameters determined by a new instrumented treadmill system.

    Science.gov (United States)

    Reed, Lloyd F; Urry, Stephen R; Wearing, Scott C

    2013-08-21

    Despite the emerging use of treadmills integrated with pressure platforms as outcome tools in both clinical and research settings, published evidence regarding the measurement properties of these new systems is limited. This study evaluated the within- and between-day repeatability of spatial, temporal and vertical ground reaction force parameters measured by a treadmill system instrumented with a capacitance-based pressure platform. Thirty three healthy adults (mean age, 21.5 ± 2.8 years; height, 168.4 ± 9.9 cm; and mass, 67.8 ± 18.6 kg), walked barefoot on a treadmill system (FDM-THM-S, Zebris Medical GmbH) on three separate occasions. For each testing session, participants set their preferred pace but were blinded to treadmill speed. Spatial (foot rotation, step width, stride and step length), temporal (stride and step times, duration of stance, swing and single and double support) and peak vertical ground reaction force variables were collected over a 30-second capture period, equating to an average of 52 ± 5 steps of steady-state walking. Testing was repeated one week following the initial trial and again, for a third time, 20 minutes later. Repeated measures ANOVAs within a generalized linear modelling framework were used to assess between-session differences in gait parameters. Agreement between gait parameters measured within the same day (session 2 and 3) and between days (session 1 and 2; 1 and 3) were evaluated using the 95% repeatability coefficient. There were statistically significant differences in the majority (14/16) of temporal, spatial and kinetic gait parameters over the three test sessions (P < .01). The minimum change that could be detected with 95% confidence ranged between 3% and 17% for temporal parameters, 14% and 33% for spatial parameters, and 4% and 20% for kinetic parameters between days. Within-day repeatability was similar to that observed between days. Temporal and kinetic gait parameters were typically more

  2. Mechanistic analysis of multi-omics datasets to generate kinetic parameters for constraint-based metabolic models

    Directory of Open Access Journals (Sweden)

    Cotten Cameron

    2013-01-01

    Full Text Available Abstract Background Constraint-based modeling uses mass balances, flux capacity, and reaction directionality constraints to predict fluxes through metabolism. Although transcriptional regulation and thermodynamic constraints have been integrated into constraint-based modeling, kinetic rate laws have not been extensively used. Results In this study, an in vivo kinetic parameter estimation problem was formulated and solved using multi-omic data sets for Escherichia coli. To narrow the confidence intervals for kinetic parameters, a series of kinetic model simplifications were made, resulting in fewer kinetic parameters than the full kinetic model. These new parameter values are able to account for flux and concentration data from 20 different experimental conditions used in our training dataset. Concentration estimates from the simplified kinetic model were within one standard deviation for 92.7% of the 790 experimental measurements in the training set. Gibbs free energy changes of reaction were calculated to identify reactions that were often operating close to or far from equilibrium. In addition, enzymes whose activities were positively or negatively influenced by metabolite concentrations were also identified. The kinetic model was then used to calculate the maximum and minimum possible flux values for individual reactions from independent metabolite and enzyme concentration data that were not used to estimate parameter values. Incorporating these kinetically-derived flux limits into the constraint-based metabolic model improved predictions for uptake and secretion rates and intracellular fluxes in constraint-based models of central metabolism. Conclusions This study has produced a method for in vivo kinetic parameter estimation and identified strategies and outcomes of kinetic model simplification. We also have illustrated how kinetic constraints can be used to improve constraint-based model predictions for intracellular fluxes and biomass

  3. Mechanistic analysis of multi-omics datasets to generate kinetic parameters for constraint-based metabolic models.

    Science.gov (United States)

    Cotten, Cameron; Reed, Jennifer L

    2013-01-30

    Constraint-based modeling uses mass balances, flux capacity, and reaction directionality constraints to predict fluxes through metabolism. Although transcriptional regulation and thermodynamic constraints have been integrated into constraint-based modeling, kinetic rate laws have not been extensively used. In this study, an in vivo kinetic parameter estimation problem was formulated and solved using multi-omic data sets for Escherichia coli. To narrow the confidence intervals for kinetic parameters, a series of kinetic model simplifications were made, resulting in fewer kinetic parameters than the full kinetic model. These new parameter values are able to account for flux and concentration data from 20 different experimental conditions used in our training dataset. Concentration estimates from the simplified kinetic model were within one standard deviation for 92.7% of the 790 experimental measurements in the training set. Gibbs free energy changes of reaction were calculated to identify reactions that were often operating close to or far from equilibrium. In addition, enzymes whose activities were positively or negatively influenced by metabolite concentrations were also identified. The kinetic model was then used to calculate the maximum and minimum possible flux values for individual reactions from independent metabolite and enzyme concentration data that were not used to estimate parameter values. Incorporating these kinetically-derived flux limits into the constraint-based metabolic model improved predictions for uptake and secretion rates and intracellular fluxes in constraint-based models of central metabolism. This study has produced a method for in vivo kinetic parameter estimation and identified strategies and outcomes of kinetic model simplification. We also have illustrated how kinetic constraints can be used to improve constraint-based model predictions for intracellular fluxes and biomass yield and identify potential metabolic limitations through the

  4. A methodology for modeling photocatalytic reactors for indoor pollution control using previously estimated kinetic parameters

    Energy Technology Data Exchange (ETDEWEB)

    Passalia, Claudio; Alfano, Orlando M. [INTEC - Instituto de Desarrollo Tecnologico para la Industria Quimica, CONICET - UNL, Gueemes 3450, 3000 Santa Fe (Argentina); FICH - Departamento de Medio Ambiente, Facultad de Ingenieria y Ciencias Hidricas, Universidad Nacional del Litoral, Ciudad Universitaria, 3000 Santa Fe (Argentina); Brandi, Rodolfo J., E-mail: rbrandi@santafe-conicet.gov.ar [INTEC - Instituto de Desarrollo Tecnologico para la Industria Quimica, CONICET - UNL, Gueemes 3450, 3000 Santa Fe (Argentina); FICH - Departamento de Medio Ambiente, Facultad de Ingenieria y Ciencias Hidricas, Universidad Nacional del Litoral, Ciudad Universitaria, 3000 Santa Fe (Argentina)

    2012-04-15

    Highlights: Black-Right-Pointing-Pointer Indoor pollution control via photocatalytic reactors. Black-Right-Pointing-Pointer Scaling-up methodology based on previously determined mechanistic kinetics. Black-Right-Pointing-Pointer Radiation interchange model between catalytic walls using configuration factors. Black-Right-Pointing-Pointer Modeling and experimental validation of a complex geometry photocatalytic reactor. - Abstract: A methodology for modeling photocatalytic reactors for their application in indoor air pollution control is carried out. The methodology implies, firstly, the determination of intrinsic reaction kinetics for the removal of formaldehyde. This is achieved by means of a simple geometry, continuous reactor operating under kinetic control regime and steady state. The kinetic parameters were estimated from experimental data by means of a nonlinear optimization algorithm. The second step was the application of the obtained kinetic parameters to a very different photoreactor configuration. In this case, the reactor is a corrugated wall type using nanosize TiO{sub 2} as catalyst irradiated by UV lamps that provided a spatially uniform radiation field. The radiative transfer within the reactor was modeled through a superficial emission model for the lamps, the ray tracing method and the computation of view factors. The velocity and concentration fields were evaluated by means of a commercial CFD tool (Fluent 12) where the radiation model was introduced externally. The results of the model were compared experimentally in a corrugated wall, bench scale reactor constructed in the laboratory. The overall pollutant conversion showed good agreement between model predictions and experiments, with a root mean square error less than 4%.

  5. An Evaluation of Kinetic Parameters of Cadmium and Copper Biosorption by Immobilized Cells

    Directory of Open Access Journals (Sweden)

    Nelly Georgieva

    2007-10-01

    Full Text Available Bioremediation is the use of living organisms to reduce or eliminate environmental hazards resulting from the accumulation of toxic chemicals and other hazardous wastes. This technology is based on the utilization of microorganisms to transform organic and inorganic compounds. The filamentous yeast Trichosporon cutaneum strain R57, immobilized and free cells was cultivated as batch culture on a liquid medium in the presence of various concentrations of cadmium and copper ions. The simultaneous uptake and accumulation of Cd2+ and Cu2+ ions by Tr. cutaneum cells depending on the initial concentration of Cd2+ and Cu2+ in the medium were studied. The potential use of the free and immobilized cells of Trichosporon cutaneum to remove cadmium and copper ions, from aqueous solutions was evaluated. Two important physicochemical aspects for the evaluation of the sorption process as a unit operation are the equilibrium of sorption and the kinetics. The Cd2+ and Cu2+ ions biosorption capacities of all tested adsorbent were presented as a function of the initial concentration of metal ions within the aqueous biosorption medium. The individual, as well as bicomponent sorption kinetics of copper and cadmium ions by immobilised cells of Trichosporon cutaneum R57 is presented. A second order kinetic model obtains kinetic parameters for the copper and cadmium ions.

  6. Comparison of Parameter Estimation Methods in Stochastic Chemical Kinetic Models: Examples in Systems Biology.

    Science.gov (United States)

    Gupta, Ankur; Rawlings, James B

    2014-04-01

    Stochastic chemical kinetics has become a staple for mechanistically modeling various phenomena in systems biology. These models, even more so than their deterministic counterparts, pose a challenging problem in the estimation of kinetic parameters from experimental data. As a result of the inherent randomness involved in stochastic chemical kinetic models, the estimation methods tend to be statistical in nature. Three classes of estimation methods are implemented and compared in this paper. The first is the exact method, which uses the continuous-time Markov chain representation of stochastic chemical kinetics and is tractable only for a very restricted class of problems. The next class of methods is based on Markov chain Monte Carlo (MCMC) techniques. The third method, termed conditional density importance sampling (CDIS), is a new method introduced in this paper. The use of these methods is demonstrated on two examples taken from systems biology, one of which is a new model of single-cell viral infection. The applicability, strengths and weaknesses of the three classes of estimation methods are discussed. Using simulated data for the two examples, some guidelines are provided on experimental design to obtain more information from a limited number of measurements.

  7. Determination of kinetic parameters for 123-I thyroid uptake in healthy Japanese

    Science.gov (United States)

    Kusuhara, Hiroyuki; Maeda, Kazuya

    2017-09-01

    The purpose of this study was to compare the kinetic parameters for iodide thyroid accumulation in Japanese today with previously reported values. We determined the thyroid uptake of 123-I at 24 hours after the oral administration in healthy male Japanese without any diet restriction. The mean value was 16.1±5.4%, which was similar or rather lower than those previously reported in Japan (1958-1972). Kinetic model analysis was conducted to obtain the clearance for thyroid uptake from the blood circulation. The thyroid uptake clearance of 123-I was 0.540±0.073 ml/min, which was almost similar to those reported previously. There is no obvious difference in the thyroid uptake for 24 hours, and kinetic parameters in healthy Japanese for these 50 years. The fraction of distributed to the thyroid gland is lower than the ICRP reference man, and such difference must be taken into consideration to estimate the radiation exposure upon Fukushima accident in Japan.

  8. Estimating kinetic parameters in TGA using B-spline smoothing and the Friedman method

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xiaojie; Preto, Fernando [CANMET Energy Technology Centre (CETC), Natural Resources (Canada); de Jong, Wiebren [Faculty 3mE, Department of Process and Energy, ET Section, Delft University of Technology, Leeghwaterstraat 44, 2628 CD Delft (Netherlands)

    2009-10-15

    The pyrolysis of biomass occurs via several parallel/serial decomposition reactions. The kinetic parameters, namely the activation energy (E) and the pre-exponential factor (k{sub o}), do not remain constant during the pyrolysis process. A modified empirical method is introduced for calculating the activation energy (E) and the pre-exponential factor (k{sub 0}) based on the Friedman analysis [Friedman HL. Kinetics of thermal degradation of char-forming plastics from thermogravimetry - application to a phenolic plastic. [J Polym Sci C 1963;6: 183-95]. The kinetic parameters are expressed as a function of the conversion (x) during the biomass pyrolysis process. The reactions are assumed to be of first order. At least three data sets obtained at different dynamic heating rates are required. From the Friedman analysis, the conversion (x) related functions E = E(x) and k{sub o} = k{sub o}(x) can be obtained by a B-spline regression method. The pyrolysis can hence be described as: dx/ dt=k(1-x)=k{sub o}(x). exp (-E(x)/RT)(1-x). In this paper, the adapted method is applied to pyrolysis of cellulose and two biomass fuels (meat and bone meal, chicken litter). Experiments were carried out at 2, 10 and 50 K min{sup -1} by thermogravimetric analysis. A good fit of the calculated conversion with experimental data was found. (author)

  9. Parameter inference for discretely observed stochastic kinetic models using stochastic gradient descent

    Directory of Open Access Journals (Sweden)

    Christley Scott

    2010-07-01

    Full Text Available Abstract Background Stochastic effects can be important for the behavior of processes involving small population numbers, so the study of stochastic models has become an important topic in the burgeoning field of computational systems biology. However analysis techniques for stochastic models have tended to lag behind their deterministic cousins due to the heavier computational demands of the statistical approaches for fitting the models to experimental data. There is a continuing need for more effective and efficient algorithms. In this article we focus on the parameter inference problem for stochastic kinetic models of biochemical reactions given discrete time-course observations of either some or all of the molecular species. Results We propose an algorithm for inference of kinetic rate parameters based upon maximum likelihood using stochastic gradient descent (SGD. We derive a general formula for the gradient of the likelihood function given discrete time-course observations. The formula applies to any explicit functional form of the kinetic rate laws such as mass-action, Michaelis-Menten, etc. Our algorithm estimates the gradient of the likelihood function by reversible jump Markov chain Monte Carlo sampling (RJMCMC, and then gradient descent method is employed to obtain the maximum likelihood estimation of parameter values. Furthermore, we utilize flux balance analysis and show how to automatically construct reversible jump samplers for arbitrary biochemical reaction models. We provide RJMCMC sampling algorithms for both fully observed and partially observed time-course observation data. Our methods are illustrated with two examples: a birth-death model and an auto-regulatory gene network. We find good agreement of the inferred parameters with the actual parameters in both models. Conclusions The SGD method proposed in the paper presents a general framework of inferring parameters for stochastic kinetic models. The method is

  10. Inferring Mechanistic Parameters from Amyloid Formation Kinetics by Approximate Bayesian Computation.

    Science.gov (United States)

    Nakatani-Webster, Eri; Nath, Abhinav

    2017-03-14

    Amyloid formation is implicated in a number of human diseases, and is thought to proceed via a nucleation-dependent polymerization mechanism. Experimenters often wish to relate changes in amyloid formation kinetics, for example, in response to small molecules to specific mechanistic steps along this pathway. However, fitting kinetic fibril formation data to a complex model including explicit rate constants results in an ill-posed problem with a vast number of potential solutions. The levels of uncertainty remaining in parameters calculated from these models, arising both from experimental noise and high levels of degeneracy or codependency in parameters, is often unclear. Here, we demonstrate that a combination of explicit mathematical models with an approximate Bayesian computation approach can be used to assign the mechanistic effects of modulators on amyloid fibril formation. We show that even when exact rate constants cannot be extracted, parameters derived from these rate constants can be recovered and used to assign mechanistic effects and their relative magnitudes with a great deal of confidence. Furthermore, approximate Bayesian computation provides a robust method for visualizing uncertainty remaining in the model parameters, regardless of its origin. We apply these methods to the problem of heparin-mediated tau polymerization, which displays complex kinetic behavior not amenable to analysis by more traditional methods. Our analysis indicates that the role of heparin cannot be explained by enhancement of nucleation alone, as has been previously proposed. The methods described here are applicable to a wide range of systems, as models can be easily adapted to account for new reactions and reversibility.

  11. Accounting for the kinetics in order parameter analysis: lessons from theoretical models and a disordered peptide

    CERN Document Server

    Berezovska, Ganna; Mostarda, Stefano; Rao, Francesco

    2012-01-01

    Molecular simulations as well as single molecule experiments have been widely analyzed in terms order parameters, the latter representing candidate probes for the relevant degrees of freedom. Notwithstanding this approach is very intuitive, mounting evidence showed that such description is not accurate, leading to ambiguous definitions of states and wrong kinetics. To overcome these limitations a framework making use of order parameter fluctuations in conjunction with complex network analysis is investigated. Derived from recent advances in the analysis of single molecule time traces, this approach takes into account of the fluctuations around each time point to distinguish between states that have similar values of the order parameter but different dynamics. Snapshots with similar fluctuations are used as nodes of a transition network, the clusterization of which into states provides accurate Markov-State-Models of the system under study. Application of the methodology to theoretical models with a noisy orde...

  12. Castor oil transesterification reaction: A kinetic study and optimization of parameters

    Energy Technology Data Exchange (ETDEWEB)

    Ramezani, K. [Fuel Cell Research Laboratory, Green Research Center, Iran University of Science and Technology, Tehran (Iran); Rowshanzamir, S. [Fuel Cell Research Laboratory, Green Research Center, Iran University of Science and Technology, Tehran (Iran); School of Chemical Engineering, Iran University of Science and Technology, Tehran (Iran); Eikani, M.H. [Department of Chemical Industries, Iranian Research Organization for Science and Technology (IROST), Tehran (Iran)

    2010-10-15

    In this paper, parameters affecting castor oil transesterification reaction were investigated. Applying four basic catalysts including NaOCH{sub 3}, NaOH, KOCH{sub 3} and KOH the best one with maximum biodiesel yield was identified. Using Taguchi method consisting four parameters and three levels, the best experimental conditions were determined. Reaction temperature (25, 65 and 80 C), mixing intensity (250, 400 and 600 rpm), alcohol/oil ratio (4:1, 6:1 and 8:1) and catalyst concentration (0.25, 0.35 and 0.5%) were selected as experimental parameters. It was concluded that reaction temperature and mixing intensity can be optimized. Using the optimum results, we proposed a kinetic model which resulted in establishing an equation for the beginning rate of transesterification reaction. Furthermore, applying ASTM D 976 correlation, minimum cetane number of produced biodiesel was determined as 37.1. (author)

  13. Identification of the crystallization kinetic parameters of a semi-crystalline polymer by using PVTα measurement

    Science.gov (United States)

    Tardif, X.; Sobotka, V.; Boyard, N.; Delaunay, D.

    2011-05-01

    Injection molding is the most widely used process in the plastic industry. In the case of semi-crystalline polymer, crystallization kinetics impacts directly the quality of the piece, both on dimensional and mechanical aspects. The characterization of these kinetics is therefore of primary importance to model the process, in particular during the cooling phase. To be representative, this characterization must be carried out under conditions as close as possible to those encountered in the process: high pressure, high cooling rate, shearing, and potential presence of fibers. However, conventional apparatus such as the differential scanning calorimeter do not allow to reach these conditions. A PVTα apparatus, initially developed in the laboratory for the characterization of thermoset composites, was adapted to identify the crystallization kinetics. The aim of the presented study is to demonstrate the feasibility of the identification. This device allows the molding of a circular sample of 40 mm diameter and 6 mm thick by controlling the applied pressure on the sample and the temperature field on its surfaces. This mold is designed such as heat transfer is 1D within the thickness of the sample. It is equipped with two heat flux sensors to determine the average crystallization rate through the thickness and a displacement sensor for the determination of the volume change. The heat transfer problem between the polymer and the molding cavity is modeled by using a 1D conduction problem with a moving boundary, in which the control volume is a uniform temperature disk with a variable volume, and coupled to a crystallization kinetic model. An inverse method is used to identify the parameters of the crystallization kinetic model by minimizing an objective function based on the difference between the evolutions of the experimental and computed volume of the sample. The first validation of this methodology was to compare the kinetic parameters identified with this apparatus

  14. Establishment and application of a new method for the determination of kinetic parameters by plug-plug kinetic capillary electrophoresis (ppKCE)

    Institute of Scientific and Technical Information of China (English)

    XIONG CaiQiao; XIA ZhiNing; HUANG Rui; CHEN Hua; XU Pan

    2008-01-01

    A novel plug-plug kinetic capillary electrophoresis method was established, which can be used to si-multaneously determine the kinetic parameters kon and koff in interaction systems. The method is comparatively simple and some restrictions in conventional ppKCE methods can be effectively avoided, The requirements for resolution and detection sensitivity in this method are much lower than those of conventional ppKCE, The successful determination of the kinetic parameters and the binding constant Kb between citalopram and BSA showed availability of this method, The results were confirmed by us-ing the time ratio method. The application field of kinetic capillary electrophoresis can be expanded with this new method,

  15. Establishment and application of a new method for the determination of kinetic parameters by plug-plug kinetic capillary electrophoresis (ppKCE)

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A novel plug-plug kinetic capillary electrophoresis method was established, which can be used to si-multaneously determine the kinetic parameters kon and koff in interaction systems. The method is comparatively simple and some restrictions in conventional ppKCE methods can be effectively avoided. The requirements for resolution and detection sensitivity in this method are much lower than those of conventional ppKCE. The successful determination of the kinetic parameters and the binding constant Kb between citalopram and BSA showed availability of this method. The results were confirmed by us-ing the time ratio method. The application field of kinetic capillary electrophoresis can be expanded with this new method.

  16. Calculating kinetics parameters and reactivity changes with continuous-energy Monte Carlo

    Energy Technology Data Exchange (ETDEWEB)

    Kiedrowski, Brian C [Los Alamos National Laboratory; Brown, Forrest B [Los Alamos National Laboratory; Wilson, Paul [UNIV. WISCONSIN

    2009-01-01

    The iterated fission probability interpretation of the adjoint flux forms the basis for a method to perform adjoint weighting of tally scores in continuous-energy Monte Carlo k-eigenvalue calculations. Applying this approach, adjoint-weighted tallies are developed for two applications: calculating point reactor kinetics parameters and estimating changes in reactivity from perturbations. Calculations are performed in the widely-used production code, MCNP, and the results of both applications are compared with discrete ordinates calculations, experimental measurements, and other Monte Carlo calculations.

  17. Gas phase NMR spectra of N,N-dimethylnitrosamine. Environmental effects on kinetic parameters

    Science.gov (United States)

    Chauvel, J. Paul; Leung, Doris Y.; True, Nancy S.

    1984-04-01

    Gas phase 1H NMR spectra of N,N-dimethylnitrosamine are consistent with first order chemical exchange rate constants which are ca. 25 times faster than those observed in neat liquids at corresponding temperatures. The associated kinetic parameters: Eact(∞), 20.5(1.1) kcal mol -1, Δ H‡, 19.7(1.0) kcal mol -1 and Δ G‡, 21.1(0.4) kcal mol -1 are approximately 2.5 kcal mol -1 lower than the most recently reported values for the neat liquid. The observed phase dependence is consistent with a process proceeding via a freely rotating transition state.

  18. The strong prognostic value of KELIM, a model-based parameter from CA 125 kinetics in ovarian cancer

    DEFF Research Database (Denmark)

    You, Benoit; Colomban, Olivier; Heywood, Mark;

    2013-01-01

    Unexpected results were recently reported about the poor surrogacy of Gynecologic Cancer Intergroup (GCIG) defined CA-125 response in recurrent ovarian cancer (ROC) patients. Mathematical modeling may help describe CA-125 decline dynamically and discriminate prognostic kinetic parameters....

  19. Sensitivity analysis in oxidation ditch modelling: the effect of variations in stoichiometric, kinetic and operating parameters on the performance indices

    NARCIS (Netherlands)

    Abusam, A.A.A.; Keesman, K.J.; Straten, van G.; Spanjers, H.; Meinema, K.

    2001-01-01

    This paper demonstrates the application of the factorial sensitivity analysis methodology in studying the influence of variations in stoichiometric, kinetic and operating parameters on the performance indices of an oxidation ditch simulation model (benchmark). Factorial sensitivity analysis investig

  20. Classical nucleation theory of homogeneous freezing of water: thermodynamic and kinetic parameters.

    Science.gov (United States)

    Ickes, Luisa; Welti, André; Hoose, Corinna; Lohmann, Ulrike

    2015-02-28

    The probability of homogeneous ice nucleation under a set of ambient conditions can be described by nucleation rates using the theoretical framework of Classical Nucleation Theory (CNT). This framework consists of kinetic and thermodynamic parameters, of which three are not well-defined (namely the interfacial tension between ice and water, the activation energy and the prefactor), so that any CNT-based parameterization of homogeneous ice formation is less well-constrained than desired for modeling applications. Different approaches to estimate the thermodynamic and kinetic parameters of CNT are reviewed in this paper and the sensitivity of the calculated nucleation rate to the choice of parameters is investigated. We show that nucleation rates are very sensitive to this choice. The sensitivity is governed by one parameter - the interfacial tension between ice and water, which determines the energetic barrier of the nucleation process. The calculated nucleation rate can differ by more than 25 orders of magnitude depending on the choice of parameterization for this parameter. The second most important parameter is the activation energy of the nucleation process. It can lead to a variation of 16 orders of magnitude. By estimating the nucleation rate from a collection of droplet freezing experiments from the literature, the dependence of these two parameters on temperature is narrowed down. It can be seen that the temperature behavior of these two parameters assumed in the literature does not match with the predicted nucleation rates from the fit in most cases. Moreover a comparison of all possible combinations of theoretical parameterizations of the dominant two free parameters shows that one combination fits the fitted nucleation rates best, which is a description of the interfacial tension coming from a molecular model [Reinhardt and Doye, J. Chem. Phys., 2013, 139, 096102] in combination with the activation energy derived from self-diffusion measurements [Zobrist

  1. Prediction of pyrolysis kinetic parameters from biomass constituents based on simplex-lattice mixture design☆

    Institute of Scientific and Technical Information of China (English)

    Panusit Sungsuk; Sasiporn Chayaporn; Sasithorn Sunphorka; Prapan Kuchonthara; Pornpote Piumsomboon; Benjapon Chalermsinsuwan

    2016-01-01

    The aim of this study is to determine the effect of the main chemical components of biomass:cel ulose, hemicel-lulose and lignin, on chemical kinetics of biomass pyrolysis. The experiments were designed based on a simplex-lattice mixture design. The pyrolysis was observed by using a thermogravimetric analyzer. The curves obtained from the employed analytical method fit the experimental data (R2 N 0.9). This indicated that this method has the potential to determine the kinetic parameters such as the activation energy (Ea), frequency factor (A) and re-action order (n) for each point of the experimental design. The results obtained from the simplex-lattice mixture design indicated that cellulose had a significant effect on Ea and A, and the interaction between cellulose and lignin had an important effect on the reaction order, n. The proposed models were then proved to be useful for predicting pyrolysis behavior in real biomass and so could be used as a simple approximation for predicting the overall trend of chemical reaction kinetics.

  2. Effect of diet-induced obesity on kinetic parameters of amino acid uptake by rat erythrocytes.

    Science.gov (United States)

    Picó, C; Pons, A; Palou, A

    1992-11-01

    The effects of cafeteria diet-induced obesity upon in vitro uptake of L-Alanine, Glycine, L-Lysine, L-Glutamine, L-Glutamic acid, L-Phenylalanine and L-Leucine by isolated rat erythrocytes have been studied. The total Phe and Leu uptakes followed Michaelis-Menten kinetics. The Glu uptake was fitted to diffusion kinetics. The uptakes of Ala, Gly, Lys and Gln were best explained by a two-component transport: one saturable and one diffusion. Obesity increased the Km value for Ala, Gln and Leu, and the Vmax value for Ala, but decreased the Vmax for Lys. Kinetic parameters of Phe uptake were unaffected by obesity. In addition, the pseudo-first order rate constant (Vmax/Km) for Ala, Gly, Gln, Lys and Leu uptake decreased as a result of cafeteria diet-induced obesity. The Kd value for Ala, Gly, Gln and Glu decreased and that of Lys increased as result of obesity. These adaptations could, at least in part, explain alterations in amino acid distribution between blood cells and plasma related to overfeeding or obesity.

  3. Determination of the kinetic parameters of Be O using isothermal decay method

    Energy Technology Data Exchange (ETDEWEB)

    Azorin N, J.; Torijano C, E. [Universidad Autonoma Metropolitana, Unidad Iztapalapa, Av. San Rafael Atlixco 186, Col. Vicentina, 09340 Mexico D. F. (Mexico); Azorin V, C.; Rivera M, T., E-mail: azorin@xanum.uam.mx [IPN, Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada, Av. Legaria 694, Col. Irrigacion, 11500 Mexico D. F. (Mexico)

    2015-10-15

    Full text: Most of the existing methods for obtaining the frequency factors make use of the trap depth (activation energy) making some assumptions about the order of the kinetics. This causes inconsistencies in the reported values of trapping parameters due that the values of the activation energy obtained by different methods differ appreciably among them. Then, it is necessary to use a method independent of the trap depth making use of the isothermal luminescence decay method. The trapping parameters associated with the prominent glow peak of Be O (280 degrees C) are reported using isothermal luminescence decay method. As a check, the trap parameters are also calculated by glow curve shape (Chen s) method after isolating the prominent glow peak by thermal cleaning technique. Our results show a very good agreement between the trapping parameters calculated by the two methods. Isothermal luminescence decay method was used for determining the trapping parameters of Be O. Results obtained applying this method are in good agreement with those obtained using other methods, except in the value of the frequency factor. (Author)

  4. Electron transport parameters in CO$_2$: scanning drift tube measurements and kinetic computations

    CERN Document Server

    Vass, M; Loffhagen, D; Pinhao, N; Donko, Z

    2016-01-01

    This work presents transport coefficients of electrons (bulk drift velocity, longitudinal diffusion coefficient, and effective ionization frequency) in CO2 measured under time-of-flight conditions over a wide range of the reduced electric field, 15Td <= E/N <= 2660Td in a scanning drift tube apparatus. The data obtained in the experiments are also applied to determine the effective steady-state Townsend ionization coefficient. These parameters are compared to the results of previous experimental studies, as well as to results of various kinetic computations: solutions of the electron Boltzmann equation under different approximations (multiterm and density gradient expansions) and Monte Carlo simulations. The experimental data extend the range of E/N compared with previous measurements and are consistent with most of the transport parameters obtained in these earlier studies. The computational results point out the range of applicability of the respective approaches to determine the different measured tr...

  5. Sensitivity of benzene natural attenuation to variations in kinetic and transport parameters in Liwa Aquifer, UAE.

    Science.gov (United States)

    Mohamed, Mohamed M; Saleh, Nawal E; Sherif, Mohsen M

    2010-04-01

    Dissolved benzene was detected in the shallow unconfined Liwa aquifer (UAE). This aquifer represents the main freshwater source for a nearby residence camp area. A finite element model is used to simulate the fate, transport, and attenuation of the dissolved benzene plume to help decision makers assess natural attenuation as a viable remediation option. Sensitivity of benzene attenuation to uncertainties in the estimation of some of the kinetic and transport parameters is studied. It was found that natural attenuation is more sensitive to microbial growth rate and half saturation coefficients of both benzene and oxygen than initial biomass concentration and dispersivity coefficients. Increasing microbial growth rate by fourfold increased natural attenuation effectiveness after 40 years by 10%; while decreasing it by fourfold decreased natural attenuation effectiveness by 77%. On the other hand, increasing half saturation coefficient by fourfold decreased natural attenuation effectiveness by 46% in 40 years. Decreasing the same parameter fourfold caused natural attenuation effectiveness to increase by 9%.

  6. Estimation of kinetics parameters in Beckmann rearrangement of cyclohexanone oxime using genetic algorithm

    Institute of Scientific and Technical Information of China (English)

    WU Jian; LI Zhong; LUO He-an

    2006-01-01

    Beckmann rearrangement mechanism of cyclohexanone oxime, based on the characteristic of self-catalyzed reaction and polymorphism was proposed. According to the suggested mechanism, the basic approach was the rearrangement of OXH+ while the SO3 acts as dehydrating agent and OXSO3 can turn to CPLSO3 ultimately. Considering self-catalyzed reaction between OXSO3 and CPLH+ , kinetic model for Beckmann rearrangement was established. Corresponding parameters were estimated by using float genetic algorithm (GA) and simulation results agree well with the experimental data below -19.3℃. Industrial equipment was simulated and analyzed. Effects of key process parameters such as molar ratio of sulfuric acid to oxime and circulation ratio on the residual oxime are also discussed. The results show that the caprolactam exists as CPLH+ finally in oleum and the minimum molecular ratio of sulfuric acid to oxime can be 0.5 theoretically.

  7. Ethanol Production from Whey by Kluyveromyces marxianus in Batch Fermentation System: Kinetics Parameters Estimation

    Directory of Open Access Journals (Sweden)

    Dessy Ariyanti

    2013-03-01

    Full Text Available Whey is the liquid remaining after milk has been curdled and strained. It is a by-product of the manufacture of cheese or casein and has several commercial uses. In environmental point of view, whey is kind of waste which has high pollution level due to it’s contain high organic compound with BOD and COD value 50 and 80 g/L respectively. On the other side, whey also contain an amount of lactose (4.5%-5%; lactose can be used as carbon source and raw material for producing ethanol via fermentation using yeast strain Kluyveromyces marxianus. The objective of this research is to investigate the ethanol production kinetics from crude whey through fermentation using Kluyveromyces marxianus and to predict the model kinetics parameter. The yeast was able to metabolize most of the lactose within 16 h to give 8.64 g/L ethanol, 4.43 g/L biomass, and remain the 3.122 g/L residual lactose. From the results presented it also can be concluded that common kinetic model for microbial growth, substrate consumption, and product formation is a good alternative to describe an experimental batch fermentation of Kluyveromyces marxianus grown on a medium composed of whey. The model was found to be capable of reflecting all batch culture phases to a certain degree of accuracy, giving the parameter value: μmax, Ks, YX/S, α, β : 0.32, 10.52, 0.095, 1.52, and 0.11 respectively. © 2013 BCREC UNDIP. All rights reserved(Selected Paper from International Conference on Chemical and Material Engineering (ICCME 2012Received: 27th September 2012; Revised: 29th November 2012; Accepted: 7th December 2012[How to Cite: D. Ariyanti, H. Hadiyanto, (2013. Ethanol Production from Whey by Kluyveromyces marxianus in Batch Fermentation System: Kinetics Parameters Estimation. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (3: 179-184. (doi:10.9767/bcrec.7.3.4044.179-184][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.7.3.4044.179-184 ] View in  |

  8. Development of a spontaneous heating liability index of coal from kinetic parameters

    Energy Technology Data Exchange (ETDEWEB)

    Panigrahi, D.C.; Mishra, N.M. [Indian School of Mines, Dhanbad (India); Sahu, H.B. [National Inst. of Technology, Rourkela (India)

    2008-06-15

    This paper presented a newly developed spontaneous heating liability index (SHLI) of coal using a kinetics of low temperature oxidation approach. The oxidation rate was seen as a function of the temperature-dependent rate constant and a reaction model. An Arrhenius equation was used to examine the effects of temperature on the constant rate. Energy transferred through the coal during the reaction process was predicted using a Frank-Kamenetski model for conductive heat flow. Parameters examined in the study included the enthalpy change; the specific heat of the coal; the rate constant; and the time required to reach a specific temperature. Thirty-one coal samples were used to test the validity of the model. Experiments were conducted to obtain kinetic parameters for the samples. The susceptibility of the samples to spontaneous combustion was ascertained using a standard crossing-point temperature measurement method. The moisture percentage of the samples was obtained using a proximate analysis. A comparison of the SHLI and the crossing point temperature method demonstrated that the SHLI predicted the susceptibility of the coal to spontaneous heating more accurately than the crossing point temperature method.

  9. Effect of Drop Foot on Spatiotemporal, Kinematic, and Kinetic Parameters during Gait

    Directory of Open Access Journals (Sweden)

    Ida Wiszomirska

    2017-01-01

    Full Text Available Background. The complexity of the structure and function of a living body can be affected by disorders and can cause various dysfunctions. Objective. The aim of this study was to determine compensatory mechanisms in subjects with drop foot during gait. Methods. The study evaluated 10 subjects with drop foot (DF whose results were compared to a group of 10 healthy controls (C. Spatiotemporal, kinematic, and kinetic parameters during the gait cycle were collected using Vicon system synchronized with Kistler platforms. Results. Spatiotemporal, kinematic, and kinetic parameters were significantly different between the analysed groups. In the DF group, the subjects walked almost 47% slower and performed 60% less steps per minute compared to the C group. The main problem in the DF group was insufficient ankle dorsiflexion in the 0–10% of the gait cycle. Mean values in the groups during the first 10% of the gait cycle were as follows: DF (−10.42 ± 5.7° and C (−2.37 ± 1.47°, which affected the substantial differences in the values of muscle torque: DF (0.2 ± 0.1 Nm/kg and C (−0.26 ± 0.06 Nm/kg. Conclusions. Comparative analysis for joint angles and torques demonstrated that the mechanism of compensation is the most noticeable in the knee joint and less in the hip joint.

  10. Determination of kinetic parameters for monitoring source driven subcritical transmutation devices

    Energy Technology Data Exchange (ETDEWEB)

    Becker, Maarten

    2014-03-15

    ADS are considered as an option for the irradiation facility in partitioning and transmutation concepts for highly radioactive waste from spent nuclear fuel. Due to the hard neutron energy spectrum and the subcriticality of the reactor ADS provide a good compromise between transmutation performance and safety aspects. For the safe operation, but also for the overall optimization of the facility, the determination of the subcriticality level is essential. To investigate experimental methods in Pulsed Neutron Source (PNS) experiments for the determination of the subcriticality level the ADS experiment YALINA-Thermal is thoroughly analyzed in this work. The experiment has been performed from 2005-2010 in Minsk, Belarus. Most of the related experimental methods rely on point kinetic equations. This approach introduces two main approximations. Firstly, the point kinetic equation cannot describe the transition of the neutron distribution from the source operation to the source shutdown. After shutdown, the neutron population would redistribute to establish the fundamental decay mode. This violates the point kinetic assumption of neutron flux spectra constant in time. Secondly, to calculate kinetic parameters like the neutron mean generation time and the effective delayed neutron fraction the neutron flux distribution of the effective multiplication factor equation is typically used, which is equivalent to an artificial critical steady-state reactor. However, it is the time-dependence of the decay of the neutron populations including their redistribution in space and energy, which affects the analyzed kinetic parameters. Consequently, this work aims for the accurate simulation of these phenomena with particular emphasis on the quality of the effective neutron cross sections. In this work new microscopic master libraries based on the JEFF 3.1, JEFF 3.1.1 and ENDF/B VII.0 evaluations are developed with a general purpose 350 energy groups structure for the deterministic

  11. Synergistic improvement of gas sensing performance by micro-gravimetrically extracted kinetic/thermodynamic parameters

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Shuanbao; Xu, Pengcheng; Yu, Haitao; Cheng, Zhenxing; Li, Xinxin, E-mail: xxli@mail.sim.ac.cn

    2015-03-10

    Highlights: • Sensing material can be comprehensively optimized by using gravimetric cantilever. • Kinetic-thermodynamic model parameters are quantitatively extracted by experiment • Sensing-material performance is synergistically optimized by extracted parameters. - Abstract: A novel method is explored for comprehensive design/optimization of organophosphorus sensing material, which is loaded on mass-type microcantilever sensor. Conventionally, by directly observing the gas sensing response, it is difficult to build quantitative relationship with the intrinsic structure of the material. To break through this difficulty, resonant cantilever is employed as gravimetric tool to implement molecule adsorption experiment. Based on the sensing data, key kinetic/thermodynamic parameters of the material to the molecule, including adsorption heat −ΔH°, adsorption/desorption rate constants K{sub a} and K{sub d}, active-site number per unit mass N′ and surface coverage θ, can be quantitatively extracted according to physical–chemistry theories. With gaseous DMMP (simulant of organophosphorus agents) as sensing target, the optimization route for three sensing materials is successfully demonstrated. Firstly, a hyper-branched polymer is evaluated. Though suffering low sensitivity due to insufficient N′, the bis(4-hydroxyphenyl)-hexafluoropropane (BHPF) sensing-group exhibits satisfactory reproducibility due to appropriate −ΔH°. To achieve more sensing-sites, KIT-5 mesoporous-silica with higher surface-area is assessed, resulting in good sensitivity but too high −ΔH° that brings poor repeatability. After comprehensive consideration, the confirmed BHPF sensing-group is grafted on the KIT-5 carrier to form an optimized DMMP sensing nanomaterial. Experimental results indicate that, featuring appropriate kinetic/thermodynamic parameters of −ΔH°, K{sub a}, K{sub d}, N′ and θ, the BHPF-functionalized KIT-5 mesoporous silica exhibits synergistic

  12. Kinetic modeling of molecular motors: pause model and parameter determination from single-molecule experiments

    Science.gov (United States)

    Morin, José A.; Ibarra, Borja; Cao, Francisco J.

    2016-05-01

    Single-molecule manipulation experiments of molecular motors provide essential information about the rate and conformational changes of the steps of the reaction located along the manipulation coordinate. This information is not always sufficient to define a particular kinetic cycle. Recent single-molecule experiments with optical tweezers showed that the DNA unwinding activity of a Phi29 DNA polymerase mutant presents a complex pause behavior, which includes short and long pauses. Here we show that different kinetic models, considering different connections between the active and the pause states, can explain the experimental pause behavior. Both the two independent pause model and the two connected pause model are able to describe the pause behavior of a mutated Phi29 DNA polymerase observed in an optical tweezers single-molecule experiment. For the two independent pause model all parameters are fixed by the observed data, while for the more general two connected pause model there is a range of values of the parameters compatible with the observed data (which can be expressed in terms of two of the rates and their force dependencies). This general model includes models with indirect entry and exit to the long-pause state, and also models with cycling in both directions. Additionally, assuming that detailed balance is verified, which forbids cycling, this reduces the ranges of the values of the parameters (which can then be expressed in terms of one rate and its force dependency). The resulting model interpolates between the independent pause model and the indirect entry and exit to the long-pause state model

  13. The role of test parameters on the kinetics and thermodynamics of glass leaching. [None

    Energy Technology Data Exchange (ETDEWEB)

    Jantzen, C M

    1988-01-01

    The relative durabilities of nuclear waste, natural, and ancient glasses have been assessed by standard laboratory leach tests. Different test conditions result in different glass surface areas (SA), leachant volumes (V), and test durations (t). Leachate concentrations are known to be a parabolic function of the kinetic test parameter SAV/center dot/t. Based on durability experiments of glass monoliths at low (SAV)/center dot/ glass durability has been shown to be a logarithmic function of the thermodynamic hydration free energy, ..delta..G/sub hyd/. The thermodynamic hydration free energy, ..delta..G/sub hyd/, can be calculated from glass composition and solution pH. In the repository environment high effective glass surface areas to solution volume ratios may occur as a result of slow groundwater flow rates. The application of hydration thermodynamics to crushed glass, high (SAV)/center dot/t, durability tests has been demonstrated. The relative contributions of the kinetic test parameters, (SAV)/center dot/t, and the thermodynamic parameter, ..delta..G/sub hyd/, have been shown to define a plane in ..delta..G/sub hyd/-concentration-(SAV)/center dot/t space. At constant test conditions, e.g. constant (SAV/center dot/t, the intersection with this surface indicates that all /delta G//sub hyd/-concentration plots should have similar slopes and predict the same relative durabilities for various glasses as a function of glass composition. Using this approach, the durability of nuclear waste glasses has been interpolated to be -- 10/sup 6/ years and no less than 10/sup 3/ years. 28 refs., 24 figs.

  14. Evaluation of kinetic parameters of PAN fibre modified by electron beam radiation

    Energy Technology Data Exchange (ETDEWEB)

    Giovedi, Claudia; Arruda, Clarissa P. Zelinschi de; Carolino, Ana Claudia V., E-mail: giovedi@ctmsp.mar.mil.b [Centro Tecnologico da Marinha em Sao Paulo (CTMSP), SP (Brazil). Dept. de Tecnologia do Combustivel. Lab. de Caracterizacao de Materiais; Machado, Luci D.B.; Pino, Eddy S., E-mail: lmachado@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2009-07-01

    Carbon fibers used for structural application are about 90% based on polyacrylonitrile (PAN) precursors due to their physical and mechanical properties. The thermal process is the conventional way to obtain a carbon fiber from PAN precursors. However, the use of ionizing radiation is given as an alternative technology to improve the physical and mechanical properties of the resulting carbon fiber. The aim of this paper was to obtain kinetic parameters (activation energy, conversion and isoconversion data) from DSC curves of PAN fibers irradiated with electron beam (EB) at different doses using the software Model Free Kinetics. The EB irradiation doses applied were: 0.2; 0.4; 0.6; 0.8; 1.0 and 1.2 MGy. The effect of ionizing radiation was evaluated by the thermal behavior of PAN precursors studied by Differential Scanning Calorimetry (DSC), which presents an exothermic peak in the range of 200 deg C to 400 deg C, depending on the experimental conditions of the DSC measurements. The obtained results showed that non-irradiated PAN fiber needs higher temperatures or longer reaction times to reach the same conversion degrees of the irradiated PAN fibers. Among the irradiated fibers, the reaction times decrease as a function of the radiation dose applied. However, the most important changes were observed for doses up to 0.4 MGy. The experimental results indicate that the EB radiation induces modification in the PAN fibers, which became them more liable in the oxidation process. (author)

  15. Integrated modeling methodology for microtubule dynamics and Taxol kinetics with experimentally identifiable parameters.

    Science.gov (United States)

    Zhao, He; Sokhansanj, Bahrad A

    2007-10-01

    Microtubule dynamics play a critical role in cell function and stress response, modulating mitosis, morphology, signaling, and transport. Drugs such as paclitaxel (Taxol) can impact tubulin polymerization and affect microtubule dynamics. While theoretical methods have been previously proposed to simulate microtubule dynamics, we develop a methodology here that can be used to compare model predictions with experimental data. Our model is a hybrid of (1) a simple two-state stochastic formulation of tubulin polymerization kinetics and (2) an equilibrium approximation for the chemical kinetics of Taxol drug binding to microtubule ends. Model parameters are biologically realistic, with values taken directly from experimental measurements. Model validation is conducted against published experimental data comparing optical measurements of microtubule dynamics in cultured cells under normal and Taxol-treated conditions. To compare model predictions with experimental data requires applying a "windowing" strategy on the spatiotemporal resolution of the simulation. From a biological perspective, this is consistent with interpreting the microtubule "pause" phenomenon as at least partially an artifact of spatiotemporal resolution limits on experimental measurement.

  16. A new multi-wavelength model-based method for determination of enzyme kinetic parameters

    Indian Academy of Sciences (India)

    Mohammad-Hossein Sorouraddin; Kaveh Amini; Abdolhossein Naseri; Javad Vallipour; Jalal Hanaee; Mohammad-Reza Rashidi

    2010-09-01

    Lineweaver–Burk plot analysis is the most widely used method to determine enzyme kinetic parameters. In the spectrophotometric determination of enzyme activity using the Lineweaver–Burk plot, it is necessary to find a wavelength at which only the substrate or the product has absorbance without any spectroscopic interference of the other reaction components. Moreover, in this method, different initial concentrations of the substrate should be used to obtain the initial velocities required for Lineweaver–Burk plot analysis. In the present work, a multi-wavelength model-based method has been developed and validated to determine Michaelis–Menten constants for some enzyme reactions. In this method, a selective wavelength region and several experiments with different initial concentrations of the substrate are not required. The absorbance data of the kinetic assays are fitted by non-linear regression coupled to the numeric integration of the related differential equation. To indicate the applicability of the proposed method, the Michaelis–Menten constants for the oxidation of phenanthridine, 6-deoxypenciclovir and xanthine by molybdenum hydroxylases were determined using only a single initial concentration of the substrate, regardless of any spectral overlap.

  17. Kinetic parameter estimation and fluctuation analysis of CO at SnO 2 single nanowires

    KAUST Repository

    Tulzer, Gerhard

    2013-07-12

    In this work, we present calculated numerical values for the kinetic parameters governing adsorption/desorption processes of carbon monoxide at tin dioxide single-nanowire gas sensors. The response of such sensors to pulses of 50 ppm carbon monoxide in nitrogen is investigated at different temperatures to extract the desired information. A rate-equation approach is used to model the reaction kinetics, which results in the problem of determining coefficients in a coupled system of nonlinear ordinary differential equations. The numerical values are computed by inverse-modeling techniques and are then used to simulate the sensor response. With our model, the dynamic response of the sensor due to the gas-surface interaction can be studied in order to find the optimal setup for detection, which is an important step towards selectivity of these devices. We additionally investigate the noise in the current through the nanowire and its changes due to the presence of carbon monoxide in the sensor environment. Here, we propose the use of a wavelet transform to decompose the signal and analyze the noise in the experimental data. This method indicates that some fluctuations are specific for the gas species investigated here. © 2013 IOP Publishing Ltd.

  18. Determination of kinetic parameters of Phlomis bovei de Noé using thermogravimetric analysis.

    Science.gov (United States)

    Yahiaoui, Meriem; Hadoun, Hocine; Toumert, Idir; Hassani, Aicha

    2015-11-01

    This paper reports the pyrolysis study of Phlomis bovei biomass by thermogravimetric experiments in order to determine the thermal degradation behavior and kinetic parameters. The weight losses were found to occur in three stages. In the DTG thermograms, an increase of the heating rate tended to delay thermal degradation processes towards higher temperatures. The average values of activation energy and pre-exponential factor calculated from Ozawa-Flynn-Wall, Kissinger-Akahira-Sunose and Kissinger methods are 134.83, 134.06, 223.31kJ/mol and 4.1610(13), 1.1810(10), 2.8110(11)/s, respectively. The three-pseudo-component method shows that the activation energy increases with increasing the heating rate for hemicellulose and cellulose while the activation energy of the lignin decreased with an increase of the heating rate. Predicted results and experimental data exhibit similar tendencies and the three pseudo-components model with n different from unity 1 is recommended as the most suitable for prediction of kinetic behavior of Phlomis bovei de Noé.

  19. A new multi-wavelength model-based method for determination of enzyme kinetic parameters.

    Science.gov (United States)

    Sorouraddin, Mohammad-Hossein; Amini, Kaveh; Naseri, Abdolhossein; Vallipour, Javad; Hanaee, Jalal; Rashidi, Mohammad-Reza

    2010-09-01

    Lineweaver-Burk plot analysis is the most widely used method to determine enzyme kinetic parameters. In the spectrophotometric determination of enzyme activity using the Lineweaver-Burk plot, it is necessary to find a wavelength at which only the substrate or the product has absorbance without any spectroscopic interference of the other reaction components. Moreover, in this method, different initial concentrations of the substrate should be used to obtain the initial velocities required for Lineweaver-Burk plot analysis. In the present work, a multi-wavelength model-based method has been developed and validated to determine Michaelis-Menten constants for some enzyme reactions. In this method, a selective wavelength region and several experiments with different initial concentrations of the substrate are not required. The absorbance data of the kinetic assays are fitted by non-linear regression coupled to the numeric integration of the related differential equation. To indicate the applicability of the proposed method, the Michaelis-Menten constants for the oxidation of phenanthridine, 6-deoxypenciclovir and xanthine by molybdenum hydroxylases were determined using only a single initial concentration of the substrate, regardless of any spectral overlap.

  20. Does Vibration Warm-up Enhance Kinetic and Temporal Sprint Parameters?

    Science.gov (United States)

    Cochrane, D J; Cronin, M J; Fink, P W

    2015-08-01

    The aim of this study was to investigate the efficacy of vibration warm-up to enhance sprint performance. 12 males involved in representative team sports performed 4 warm-up conditions in a randomised order performed at least 24 h apart; VbX warm-up (VbX-WU); Neural activation warm-up (Neu-WU); Dynamic warm-up (Dyn-WU) and Control (No VbX). Participants completed 5 m sprint at 30 s, 2:30 min and 5 min post warm-up where sprint time, kinetics, and temporal components were recorded. There was no significant (p>0.05) main effect or interaction effect between the split sprint times of 1 m, 2.5 m, and 5 m. There was a condition effect where vertical mean force was significantly higher (p0.05) main and interaction effects in sprint kinetic and temporal parameters existed. Overall, all 4 warm-up conditions produced comparable results for sprint performance, and there was no detrimental effect on short-duration sprint performance using VbX-WU. Therefore, VbX could be useful for adding variety to the training warm-up or be included into the main warm-up routine as a supplementary modality.

  1. Calculation of kinetic parameters of Caliban metallic core experimental reactor from stochastic neutron measurements

    Energy Technology Data Exchange (ETDEWEB)

    Casoli, P.; Authier, N.; Baud, J. [Commissariat a l' energie Atomique, Centre de Valduc, 21120 Is-sur-Tille (France)

    2009-07-01

    Several experimental devices are operated by the Criticality and Neutron Science Research Department of the CEA Valduc Laboratory. One of these is the metallic core reactor Caliban. The knowledge of the fundamental kinetic parameters of the reactor is very useful, indeed necessary, to the operator. The purpose of this study was to develop and perform experiments allowing to determinate some of these parameters. The prompt neutron decay constant and particularly its value at criticality can be measured with reactor noise techniques such as the interval-distribution, the Feynman variance-to-mean, and the Rossi-{alpha} methods. By introducing the Nelson number, the effective delayed neutron fraction and the average neutron lifetime can also be calculated with the Rossi-{alpha} method. Subcritical, critical, and even supercritical experiments were performed. With the Rossi-{alpha} technique, it was found that the prompt neutron decay constant at criticality was (6.02*10{sup 5} {+-} 9%). Experiments also brought out the limitations of the used experimental parameters. (authors)

  2. Kinetic study of the anaerobic biodegradation of alkyl polyglucosides and the influence of their structural parameters.

    Science.gov (United States)

    Ríos, Francisco; Fernández-Arteaga, Alejandro; Lechuga, Manuela; Jurado, Encarnación; Fernández-Serrano, Mercedes

    2016-05-01

    This paper reports a study of the anaerobic biodegradation of non-ionic surfactants alkyl polyglucosides applying the method by measurement of the biogas production in digested sludge. Three alkyl polyglucosides with different length alkyl chain and degree of polymerization of the glucose units were tested. The influence of their structural parameters was evaluated, and the characteristics parameters of the anaerobic biodegradation were determined. Results show that alkyl polyglucosides, at the standard initial concentration of 100 mgC L(-1), are not completely biodegradable in anaerobic conditions because they inhibit the biogas production. The alkyl polyglucoside having the shortest alkyl chain showed the fastest biodegradability and reached the higher percentage of final mineralization. The anaerobic process was well adjusted to a pseudo first-order equation using the carbon produced as gas during the test; also, kinetics parameters and a global rate constant for all the involved metabolic process were determined. This modeling is helpful to evaluate the biodegradation or the persistence of alkyl polyglucosides under anaerobic conditions in the environment and in the wastewater treatment.

  3. Kinetic parameters of the thermal degradation of the PP and nondegraded and degraded HDPE blends

    Energy Technology Data Exchange (ETDEWEB)

    Albano, C.; Freitas, E. [Universidad Central de Venezuela, Caracas (Venezuela)

    1996-12-31

    We study the thermodegradative behavior of PP, of non-degraded and degraded HDPE and their blends, in order to analyze the thermal stability of such materials. Van-Krevelen (V-K), Coats-Redfern (C-R) and Horowitz-Metzger (H-M) integral methods as well as the Freeman-Carroll (F-C) differential one, were used to determine the kinetic parameters. The activation energy (E{sub a}) obtained for the PP mixed with non-degraded HDPE (5 to 50%) is lower than the E{sub a} correspondent to pure polymers and does not depend on the HDPE concentration. Blends of degraded materials, show an approximate value of E{sub a} of 200 kJ/mol for mixtures with concentrations by weight of HDPE up to 20%, but its value decreases drastically with higher concentrations. 11 refs., 2 tabs.

  4. Calculation of Reactor Kinetics Parameters βeff and Λ with Monte Carlo Differential Operator Sampling

    Science.gov (United States)

    Nagaya, Yasunobu

    2014-06-01

    The methods to calculate the kinetics parameters of βeff and Λ with the differential operator sampling have been reviewed. The comparison of the results obtained with the differential operator sampling and iterated fission probability approaches has been performed. It is shown that the differential operator sampling approach gives the same results as the iterated fission probability approach within the statistical uncertainty. In addition, the prediction accuracy of the evaluated nuclear data library JENDL-4.0 for the measured βeff/Λ and βeff values is also examined. It is shown that JENDL-4.0 gives a good prediction except for the uranium-233 systems. The present results imply the need for revisiting the uranium-233 nuclear data evaluation and performing the detailed sensitivity analysis.

  5. One-Dimensional Modeling of an Entrained Coal Gasification Process Using Kinetic Parameters

    Directory of Open Access Journals (Sweden)

    Moonkyeong Hwang

    2016-02-01

    Full Text Available A one-dimensional reactor model was developed to simulate the performance of an entrained flow gasifier under various operating conditions. The model combined the plug flow reactor (PFR model with the well-stirred reactor (WSR model. Reaction kinetics was considered together with gas diffusion for the solid-phase reactions in the PFR model, while equilibrium was considered for the gas-phase reactions in the WSR model. The differential and algebraic equations of mass balance and energy balance were solved by a robust ODE solver, i.e., an semi-implicit Runge–Kutta method, and by a nonlinear algebraic solver, respectively. The computed gasifier performance was validated against experimental data from the literature. The difference in product gas concentration from the equilibrium model, and the underlying mechanisms were discussed further. The optimal condition was found after parameter studies were made for various operating conditions.

  6. Evaluation of kinetic parameters and redox mechanism of quinoxaline at glassy carbon electrode

    Directory of Open Access Journals (Sweden)

    Aleksić Mara M.

    2014-01-01

    Full Text Available The electrochemical behavior of a biologically important heterocyclic compound quinoxaline (QUI was investigated by cyclic voltammetry (CV in solutions of differing pH, using a glassy carbon electrode (GCE. The reduction of QUI occurs as a quasi-reversible reaction in acid medium, reaching reversibility in alkaline solutions. The kinetic parameters of the electrode process such as αnα, diffusion coefficient (D and heterogeneous rate constant (ks, were evaluated and discussed. Redox mechanism of QUI was proposed on the basis of experimental results. Reduction process involves a transfer of two electrons and two protons at the pyrazine ring of QUI forming a dihydro-derivative. In acid solutions, the product of QUI reduction undergoes irreversible oxidation in a one-electron process. The electrode processes was found to be diffusion controlled. [Projekat Ministarstva nauke Republike Srbije, br. 172033

  7. Sensitivity of natural gas HCCI combustion to fuel and operating parameters using detailed kinetic modeling

    Energy Technology Data Exchange (ETDEWEB)

    Aceves, S; Dibble, R; Flowers, D; Smith, J R; Westbrook, C K

    1999-07-19

    This paper uses the HCT (Hydrodynamics, Chemistry and Transport) chemical kinetics code to analyze natural gas HCCI combustion in an engine. The HCT code has been modified to better represent the conditions existing inside an engine, including a wall heat transfer correlation. Combustion control and low power output per displacement remain as two of the biggest challenges to obtaining satisfactory performance out of an HCCI engine, and these are addressed in this paper. The paper considers the effect of natural gas composition on HCCI combustion, and then explores three control strategies for HCCI engines: DME (dimethyl ether) addition, intake heating and hot EGR addition. The results show that HCCI combustion is sensitive to natural gas composition, and an active control may be required to compensate for possible changes in composition. The three control strategies being considered have a significant effect in changing the combustion parameters for the engine, and should be able to control HCCI combustion.

  8. Study of kinetic parameters of K 2Ca 2(SO 4)3 thermoluminescence dosimeter

    Science.gov (United States)

    Choubey, A.; Das, S.; Sharma, S. K.; Manam, J.

    The dosimetry study of thermoluminescence materials is based on a good knowledge of its kinetics para-meters. A polycrystalline sample of K 2Ca 2(SO 4)3 was prepared by the solid-state diffusion method. Formation of the compound was checked by using X-ray diffraction and Fourier-transform infrared spectroscopy. Thermally stimulated luminescence (TSL) glow curves of X-ray-irradiated K 2Ca 2(SO 4)3 phosphor exhibit one glow peak at 195 °C and a shoulder at around 120 °C, indicating that two different sets of traps are being activated within the particular temperature range, each with its own value of activation energy (E) and frequency factor (s). The kinetic parameters associated with the prominent glow peak of K 2Ca 2(SO 4)3 were calculated using the isothermal luminescence decay method. The electron spin resonance study of the prepared compound exhibits the presence of img style="vertical-align: text-bottom;" class="inlinematheqn" src="/ampp/image?path=/713648881/917117136/grad_a_438565_o_ilm0001.gif" alt="./GRAD_A_438565_O_XML_IMAGES/GRAD_A_438565_O_ILM0001.gif" border="0" /> and img style="vertical-align: text-bottom;" class="inlinematheqn" src="/ampp/image?path=/713648881/917117136/grad_a_438565_o_ilm0002.gif" alt="./GRAD_A_438565_O_XML_IMAGES/GRAD_A_438565_O_ILM0002.gif" border="0" /> radical ions that are responsible for the observed TSL glow peaks. The release of hole/electron from trap centres at the characteristic trap site initiates the luminescence process in these materials.

  9. Synergistic improvement of gas sensing performance by micro-gravimetrically extracted kinetic/thermodynamic parameters.

    Science.gov (United States)

    Guo, Shuanbao; Xu, Pengcheng; Yu, Haitao; Cheng, Zhenxing; Li, Xinxin

    2015-03-10

    A novel method is explored for comprehensive design/optimization of organophosphorus sensing material, which is loaded on mass-type microcantilever sensor. Conventionally, by directly observing the gas sensing response, it is difficult to build quantitative relationship with the intrinsic structure of the material. To break through this difficulty, resonant cantilever is employed as gravimetric tool to implement molecule adsorption experiment. Based on the sensing data, key kinetic/thermodynamic parameters of the material to the molecule, including adsorption heat -ΔH°, adsorption/desorption rate constants Ka and Kd, active-site number per unit mass N' and surface coverage θ, can be quantitatively extracted according to physical-chemistry theories. With gaseous DMMP (simulant of organophosphorus agents) as sensing target, the optimization route for three sensing materials is successfully demonstrated. Firstly, a hyper-branched polymer is evaluated. Though suffering low sensitivity due to insufficient N', the bis(4-hydroxyphenyl)-hexafluoropropane (BHPF) sensing-group exhibits satisfactory reproducibility due to appropriate -ΔH°. To achieve more sensing-sites, KIT-5 mesoporous-silica with higher surface-area is assessed, resulting in good sensitivity but too high -ΔH° that brings poor repeatability. After comprehensive consideration, the confirmed BHPF sensing-group is grafted on the KIT-5 carrier to form an optimized DMMP sensing nanomaterial. Experimental results indicate that, featuring appropriate kinetic/thermodynamic parameters of -ΔH°, Ka, Kd, N' and θ, the BHPF-functionalized KIT-5 mesoporous silica exhibits synergistic improvement among reproducibility, sensitivity and response/recovery speed. The optimized material shows complete signal recovery, 55% sensitivity improvement than the hyper-branched polymer and 2∼3 folds faster response/recovery speed than the KIT-5 mesoporous silica.

  10. Ammonium Removal from Aqueous Solutions by Clinoptilolite: Determination of Isotherm and Thermodynamic Parameters and Comparison of Kinetics by the Double Exponential Model and Conventional Kinetic Models

    Directory of Open Access Journals (Sweden)

    İsmail Tosun

    2012-03-01

    Full Text Available The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R and four three-parameter (Redlich-Peterson (R-P, Sips, Toth and Khan isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R2 of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°, enthalpy (∆H° and entropy (∆S° of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients.

  11. Ammonium removal from aqueous solutions by clinoptilolite: determination of isotherm and thermodynamic parameters and comparison of kinetics by the double exponential model and conventional kinetic models.

    Science.gov (United States)

    Tosun, Ismail

    2012-03-01

    The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R)) and four three-parameter (Redlich-Peterson (R-P), Sips, Toth and Khan) isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E) from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R(2)) of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM) showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients.

  12. Estimation of Kinetic Parameters for Enzyme Catalysed Batch Bioreactor for the Production of Ethanol from Corn

    Directory of Open Access Journals (Sweden)

    Z. R. Yelebe

    2014-03-01

    Full Text Available This paper addresses the challenge of estimating various kinetic parameters for the design of an optimized enzyme catalysed batch bioreactor of high efficiency and yield. Mathematical models were developed to describe the batch reaction time in relation to the substrate, enzyme and product concentration. The results obtained from the plots generated were: 35.50gmol/l.hr for the velocity of reaction of the enzymes (Vmax, 0.10049hr-1 for the maximum specific growth rate (µmax 826.45gmol/l for the Michaelis-Menten constant (Km, 0.005402577 for maintenance coefficient (Ms, 10.104kgCx/kgCs for yield of cell weight per unit weight of substrate (Ycx/CS, 0.05436kgCp/kgCs for yield of product weight per unit weight of substrate utilized (Ycp/CS and 0.01416 for endogenous decay coefficient (Kd for the design of the batch biochemical reactor. Hence, they are useful parameters for predicting the most appropriate batch reaction conditions and the efficiency of the bioreactor. The mathematical model predictions showed that it can be considered as a good complimentary tool to real system since the simulation results of the mathematical model agrees with experimental data reported in literature.

  13. REMOVAL OF BORON USING CLAY-EFFECT OF PROCESS PARAMETERS,KINETIC AND ISOTHERM STUDIES

    Directory of Open Access Journals (Sweden)

    N. RAJAMOHAN

    2016-03-01

    Full Text Available In this study, a low-cost eco-friendly adsorbent was prepared from naturally available sarooj clay and is proposed for the removal of boron from aqueous phase. The effect of process parameters, namely initial pH, sorbent quantity, initial boron concentration, shaking speed and temperature were studied on the metal uptake under batch conditions. The process efficiency was observed to be strongly parameter dependent and the optimal pH was found to be 10.0.The uptake capacity decreased with increase in sorbent dose and increased with boron concentration. Temperature was found to have a positive influence confirming the endothermic nature of the process. Equilibrium sorption data were analysed using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm and represented well by Freundlich isotherm. The Freundlich constant was evaluated as 14.791 L g-1 at 35 °C.The mechanism of sorption was investigated using kinetic models, namely, pseudo-second order and intraparticle diffusion models .The batch experimental fitted well to pseudo-second order model and the rate constant was found to be 0.0017 g mg-1min-1 with an initial boron concentration of 100 mg L-1. The sorbent characteristics were studied using X-ray diffraction, scanning electron microscope with energy dispersive X-ray detector and X-ray fluorescence methods.

  14. Removal of methylene blue by adsorption on aluminosilicate waste: equilibrium, kinetic and thermodynamic parameters.

    Science.gov (United States)

    Policiano Almeida, Carlos Alberto; Zanela, Tânia Marina Palhano; Machado, Clodoaldo; Altamirano Flores, Juan Antônio; Scheibe, Luiz Fernando; Hankins, Nicholas P; Debacher, Nito Angelo

    2016-11-01

    An aluminosilicate waste (AW) was investigated as adsorbent for methylene blue (MB) dye. AW was characterized by petrography, X-ray diffractometry, X-ray fluorescence, scanning electron microscopy, thermogravimetry and zeta potential measurements. It was found that AW contains kaolinite, and other minor components such as quartz, muscovite, smectite, siderite, pyrite and organic compounds. The chemical composition of AW is mainly SiO2 (49%) and Al2O3 (23%) and it has negative superficial charge above pH 1.73. Adsorption of MB dye was studied in a batch system under different conditions of initial dye concentration, contact time and temperature. The isothermal data from batch experiments were fitted to Langmuir and Freundlich equations, with a better fit shown by the Langmuir isotherm equation. Also, pseudo-first-order, pseudo-second-order and intraparticle diffusion models were considered to evaluate the rate parameters. The experimental data fitted the pseudo-first-order kinetic model best. Thermodynamic parameters were calculated, showing the adsorption to be an endothermic yet spontaneous process, with the activation energy of +37.8 kJ mol(-1). The results indicate that AW adsorbs MB efficiently, and can be employed as a low-cost alternative in wastewater treatment for the removal of cationic dyes.

  15. The basal kinetic parameters of glycogen synthase in human myotube cultures are not affected by chronic high insulin exposure

    DEFF Research Database (Denmark)

    Gaster, M; Schrøder, H D; Handberg, A

    2001-01-01

    There is no consensus regarding the results from in vivo and in vitro studies on the impact of chronic high insulin and/or high glucose exposure on acute insulin stimulation of glycogen synthase (GS) kinetic parameters in human skeletal muscle. The aim of this study was to evaluate the kinetic...... parameters of glycogen synthase activity in human myotube cultures at conditions of chronic high insulin combined or not with high glucose exposure, before and after a subsequent acute insulin stimulation. Acute insulin stimulation significantly increased the fractional activity (FV(0.1)) of GS, increased...

  16. Kinetic parameter determination of roasted and unroasted argan oil oxidation under Rancimat test conditions

    Directory of Open Access Journals (Sweden)

    Zaanoun, I.

    2014-09-01

    Full Text Available The present study investigated the Kinetic parameter determination of edible argan oil (coldpressed from roasted argan kernels and cosmetic argan oil (cold-pressed from unroasted argan kernels under the Rancimat test conditions. The physicochemical parameters of edible and cosmetic argan oil immediately after preparation and after accelerated oxidation test Rancimat at different temperatures 90 °C, 100 °C, 110 °C, 120 °C, 130 °C and 140 °C were determined and compared. The natural logarithms of the kinetic rate constant (kvalue varied linearly with respect to temperature. An increasing rate of oxidation could be observed as temperature increased. On the basis of the Arrhenius equation and the activated complex theory, frequency factors A, activation energies Ea, Q10 numbers, activation enthalpies ΔH, and activation entropies ΔS for oxidative stability of the vegetable oils were calculated. The accelerated oxidation and Kinetic parameters have shown that edible argan oil can be stored much better than cosmetic oil.En presente estudio se determinaron los parámetros cinéticosde aceites de argán comestible (prensado en frío a partir de granos tostados de argán y cosmético (prensado en frío a partir de granos de argán sin tostar bajo las condiciones del método Rancimat. Se determinó y comparó los parámetros físico-químicos de aceites de argán comestible y cosmético inmediatamente después de la preparación y después de la oxidación acelerada mediante Rancimat a temperaturas de 90 °C, 100 °C, 110 °C, 120 °C, 130 °C y 140 °C Los logaritmos naturales de la constante de velocidad cinética (valor k variaron linealmente con respecto a la temperatura. Se pudo observar un valor creciente de la oxidación conel aumento de la temperatura. Se calculó para la estabilidad oxidativa de los aceites vegetalesy sobre la base de la ecuación de Arrhenius y la teoría del complejo activado, la frecuencia de los factores A, energ

  17. Computer controlled automated assay for comprehensive studies of enzyme kinetic parameters.

    Directory of Open Access Journals (Sweden)

    Felix Bonowski

    Full Text Available Stability and biological activity of proteins is highly dependent on their physicochemical environment. The development of realistic models of biological systems necessitates quantitative information on the response to changes of external conditions like pH, salinity and concentrations of substrates and allosteric modulators. Changes in just a few variable parameters rapidly lead to large numbers of experimental conditions, which go beyond the experimental capacity of most research groups. We implemented a computer-aided experimenting framework ("robot lab assistant" that allows us to parameterize abstract, human-readable descriptions of micro-plate based experiments with variable parameters and execute them on a conventional 8 channel liquid handling robot fitted with a sensitive plate reader. A set of newly developed R-packages translates the instructions into machine commands, executes them, collects the data and processes it without user-interaction. By combining script-driven experimental planning, execution and data-analysis, our system can react to experimental outcomes autonomously, allowing outcome-based iterative experimental strategies. The framework was applied in a response-surface model based iterative optimization of buffer conditions and investigation of substrate, allosteric effector, pH and salt dependent activity profiles of pyruvate kinase (PYK. A diprotic model of enzyme kinetics was used to model the combined effects of changing pH and substrate concentrations. The 8 parameters of the model could be estimated from a single two-hour experiment using nonlinear least-squares regression. The model with the estimated parameters successfully predicted pH and PEP dependence of initial reaction rates, while the PEP concentration dependent shift of optimal pH could only be reproduced with a set of manually tweaked parameters. Differences between model-predictions and experimental observations at low pH suggest additional protonation

  18. Kinetic parameters for nutrient enhanced crude oil biodegradation in intertidal marine sediments

    Directory of Open Access Journals (Sweden)

    Arvind K Singh

    2014-04-01

    Full Text Available Availability of inorganic nutrients, particularly N and P, is often a primary control on crude oil hydrocarbon degradation in marine systems. Nevertheless, there is a paucity of information on fundamental kinetic parameters for nutrient enhanced crude oil biodegradation that can be used to model the fate of crude oil in bioremediation programmes that use inorganic nutrient addition to stimulate oil biodegradation. Here we report fundamental kinetic parameters (Ks and qmax for nitrate- and phosphate-stimulated crude oil biodegradation under nutrient limited conditions and with respect to crude oil, under conditions where N&P are not limiting. Crude oil degradation was limited by both N&P availability. When N was added alone maximum rates of CO2 production measured were 3.94±0.46 µmol CO2 /g wet sediment/day. However when the same levels of N were added in the presence of 0.5% P w/w of oil (1.6 μmol P/g wet sediment maximum rates of measured CO2 production more than doubled (11.52±0.72 µmol CO2 /g wet sediment/day. Ks and qmax estimates for N (in the form of sodium nitrate when P was not limiting were 1.57±0.56 µmol/g wet sediment and 10.57±0.63 µmol CO2 /g wet sediment/day respectively. The corresponding values for P were 80 nmol/g wet sediment and 8.76±1.15 µmol CO2 /g wet sediment/day. The qmax values with respect to N and P were not significantly different (P< 0.05. Analysis of bacterial 16S rRNA genes indicated that Alcanivorax spp. were selected in these marine sediments with increasing inorganic nutrient concentration, whereas Cycloclasticus spp. were more prevalent at lower inorganic nutrient concentrations. These data suggest that simple empirical estimates of the proportion of nutrients added relative to crude oil concentrations may not be sufficient to guarantee successful crude oil bioremediation in oxic beach sediments. The data we present also help define the maximum rates and hence timescales required for bioremediation

  19. Thermodynamic, Kinetic, and Equilibrium Parameters for the Removal of Lead and Cadmium from Aqueous Solutions with Calcium Alginate Beads

    Directory of Open Access Journals (Sweden)

    Ruth Alfaro-Cuevas-Villanueva

    2014-01-01

    Full Text Available The sorption of cadmium (Cd and lead (Pb by calcium alginate beads (CAB from aqueous solutions in batch systems was investigated. The kinetic and thermodynamic parameters, as well as the sorption capacities of CAB in each system at different temperatures, were evaluated. The rate of sorption for both metals was rapid in the first 10 minutes and reached a maximum in 50 minutes. Sorption kinetic data were fitted to Lagergren, pseudo-second-order and Elovich models and it was found that the second-order kinetic model describes these data for the two metals; comparing kinetic parameters for Cd and Pb sorption a higher kinetic rate (K2 for Pb was observed, indicating that the interaction between lead cations and alginate beads was faster than for cadmium. Similarly, isotherm data were fitted to different models reported in literature and it was found that the Langmuir-Freundlich (L-F and Dubinin-Radushkevich (D-R models describe the isotherms in all cases. CAB sorption capacity for cadmium was 27.4 mg/g and 150.4 mg/g for lead, at 25°C. Sorption capacities of Cd and Pb increase as temperature rises. According to the thermodynamic parameters, the cadmium and lead adsorption process was spontaneous and endothermic. It was also found that pH has an important effect on the adsorption of these metals by CAB, as more were removed at pH values between 6 and 7.

  20. Sorption of selenate on soils and pure phases: kinetic parameters and stabilisation

    Energy Technology Data Exchange (ETDEWEB)

    Loffredo, N. [Institut de Radioprotection et Surete Nucleaire (IRSN), DEI/SECRE/Laboratoire de Radioecologie et d' Ecotoxicologie, Cadarache, Bat 186, BP3, 13115 Saint-Paul-lez-Durance Cedex (France); Mounier, S. [Laboratoire PROTEE, Universite du Sud Toulon-Var, BP 20132, La Garde 83957 (France); Thiry, Y. [Agence Nationale pour la gestion des Dechets Radioactifs (Andra), Parc de la Croix Blanche, 1/7 rue Jean Monnet, 92298 Chatenay-Malabry Cedex (France); Coppin, F., E-mail: frederic.coppin@irsn.fr [Institut de Radioprotection et Surete Nucleaire (IRSN), DEI/SECRE/Laboratoire de Radioecologie et d' Ecotoxicologie, Cadarache, Bat 186, BP3, 13115 Saint-Paul-lez-Durance Cedex (France)

    2011-09-15

    This study was conducted to identify the principle selenate carrier phases for two selected soils, by comparing their reactivity with selenate to that of pure phases of the solids. Silica, calcium carbonate, aluminium hydroxide, goethite, bentonite and humic acid were selected as the main soil carrier phases. Comparisons were made first on the parameter values obtained with the best fit of a kinetic sorption model which can discriminate instantaneous sorption from kinetically limited sorption. Then comparisons were made of the ability for each solid to stabilise selenate by measuring the ratio of the partition coefficient for sorption (Kd{sub sorption}) over that of the desorption (Kd{sub desorption}). Kinetics and stabilisation were used to help elucidate the nature of interactions with the test solid phases for a large range of selenate concentrations. The experiments were conducted over 165 h in batch reactors, the solid being isolated from the solution by dialysis tubing, at two pH (5.4 and 8) and three selenate concentrations (1 x 10{sup -3}, 1 x 10{sup -6} and 1 x 10{sup -8} mol L{sup -1}). The results obtained showed that only aluminium hydroxide can sorb selenate throughout the studied pH range (pH 5.4 to 8.0). The sorption capacity on this mineral was high (Kd{sub sorption} > 100 to 1 x 10{sup 4} L kg{sup -1}) and the selenate was mainly stabilized by the formation of inner sphere complexes. The sorption on goethite occurred at pH 5.4 (Kd{sub sorption} 52 L kg{sup -1}), mainly as outer sphere complexes, and was null at pH 8. On silica, a weak sorption was observed only at pH 5.4 and at 165 h (Kd{sub sorption} 4 L kg{sup -1}). On bentonite, calcium carbonate and humic acid no significant sorption was observed. Concerning the two soils studied, different behaviours were observed for selenate. For soil Ro (pH 5.4), Kd{sub sorption} was low (8 L kg{sup -1}) compared to soil Bu (pH 8) (70 L kg{sup -1}). The sorption behaviour of selenate on soil Ro was mainly

  1. Predicting heavy metals' adsorption edges and adsorption isotherms on MnO2 with the parameters determined from Langmuir kinetics.

    Science.gov (United States)

    Hu, Qinghai; Xiao, Zhongjin; Xiong, Xinmei; Zhou, Gongming; Guan, Xiaohong

    2015-01-01

    Although surface complexation models have been widely used to describe the adsorption of heavy metals, few studies have verified the feasibility of modeling the adsorption kinetics, edge, and isotherm data with one pH-independent parameter. A close inspection of the derivation process of Langmuir isotherm revealed that the equilibrium constant derived from the Langmuir kinetic model, KS-kinetic, is theoretically equivalent to the adsorption constant in Langmuir isotherm, KS-Langmuir. The modified Langmuir kinetic model (MLK model) and modified Langmuir isotherm model (MLI model) incorporating pH factor were developed. The MLK model was employed to simulate the adsorption kinetics of Cu(II), Co(II), Cd(II), Zn(II) and Ni(II) on MnO2 at pH3.2 or 3.3 to get the values of KS-kinetic. The adsorption edges of heavy metals could be modeled with the modified metal partitioning model (MMP model), and the values of KS-Langmuir were obtained. The values of KS-kinetic and KS-Langmuir are very close to each other, validating that the constants obtained by these two methods are basically the same. The MMP model with KS-kinetic constants could predict the adsorption edges of heavy metals on MnO2 very well at different adsorbent/adsorbate concentrations. Moreover, the adsorption isotherms of heavy metals on MnO2 at various pH levels could be predicted reasonably well by the MLI model with the KS-kinetic constants.

  2. Predicting heavy metals' adsorption edges and adsorption isotherms on MnO2 with the parameters determined from Langmuir kinetics

    Institute of Scientific and Technical Information of China (English)

    Qinghai Hu; Zhongjin Xiao; Xinmei Xiong; Gongming Zhou; Xiaohong Guan

    2015-01-01

    Although surface complexation models have been widely used to describe the adsorption of heavy metals,few studies have verified the feasibility of modeling the adsorption kinetics,edge,and isotherm data with one pH-independent parameter.A close inspection of the derivation process of Langrnuir isotherm revealed that the equilibrium constant derived from the Langmuir kinetic model,Ks-kinetic,is theoretically equivalent to the adsorption constant in Langrnuir isotherm,Ks-Langmuir.The modified Langmuir kinetic model (MLK model) and modified Langmuir isotherm model (MLI model) incorporating pH factor were developed.The MLK model was employed to simulate the adsorption kinetics of Cu(Ⅱ),Co(Ⅱ),Cd(Ⅱ),Zn(Ⅱ) and Ni(Ⅱ) on MnO2 at pH 3.2 or 3.3 to get the values of Ks-kinetic.The adsorption edges of heavy metals could be modeled with the modified metal partitioning model (MMP model),and the values of Ks-Langrnuir were obtained.The values of Ks-kinetic and Ks-Langrnuir are very close to each other,validating that the constants obtained by these two methods are basically the same.The MMP model with Ks-kinetic constants could predict the adsorption edges of heavy metals on MnO2 very well at different adsorbent/adsorbate concentrations.Moreover,the adsorption isotherms of heavy metals on MnO2 at various pH levels could be predicted reasonably well by the MLI model with the Ks-kinetic constants.

  3. Adsorption kinetic parameters of Fe3+ and Ni2+ ions by gyrolite

    Directory of Open Access Journals (Sweden)

    Kestutis Baltakys

    2015-03-01

    Full Text Available In this work the adsorption kinetic parameters for Fe3+ and Ni2+ ions by gyrolite are presented. Additionally, the adsoption mechanism was described by using pseudo first order and pseudo second order  equations. It was determined that the adsorption capacity of gyrolite and intrusion of heavy metals ions in its structure depends on reaction time and the pH value of adsorptive. It was observed that the incorporation of Fe3+ ions occurs more intensive than Ni2+ ions. It was found that in the acidic solution the intrusion of Fe3+ ions into gyrolite structure proceeds by two types of chemical reaction mechanisms: substitution and addition. Meanwhile, nickel ions were participated only in substitution reaction: gyrolite-Ca0 + Mex+ ↔ gyrolite-Me0 + Ca2+. It was observed that the pseudo second order model fit well for iron and nickel ions adsorption mechanism. It was estimated that the adsorption reactions are not reversible process and the crystal structure of gyrolite is stable. Moreover, synthetic adsorbent and the products of sorption were characterized by XRD, STA and FT-IR methods.DOI: http://dx.doi.org/10.5755/j01.ms.21.1.5735

  4. Methane oxidation in a landfill cover soil reactor: Changing of kinetic parameters and microorganism community structure.

    Science.gov (United States)

    Xing, Zhi L; Zhao, Tian T; Gao, Yan H; Yang, Xu; Liu, Shuai; Peng, Xu Y

    2017-02-23

    Changing of CH4 oxidation potential and biological characteristics with CH4 concentration was studied in a landfill cover soil reactor (LCSR). The maximum rate of CH4 oxidation reached 32.40 mol d(-1) m(-2) by providing sufficient O2 in the LCSR. The kinetic parameters of methane oxidation in landfill cover soil were obtained by fitting substrate diffusion and consumption model based on the concentration profile of CH4 and O2. The values of [Formula: see text] (0.93-2.29%) and [Formula: see text] (140-524 nmol kgsoil-DW(-1)·s(-1)) increased with CH4 concentration (9.25-20.30%), while the values of [Formula: see text] (312.9-2.6%) and [Formula: see text] (1.3 × 10(-5) to 9.0 × 10(-3) nmol mL(-1) h(-1)) were just the opposite. MiSeq pyrosequencing data revealed that Methylobacter (the relative abundance was decreased with height of LCSR) and Methylococcales_unclassified (the relative abundance was increased expect in H 80) became the key players after incubation with increasing CH4 concentration. These findings provide information for assessing CH4 oxidation potential and changing of biological characteristics in landfill cover soil.

  5. A study of line widths and kinetic parameters of ions in the solar corona

    CERN Document Server

    Zhao, G Q; Wang, C B

    2014-01-01

    Solar extreme-ultraviolet (EUV) lines emitted by highly charged ions have been extensively studied to discuss the issue of coronal heating and solar wind acceleration. Based on observations of the polar corona by the SUMER/SOHO spectrometer, this paper investigates the relation between the line widths and kinetic parameters of ions. It is shown that there exists a strongly linear correlation between two variables $(\\sigma/\\lambda)^2$ and $M^{-1}$, where $\\sigma$, $\\lambda$ and $M$ are the half-width of the observed line profile at $1/\\sqrt{e}$, the wavelength and the ion mass, respectively. The Pearson product-moment correlation coefficients exceed 0.9. This finding tends to suggest that the ions from a given height of polar corona have a common temperature and a common non-thermal velocity in terms of existing equation. The temperature and non-thermal velocity are obtained by linear least-square fit. The temperature is around $2.8$ MK at heights of 57$''$ and 102$''$. The non-thermal velocity is typical 21.6...

  6. Determination of the kinetic parameters of the CALIBAN metallic core reactor from stochastic neutron measurements

    Energy Technology Data Exchange (ETDEWEB)

    Casoli, P.; Authier, N.; Chapelle, A. [Commissariat a l' Energie Atomique et Aux Energies Alternatives, CEA, DAM, F-21120 Is sur Tille (France)

    2012-07-01

    Several experimental devices are operated by the Criticality and Neutron Science Research Dept. of the CEA Valduc Laboratory. One of these is the Caliban metallic core reactor. The purpose of this study is to develop and perform experiments allowing to determinate some of fundamental kinetic parameters of the reactor. The prompt neutron decay constant and particularly its value at criticality can be measured with reactor noise techniques such as Rossi-{alpha} and Feynman variance-to-mean methods. Subcritical, critical, and even supercritical experiments were performed. Fission chambers detectors were put nearby the core and measurements were analyzed with the Rossi-{alpha} technique. A new value of the prompt neutron decay constant at criticality was determined, which allows, using the Nelson number method, new evaluations of the effective delayed neutron fraction and the in core neutron lifetime. As an introduction of this paper, some motivations of this work are given in part 1. In part 2, principles of the noise measurements experiments performed at the CEA Valduc Laboratory are reminded. The Caliban reactor is described in part 3. Stochastic neutron measurements analysis techniques used in this study are then presented in part 4. Results of fission chamber experiments are summarized in part 5. Part 6 is devoted to the current work, improvement of the experimental device using He 3 neutron detectors and first results obtained with it. Finally, conclusions and perspectives are given in part 7. (authors)

  7. The determination of the kinetic parameters of electrochemical reaction in chemical power sources: A critical review

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yanhui; Wu, Jun; Li, Decheng; Zheng, Junwei [The Institute of Chemical Power Sources, Soochow (Suzhou) University, Suzhou 215006 (China); Chen, Ying [Max-Planck-Institut fuer Eisenforschung GmbH, Max-Planck-Str. 1, 40237 Duesseldorf (Germany); Ju, Hua [School of Urban Rail Transportation, Soochow (Suzhou) University, Ganjiang East Road 178, Suzhou 215021 (China)

    2010-06-15

    The derivation and proposal of major electrochemical techniques used to determine and calculate the electrochemical kinetic parameters is basically based on the electrochemical reaction taking place at liquid/solid or liquid/liquid interface in which all the reactants and products are soluble in liquid aqueous solution or liquid mercury electrode, or are volatile gas. Such electrochemical reaction system is classical and traditional (ERS1). Recently, the electrochemical behavior of some materials used as the active electrode materials in chemical power sources has attracted much attention. In chemical power source systems, either reactant or product, or both are insoluble. This kind of electrochemical reaction system (ERS2) is slightly different from ERS1. The application of these electrochemical techniques/equations to chemical power sources' system requires carefulness. The misuse of these electrochemical techniques can be easily found in the literatures and some of them even lead to a wrong conclusion. In this review, almost all the electrochemical techniques to measure the exchange current and diffusion coefficient were compiled for reference to the readers, including pulse step, electrochemical impedance, alternating cyclic voltammetry, etc. The necessary requirements/conditions to apply these techniques have been briefly discussed and some simple examples were also discussed for a better understanding. (author)

  8. Adsorption kinetic parameters of Fe3+ and Ni2+ ions by gyrolite

    Directory of Open Access Journals (Sweden)

    Kestutis Baltakys

    2015-03-01

    Full Text Available In this work the adsorption kinetic parameters for Fe3+ and Ni2+ ions by gyrolite are presented. Additionally, the adsoption mechanism was described by using pseudo first order and pseudo second order  equations. It was determined that the adsorption capacity of gyrolite and intrusion of heavy metals ions in its structure depends on reaction time and the pH value of adsorptive. It was observed that the incorporation of Fe3+ ions occurs more intensive than Ni2+ ions. It was found that in the acidic solution the intrusion of Fe3+ ions into gyrolite structure proceeds by two types of chemical reaction mechanisms: substitution and addition. Meanwhile, nickel ions were participated only in substitution reaction: gyrolite-Ca0 + Mex+ ↔ gyrolite-Me0 + Ca2+. It was observed that the pseudo second order model fit well for iron and nickel ions adsorption mechanism. It was estimated that the adsorption reactions are not reversible process and the crystal structure of gyrolite is stable. Moreover, synthetic adsorbent and the products of sorption were characterized by XRD, STA and FT-IR methods.DOI: http://dx.doi.org/10.5755/j01.ms.21.1.5735

  9. Effects of heating rate on slow pyrolysis behavior, kinetic parameters and products properties of moso bamboo.

    Science.gov (United States)

    Chen, Dengyu; Zhou, Jianbin; Zhang, Qisheng

    2014-10-01

    Effects of heating rate on slow pyrolysis behaviors, kinetic parameters, and products properties of moso bamboo were investigated in this study. Pyrolysis experiments were performed up to 700 °C at heating rates of 5, 10, 20, and 30 °C/min using thermogravimetric analysis (TGA) and a lab-scale fixed bed pyrolysis reactor. The results show that the onset and offset temperatures of the main devolatilization stage of thermogravimetry/derivative thermogravimetry (TG/DTG) curves obviously shift toward the high-temperature range, and the activation energy values increase with increasing heating rate. The heating rate has different effects on the pyrolysis products properties, including biochar (element content, proximate analysis, specific surface area, heating value), bio-oil (water content, chemical composition), and non-condensable gas. The solid yields from the fixed bed pyrolysis reactor are noticeably different from those of TGA mainly because the thermal hysteresis of the sample in the fixed bed pyrolysis reactor is more thorough.

  10. Kinetic parameters and tissue distribution of 5-oxo-L-prolinase determined by a fluorimetric assay.

    Science.gov (United States)

    Weber, P; Jäger, M; Bangsow, T; Knell, G; Piechaczek, K; Koch, J; Wolf, S

    1999-01-13

    5-Oxo-L-prolinase (5-OPase) catalyses the hydrolysis of 5-oxo-L-proline to glutamate with concomitant stoichiometric cleavage of ATP to ADP, a reaction which is known to be part of the gamma-glutamyl cycle-an interrelated series of reactions involved in the synthesis and metabolism of glutathione. As recent studies indicate, this cyclic pathway plays a crucial role in the regulation of amino acid transport. Apparently, the intermediate product 5-oxo-L-proline functions as a second messenger molecule that upregulates the activity of certain amino acid transport systems. Thus, the degradation of 5-oxo-L-proline by 5-OPase leads to the downregulation of this stimulus. In this study, a new sensitive fluorimetric assay for 5-OPase activity was established which is based on the derivatization of glutamate with o-phthaldialdehyde in the presence of thiols and subsequent separation of the products by HPLC. The method is suitable for the screening of chromatography fractions as well as for the determination of the kinetic parameters Km and Vmax of purified 5-OPase. Additionally, it can be used for the measurement of enzyme activity in crude cell extracts and evaluation of tissue distribution.

  11. Kinetic parameters of biomass growth in a UASB reactor treating wastewater from coffee wet processing (WCWP

    Directory of Open Access Journals (Sweden)

    Claudio Milton Montenegro Campos

    2014-10-01

    Full Text Available This study evaluated the treatment of wastewater from coffee wet processing (WCWP in an anaerobic treatment system at a laboratory scale. The system included an acidification/equalization tank (AET, a heat exchanger, an Upflow Anaerobic Sludge Blanket Reactor (UASB, a gas equalization device and a gas meter. The minimum and maximum flow rates and volumetric organic loadings rate (VOLR were 0.004 to 0.037 m 3 d -1 and 0.14 to 20.29 kgCOD m -3 d -1 , respectively. The kinetic parameters measured during the anaerobic biodegradation of the WCWP, with a minimal concentration of phenolic compounds of 50 mg L - ¹, were: Y = 0.37 mgTVS (mgCODremoved -1 , Kd = 0.0075 d-1 , Ks = 1.504mg L -1 , μmax = 0.2 d -1 . The profile of sludge in the reactor showed total solids (TS values from 22,296 to 55,895 mg L -1 and TVS 11,853 to 41,509 mg L -1 , demonstrating a gradual increase of biomass in the reactor during the treatment, even in the presence of phenolic compounds in the concentration already mentioned.

  12. Estimating kinetic parameters from dynamic contrast-enhanced T(1)-weighted MRI of a diffusable tracer: standardized quantities and symbols

    DEFF Research Database (Denmark)

    Tofts, P.S.; Brix, G; Buckley, D.L.

    1999-01-01

    We describe a standard set of quantity names and symbols related to the estimation of kinetic parameters from dynamic contrast-enhanced T(1)-weighted magnetic resonance imaging data, using diffusable agents such as gadopentetate dimeglumine (Gd-DTPA). These include a) the volume transfer constant K...

  13. Analysis, evaluation, and optimization of kinetic parameters for performance appraisal and design of UASB reactors.

    Science.gov (United States)

    Bhunia, Puspendu; Ghangrekar, M M

    2008-05-01

    Studies have been undertaken to explore the applicability of different kinetic models for the performance appraisal of upflow anaerobic sludge blanket (UASB) reactors treating wastewater in the range of 300-4000 mg COD/l. Three kinetic models namely, Monod, Grau second-order, and Haldane model are considered for the analysis. Both linear and nonlinear regressions have been performed to examine the best-fit among the kinetic models. In this process, five error analysis methods have been used to analyze the data. Apart from optimization of kinetic coefficients with minimization of associated errors, prediction of effluent COD has also been undertaken to verify the applicability of kinetic models. In both the cases, Grau second-order model is found to be the best class of fit for wide range of data sets in UASB reactor.

  14. Comparisons of selected methods for the determination of kinetic parameters from electrothermal atomic absorption data

    Science.gov (United States)

    Fonseca, Rodney W.; Pfefferkorn, Lisa L.; Holcombe, James A.

    1994-12-01

    Three of the methods available for the determination of kinetic parameters for atom formation in ETAAS were compared. In the approach of mcnally and holcombe [ Anal. Chem. 59, 1015 (1987)], Arrhenius-type plots are used to extract activation energy values while an approximation of the order of release is obtained by studying the alignment of the absorption maxima at increasing analyte concentrations. In the method of rojas and olivares [ Spectrochim. Acta47B, 387 (1992)], plots are prepared for different orders of release, with the correct order yielding a longer linear region from whose slope the activation energy is calculated. The method of yan et al. [ Spectrochim. Acta48B, 605 (1993)] uses a single absorption profile for the calculations. Activation energy and the order of release are obtained from the slope and intercept, respectively, on their graph. All three methods assume linear heating rate, constant activation energies, and furnace isothermality. The methods were tested with the same experimental data sets for Cu, Au and Ni using a spatially isothermal cuvette. Since intensive mathematical treatments commonly have deleterious effects on the uncertainty of the final result, the methods were compared using both the original data and a smoothed version of it. In general, the three methods yielded comparable results for the metals studied. However, choosing the most linear plot to determine the correct order of release when using Rojas and Olivares' method was sometimes subjective, and McNally and Holcombe's method provided only estimates for the orders of release that were neither zero nor unity.

  15. Evaluation of mass-transfer and kinetic parameters for Rhodospirillum rubrum in a continuous stirred tank reactor

    Energy Technology Data Exchange (ETDEWEB)

    Klasson, K.T. (Oak Ridge National Lab., TN (United States)); Gupta, A.; Clausen, E.C.; Gaddy, J.L. (Univ. of Arkansas, Fayetteville, AR (United States))

    The photosynthetic bacterium Rhodospirillum rubrum has been evaluated for its ability to produce hydrogen from carbon monoxide and water in a continuous stirred tank reactor according to the water-gas shift reaction. An assessment of mass-transfer parameters and reaction kinetics was made for this sparingly soluble substrate system. Experiments were conducted in a nonsteady-state fashion with continuous liquid and gas flow, which allowed for separation of the mass-transfer and kinetic-limited regions. Based on the data obtained, mass-transfer coefficients for the system were determined, and a mathematical expression for the reaction kinetics was formulated. The results showed that the hydrogen production was inhibited by elevated levels of dissolved carbon monoxide in the liquid. 8 refs., 4 figs., 1 tab.

  16. Comparison of Parameter Estimations Using Dual-Input and Arterial-Input in Liver Kinetic Studies of FDG Metabolism.

    Science.gov (United States)

    Cui, Yunfeng; Bai, Jing

    2005-01-01

    Liver kinetic study of [18F]2-fluoro-2-deoxy-D-glucose (FDG) metabolism in human body is an important tool for functional modeling and glucose metabolic rate estimation. In general, the arterial blood time-activity curve (TAC) and the tissue TAC are required as the input and output functions for the kinetic model. For liver study, however, the arterial-input may be not consistent with the actual model input because the liver has a dual blood supply from the hepatic artery (HA) and the portal vein (PV) to the liver. In this study, the result of model parameter estimation using dual-input function is compared with that using arterial-input function. First, a dynamic positron emission tomography (PET) experiment is performed after injection of FDG into the human body. The TACs of aortic blood, PV blood, and five regions of interest (ROIs) in liver are obtained from the PET image. Then, the dual-input curve is generated by calculating weighted sum of both the arterial and PV input curves. Finally, the five liver ROIs' kinetic parameters are estimated with arterial-input and dual-input functions respectively. The results indicate that the two methods provide different parameter estimations and the dual-input function may lead to more accurate parameter estimation.

  17. Determination of char combustion kinetics parameters: Comparison of point detector and imaging-based particle-sizing pyrometry

    Science.gov (United States)

    Schiemann, Martin; Geier, Manfred; Shaddix, Christopher R.; Vorobiev, Nikita; Scherer, Viktor

    2014-07-01

    In this study, the char burnout characteristics of two German coals (a lignite and a high-volatile bituminous coal) were investigated using two different experimental configurations and optical techniques in two distinct laboratories for measurement of temperature and size of burning particles. The optical diagnostic hardware is quite different in the two systems, but both perform two-color pyrometry and optical sizing measurements on individual particles burning in isolation from each other in high-temperature laminar flows to characterize the char consumption kinetics. The performance of the specialized systems is compared for two different combustion atmospheres (with 6.6 and 12 vol.% O2) and gas temperatures between 1700 and 1800 K. The measured particle temperatures and diameters are converted to char burning rate parameters for several residence times during the course of the particles' burnout. The results confirm that comparable results are obtained with the two configurations, although higher levels of variability in the measured data were observed in the imaging-based pyrometer setup. Corresponding uncertainties in kinetics parameters were larger, and appear to be more sensitive to systematic measurement errors when lower oxygen contents are used in the experiments. Consequently, burnout experiments in environments with sufficiently high O2 contents may be used to measure reliable char burning kinetics rates. Based on simulation results for the two coals, O2 concentrations in the range 10%-30% are recommended for kinetic rate measurements on 100 μm particles.

  18. Kinetic Parameters of Methane Generated from Source Rocks in the Kuqa Depression of Tarim Basin and Their Application

    Institute of Scientific and Technical Information of China (English)

    LI Xianqing; DONG Peng; XIAO Xianming; MI Jingkui; TANG Yongchun; XIAO Zhongyao; LIU Dehan; SHEN Jiagui; YANG Yunfeng; WANG Yan

    2008-01-01

    In a thermal simulation experiment of gold tubes of closed-system, calculating with the KINETICS and GOR-ISOTOPE KINETICS software, kinetic parameters of gas generation and methane carbon isotopic fractionation from Triassic-Jurassic hydrocarbon source rocks in the Kuqa depression of Tarim Basin are obtained. The activation energies of methane generated from Jurassic coal, Jurassic mudstone and Triassic mudstone in the Kuqa Depression are 197-268 kJ/mol, 180-260 kJ/mol and 214-289 kJ/mol, respectively, and their frequency factors are 5.265×1013s-1, 9.761×1011 s-1 and 2.270×1014 s-1. This reflects their differences of hydrocarbon generation behaviors. The kinetic parameters of methane carbon isotopic fractionation are also different in Jurassic coal, Jurassic mudstone and Triassic mudstone, whose average activation energies are 228 kJ/mol, 205 kJ/mol and 231 kJ/mol, respectively. Combined with the geological background, the origin of natural gas in the Yinan-2 gas pool is discussed, and an accumulation model of natural gas is thus established. The Yinan-2 gas is primarily derived from Jurassic coal-bearing source rocks in the Yangxia Sag. Main gas accumulation time is 5-0 Ma and the corresponding Ro is in the range from 1.25%-1.95%. The loss rate of natural gas is 25%-30%.

  19. Estimation of the kinetic parameters for thermal decomposition of HNIW and its adiabatic time-to-explosion by Kooij formula

    Institute of Scientific and Technical Information of China (English)

    Hong-xu GAO; Feng-qi ZHAO; Rong-zu HU; Hong-an ZHAO; Hai ZHANG

    2014-01-01

    A differential/integral method to estimate the kinetic parameters (apparent activation energy Ea and pre-exponential factor A) for thermal decomposition reaction of energetic materials based on Kooij formula are applied to study the nonisothermal decomposition reaction kinetics of hexanitrohexaazaisowurtzitane (HNIW) by analyzing nonisothermal DSC curve data. The apparent activation energy (Ea) obtained by the in-tegral isoconversional non-isothermal method based on Kooij formula is used to check the constancy and validity of apparent activation energy by the differential/integral method based on Kooij formula. The most probable mechanism function of thermal decomposition reaction of HNIW is determined by a logical choice method. The equations for calculating the critical temperatures of thermal explosion (Tb) and adiabatic time-to-explosion (tTIad) based on Kooij formula are used to calculate the values of Tb and tTIad to evaluate the thermal safety and heat-resistant ability of HNIW. All the original data needed for analyzing the kinetic parameters are from nonisothermal DSC curves. The results show that the kinetic model function in differential form and the values of Ea and A of decomposition reaction of HNIW are 3(1 ? a)[?ln(1 ? a)]2/3, 152.73 kJ mol?1 and 1011.97 s?1, respectively, and the values of self-accelerating decomposition temperature (TSADT), Tb and tTIad are 486.55 K, 493.11 K and 52.01 s, respectively.

  20. Chemical Characterization and Kinetic parameter determination under Rancimat test conditions of four monovarietal virgin olive oils grown in Morocco

    Directory of Open Access Journals (Sweden)

    Gharby Said

    2016-07-01

    Full Text Available The aim of the present investigation is to compare the chemical characterization of four monovarietal virgin olive oils obtained from fruits of olive trees grown in Morocco (Picholine, Picual, Arebiquine, Koroneiki with kinetic parameters of oxidation based on Rancimat measurements and finally to assess the oxidative stabilities. The examined oils from different varieties showed a chemical composition within the regulatory limits. Rancimat measurements of induction times were carried out under isothermal conditions in an air atmosphere at temperatures from 373 to 423 K with intervals of 10 K. Using the Arrhenius-type correlation between the inverse induction times and the absolute temperature of the measurements, Ea, Z, and k values for oil oxidation under Rancimat conditions were calculated. The primary kinetic parameters derived from this method were qualitatively consistent and help to evaluate the oxidative stabilities of oils at increased temperatures.

  1. Reproducibility of VPCT parameters in the normal pancreas: comparison of two different kinetic calculation models.

    Science.gov (United States)

    Kaufmann, Sascha; Schulze, Maximilian; Horger, Thomas; Oelker, Aenne; Nikolaou, Konstantin; Horger, Marius

    2015-09-01

    To assess the reproducibility of volume computed tomographic perfusion (VPCT) measurements in normal pancreatic tissue using two different kinetic perfusion calculation models at three different time points. Institutional ethical board approval was obtained for retrospective analysis of pancreas perfusion data sets generated by our prospective study for liver response monitoring to local therapy in patients experiencing unresectable hepatocellular carcinoma, which was approved by the institutional review board. VPCT of the entire pancreas was performed in 41 patients (mean age, 64.8 years) using 26 consecutive volume measurements and intravenous injection of 50 mL of iodinated contrast at a flow rate of 5 mL/s. Blood volume(BV) and blood flow (BF) were calculated using two mathematical methods: maximum slope + Patlak analysis versus deconvolution method. Pancreas perfusion was calculated using two volume of interests. Median interval between the first and the second VPCT was 2 days and between the second and the third VPCT 82 days. Variability was assessed with within-patient coefficients of variation (CVs) and Bland-Altman analyses. Interobserver agreement for all perfusion parameters was calculated using intraclass correlation coefficients (ICCs). BF and BV values varied widely by method of analysis as did within-patient CVs for BF and BV at the second versus the first VPCT by 22.4%/50.4% (method 1) and 24.6%/24.0% (method 2) measured in the pancreatic head and 18.4%/62.6% (method 1) and 23.8%/28.1% (method 2) measured in the pancreatic corpus and at the third versus the first VPCT by 21.7%/61.8% (method 1) and 25.7%/34.5% (method 2) measured also in the pancreatic head and 19.1%/66.1% (method 1) and 22.0%/31.8% (method 2) measured in the pancreatic corpus, respectively. Interobserver agreement measured with ICC shows fair-to-good reproducibility. VPCT performed with the presented examinational protocol is reproducible and can be used for monitoring

  2. Fourier domain closed-form formulas for estimation of kinetic parameters in reversible multi-compartment models

    Directory of Open Access Journals (Sweden)

    Zeng Gengsheng L

    2012-09-01

    Full Text Available Abstract Background Compared with static imaging, dynamic emission computed tomographic imaging with compartment modeling can quantify in vivo physiologic processes, providing useful information about molecular disease processes. Dynamic imaging involves estimation of kinetic rate parameters. For multi-compartment models, kinetic parameter estimation can be computationally demanding and problematic with local minima. Methods This paper offers a new perspective to the compartment model fitting problem where Fourier linear system theory is applied to derive closed-form formulas for estimating kinetic parameters for the two-compartment model. The proposed Fourier domain estimation method provides a unique solution, and offers very different noise response as compared to traditional non-linear chi-squared minimization techniques. Results The unique feature of the proposed Fourier domain method is that only low frequency components are used for kinetic parameter estimation, where the DC (i.e., the zero frequency component in the data is treated as the most important information, and high frequency components that tend to be corrupted by statistical noise are discarded. Computer simulations show that the proposed method is robust without having to specify the initial condition. The resultant solution can be fine tuned using the traditional iterative method. Conclusions The proposed Fourier-domain estimation method has closed-form formulas. The proposed Fourier-domain curve-fitting method does not require an initial condition, it minimizes a quadratic objective function and a closed-form solution can be obtained. The noise is easier to control, simply by discarding the high frequency components, and emphasizing the DC component.

  3. Influence of doping on the microstructure and kinetic parameters of GaSb-FeGa1.3 eutectics

    Science.gov (United States)

    Mamedov, I. Kh.; Ragimov, R. N.; Khalilova, A. A.; Arasly, D. G.; Aliev, M. I.

    2012-12-01

    Electron microscopy and X-ray spectroscopy analysis of GaSb-FeGa1.3 eutectic composite doped with tellurium atoms is performed. It is established that doping changes the GaSb-FeGa1.3 eutectics microstructure; sizes, shape, and density of FeGa1.3 metallic inclusions; and the interface regions between the matrix and inclusions. Influence of doping on the anisotropy of kinetic parameters is shown.

  4. Determination of kinetic parameters of 1,3-propanediol fermentation by Clostridium diolis using statistically optimized medium.

    Science.gov (United States)

    Kaur, Guneet; Srivastava, Ashok K; Chand, Subhash

    2012-09-01

    1,3-propanediol (1,3-PD) is a chemical compound of immense importance primarily used as a raw material for fiber and textile industry. It can be produced by the fermentation of glycerol available abundantly as a by-product from the biodiesel plant. The present study was aimed at determination of key kinetic parameters of 1,3-PD fermentation by Clostridium diolis. Initial experiments on microbial growth inhibition were followed by optimization of nutrient medium recipe by statistical means. Batch kinetic data from studies in bioreactor using optimum concentration of variables obtained from statistical medium design was used for estimation of kinetic parameters of 1,3-PD production. Direct use of raw glycerol from biodiesel plant without any pre-treatment for 1,3-PD production using this strain investigated for the first time in this work gave results comparable to commercial glycerol. The parameter values obtained in this study would be used to develop a mathematical model for 1,3-PD to be used as a guide for designing various reactor operating strategies for further improving 1,3-PD production. An outline of protocol for model development has been discussed in the present work.

  5. Thermal hydrocracking of indan. Effects of the hydrogen pressure on the kinetics and Arrhenius parameters

    NARCIS (Netherlands)

    Boven, van M.; Roskam, G.J.; Penninger, J.M.L.

    1975-01-01

    The kinetics of the thermal hydrocracking of indan were investigatedin a high-pressure flow reactor at temperatures from 470 to 530°C, total pressures of up to 300 atm, and molar ratios from 3 to 40. The effect of the hydrogen pressure was reflected especially in a change of the experimental rate eq

  6. Determination of Kinetic Parameters of Coal Pyrolysis to Simulate the Process of Underground Coal Gasification (UCG

    Directory of Open Access Journals (Sweden)

    Beata Urych

    2014-01-01

    Originality/value: The devolatilization of a homogenous lump of coal is a complex issue. Currently, the CFD technique (Computational Fluid Dynamics is commonly used for the multi-dimensional and multiphase phenomena modelling. The mathematical models, describing the kinetics of the decomposition of coal, proposed in the article can, therefore, be an integral part of models based on numerical fluid mechanics.

  7. How is the Monoclonal Antibodies Kinetic Affected by Changes of Their Physical Parameters?

    CERN Document Server

    Delgado-Correal, Camilo; Lizarazo-Pérez, Heidy Alexandra

    2010-01-01

    The study of monoclonal antibodies (MAb) is a field of great interest to science medicine, for example, anti-TNF agents (infliximab and adalimumab) represent an important tool for the management of autoimmune and inflammatory disorders. In this work we focus on the physical description of the transport kinetics of MAb in a fluid with laminar flow and parabolic profile. To simulate the kinetics of the MAb, standard equations were solved numerically (using The Verlet algorithm) to calculate the motion of a particle with a spherically symmetric inside of parabolic laminar flow, in order to find the time evolution of the antibody velocity in blood plasma in function of the increase of the radius, mass and density of the MAb, and the fluid pressure in blood vessels. In the case of we fixed the value of the antibody density, their kinetics increased when the pressure in the vessels increased. When we fixed the pressure in the vessels we found: if we reduce the antibody radius their kinetics increased, and when we i...

  8. Thermal hydrocracking of indan. Effects of the hydrogen pressure on the kinetics and Arrhenius parameters

    NARCIS (Netherlands)

    van Boven, M.; Roskam, G.J.; Penninger, J.M.L.

    1975-01-01

    The kinetics of the thermal hydrocracking of indan were investigatedin a high-pressure flow reactor at temperatures from 470 to 530°C, total pressures of up to 300 atm, and molar ratios from 3 to 40. The effect of the hydrogen pressure was reflected especially in a change of the experimental rate

  9. 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 par....... (C) 2009 Elsevier B.V. All rights reserved....

  10. Time of erythema onset after application of methyl nicotinate ointments as response parameter: influence of penetration kinetics and enhancing agents.

    Science.gov (United States)

    Remane, Y; Leopold, C S

    2006-01-01

    The time of erythema onset may be used as a response parameter for quantification of the cutaneous erythema response induced by methyl nicotinate. The vehicles light mineral oil (LMO; test) and medium chain triglycerides (MCT; standard) were compared with regard to the pharmacodynamic response. Moreover, the influence of penetration enhancers on the time of erythema onset was investigated under zero order penetration kinetics. The enhancers dimethyl sulfoxide, diethylene glycol monoethyl ether and three different glycerides in different concentrations were added to MCT as a standard vehicle. All preparations were applied to the forearms of volunteers under infinite dose conditions at different thermodynamic drug activity levels (0.2-3.2% of the saturation level) and different drug concentrations (0.051-0.816%), respectively. Different penetration kinetics do not influence data of erythema onset, as these data are comparable to those obtained under finite dose conditions (first order penetration kinetics). With regard to the penetration enhancers, a significantly enhanced penetration of methyl nicotinate could be observed only for diethylene glycol monoethyl ether and dimethyl sulfoxide. However, no significant difference between light mineral oil and MCT could be found with regard to penetration enhancement. The time of erythema onset is an easy and efficient parameter for quantification of the pharmacodynamic response caused by nicotinates.

  11. Combined Yamamoto approach for simultaneous estimation of adsorption isotherm and kinetic parameters in ion-exchange chromatography.

    Science.gov (United States)

    Rüdt, Matthias; Gillet, Florian; Heege, Stefanie; Hitzler, Julian; Kalbfuss, Bernd; Guélat, Bertrand

    2015-09-25

    Application of model-based design is appealing to support the development of protein chromatography in the biopharmaceutical industry. However, the required efforts for parameter estimation are frequently perceived as time-consuming and expensive. In order to speed-up this work, a new parameter estimation approach for modelling ion-exchange chromatography in linear conditions was developed. It aims at reducing the time and protein demand for the model calibration. The method combines the estimation of kinetic and thermodynamic parameters based on the simultaneous variation of the gradient slope and the residence time in a set of five linear gradient elutions. The parameters are estimated from a Yamamoto plot and a gradient-adjusted Van Deemter plot. The combined approach increases the information extracted per experiment compared to the individual methods. As a proof of concept, the combined approach was successfully applied for a monoclonal antibody on a cation-exchanger and for a Fc-fusion protein on an anion-exchange resin. The individual parameter estimations for the mAb confirmed that the new approach maintained the accuracy of the usual Yamamoto and Van Deemter plots. In the second case, offline size-exclusion chromatography was performed in order to estimate the thermodynamic parameters of an impurity (high molecular weight species) simultaneously with the main product. Finally, the parameters obtained from the combined approach were used in a lumped kinetic model to simulate the chromatography runs. The simulated chromatograms obtained for a wide range of gradient lengths and residence times showed only small deviations compared to the experimental data.

  12. Evaluation of reaction mechanisms and the kinetic parameters for the transesterification of castor oil by liquid enzymes

    DEFF Research Database (Denmark)

    Andrade, Thalles Allan; Errico, Massimiliano; Christensen, Knud Villy

    2017-01-01

    The use of liquid enzymes for the production of biodiesel as an alternative to chemical catalysts requires significant investigation due to the lack of experimental data for the various feedstock and catalyst combinations. In this paper, reaction rates and kinetic modeling...... of the transesterification of castor oil with methanol using the enzyme Eversa® Transform as catalyst were investigated. Reactions were carried out for 8 hours at 35 °C with: an alcohol-to-oil molar ratio equal to 6:1, a 5 wt% of liquid enzyme solution and addition of 5 wt% of water by weight of castor oil. From...... methanolysis rates of glycerides obtained, indicated that transesterification dominates over hydrolysis. The mechanism among the four models proposed that gave the best fit could be simplified, eliminating the kinetic parameters with negligible effects on the reaction rates. This model was able to fit...

  13. Methods for calculating the kinetic parameters of carbonate decomposition from thermal analysis data

    Science.gov (United States)

    Artamonova, I. V.; Gorichev, I. G.; Lainer, Yu. A.; Godunov, E. B.; Kramer, S. M.; Terekhova, M. V.

    2016-07-01

    A procedure is proposed for an analysis of the data on the decomposition of inorganic carbonates (MgCO3, CaCO3, SrCO3, MnCO3, CoCO3) on the basis of results of thermogravimetric studies. The activation energy and the rate constant for carbonate decomposition are calculated taking into account the main points of the heterogeneous reaction kinetics. A comparative analysis of the obtained results is performed.

  14. Estimation of the kinetic parameters for thermal decomposition of HNIW and its adiabatic time-to-explosion by Kooij formula

    Directory of Open Access Journals (Sweden)

    Hong-xu Gao

    2014-03-01

    Full Text Available A differential/integral method to estimate the kinetic parameters (apparent activation energy Ea and pre-exponential factor A for thermal decomposition reaction of energetic materials based on Kooij formula are applied to study the nonisothermal decomposition reaction kinetics of hexanitrohexaazaisowurtzitane (HNIW by analyzing nonisothermal DSC curve data. The apparent activation energy (Ea obtained by the integral isoconversional non-isothermal method based on Kooij formula is used to check the constancy and validity of apparent activation energy by the differential/integral method based on Kooij formula. The most probable mechanism function of thermal decomposition reaction of HNIW is determined by a logical choice method. The equations for calculating the critical temperatures of thermal explosion (Tb and adiabatic time-to-explosion (tTIad based on Kooij formula are used to calculate the values of Tb and tTIad to evaluate the thermal safety and heat-resistant ability of HNIW. All the original data needed for analyzing the kinetic parameters are from nonisothermal DSC curves. The results show that the kinetic model function in differential form and the values of Ea and A of decomposition reaction of HNIW are 3(1 − α[−ln(1 − α]2/3, 152.73 kJ mol−1 and 1011.97 s−1, respectively, and the values of self-accelerating decomposition temperature (TSADT, Tb and tTIad are 486.55 K, 493.11 K and 52.01 s, respectively.

  15. A comparison of region-based and pixel-based CEUS kinetics parameters in the assessment of arthritis

    Science.gov (United States)

    Grisan, E.; Raffeiner, B.; Coran, A.; Rizzo, G.; Ciprian, L.; Stramare, R.

    2014-03-01

    Inflammatory rheumatic diseases are leading causes of disability and constitute a frequent medical disorder, leading to inability to work, high comorbidity and increased mortality. The gold-standard for diagnosing and differentiating arthritis is based on patient conditions and radiographic findings, as joint erosions or decalcification. However, early signs of arthritis are joint effusion, hypervascularization and synovial hypertrophy. In particular, vascularization has been shown to correlate with arthritis' destructive behavior, more than clinical assessment. Contrast Enhanced Ultrasound (CEUS) examination of the small joints is emerging as a sensitive tool for assessing vascularization and disease activity. The evaluation of perfusion pattern rely on subjective semi-quantitative scales, that are able to capture the macroscopic degree of vascularization, but are unable to detect the subtler differences in kinetics perfusion parameters that might lead to a deeper understanding of disease progression and a better management of patients. Quantitative assessment is mostly performed by means of the Qontrast software package, that requires the user to define a region of interest, whose mean intensity curve is fitted with an exponential function. We show that using a more physiologically motivated perfusion curve, and by estimating the kinetics parameters separately pixel per pixel, the quantitative information gathered is able to differentiate more effectively different perfusion patterns. In particular, we will show that a pixel-based analysis is able to provide significant markers differentiating rheumatoid arthritis from simil-rheumatoid psoriatic arthritis, that have non-significant differences in clinical evaluation (DAS28), serological markers, or region-based parameters.

  16. Reliability and Validity of Kinetic and Kinematic Parameters Determined With Force Plates Embedded Under Soil-Filled Baseball Mound.

    Science.gov (United States)

    Yanai, Toshimasa; Matsuo, Akifumi; Maeda, Akira; Nakamoto, Hiroki; Mizutani, Mirai; Kanehisa, Hiroaki; Fukunaga, Tetsuo

    2017-01-13

    We developed a force measurement system in a soil-filled mound for measuring ground reaction forces (GRFs) acting on baseball pitchers and examined the reliability and validity of kinetic and kinematic parameters determined from the GRFs. Three soil-filled trays of dimensions that satisfied the official baseball rules were fixed onto three force platforms. Eight collegiate pitchers wearing baseball shoes with metal cleats were asked to throw 5 fastballs with maximum effort from the mound toward a catcher. The reliability of each parameter was determined for each subject as the coefficient of variation across the 5 pitches. The validity of the measurements was tested by comparing the outcomes either with the true values or the corresponding values computed from a motion capture system. The coefficients of variation in the repeated measurements of the peak forces ranged from 0.00 to 0.17, and were smaller for the pivot foot than the stride foot. The mean absolute errors in the impulses determined over entire duration of pitching motion were 5.3 N·s, 1.9 N·s, and 8.2 N·s for the X-, Y-, and Z-directions, respectively. These results suggest that the present method is reliable and valid for determining selected kinetic and kinematic parameters for analyzing pitching performance.

  17. Model description and kinetic parameter analysis of MTBE biodegradation in a packed bed reactor

    DEFF Research Database (Denmark)

    Waul, Christopher Kevin; Arvin, Erik; Schmidt, Jens Ejbye

    2008-01-01

    A dynamic modeling approach was used to estimate in-situ model parameters, which describe the degradation of methyl tert-butyl ether (MTBE) in a laboratory packed bed reactor. The measured dynamic response of MTBE pulses injected at the reactor's inlet was analyzed by least squares and parameter...

  18. Isolation of liver aldehyde oxidase containing fractions from different animals and determination of kinetic parameters for benzaldehyde

    Directory of Open Access Journals (Sweden)

    Kadam R

    2008-01-01

    Full Text Available Aldehyde oxidase activity containing fractions from rabbit, guinea pig, rat and mouse livers were obtained by heat treatment and ammonium sulfate precipitation. Aldehyde oxidase activity was observed in rabbit and guinea pig livers, while aldehyde oxidase activity was absent in rat and mouse liver fractions. Enzyme kinetic parameters, K m and V max , were determined for the oxidation of benzaldehyde to benzoic acid by rabbit and guinea pig liver fractions, by spectrophotometric method, with potassium ferricyanide as the electron acceptor. The K m values obtained for both animal liver fractions were in the range of 10.3-19.1 µM.

  19. KINETICS AND EQUILIBRIUM PARAMETERS OF BIOSORPTION AND BIOACCUMULATION OF LEAD IONS FROM AQUEOUS SOLUTIONS BY TRICHODERMA LONGIBRACHIATUM

    Directory of Open Access Journals (Sweden)

    Enitan S. Balogun

    2012-04-01

    Full Text Available Biosorption and bioaccumulation of Lead ions (Pb(II by Trichoderma longibrachiatum were investigated in a batch system. The effects of some important parameters such as pH, initial metal concentration, temperature and inoculum concerntration on biosorption capacity were also studied. The maximum biosorption capacity of Trichoderma longibrachiatum was at 25 ppm of lead, showed 100 % removal at pH 7 and 25 oC after fifteen days. Biosorption equilibrium was established in 150 minutes. The process fitted well into pseudo second order kinetic model and was best explained by Langmuir isotherm.

  20. Effect of Temperature and pH on Formulating the Kinetic Growth Parameters and Lactic Acid Production of Lactobacillus bulgaricus

    Directory of Open Access Journals (Sweden)

    Marzieh Aghababaie

    2014-09-01

    Results: Second order model for Xmax, μmax, P and K was significant but product formation parameters were almost constant. The optimum values of temperature and pH for attaining maximum biomass, maximum specific growth rate, and maximum acid production were obtained at 44 °C and 5.7, respectively. Conclusions: The attained empirical mathematical correlations of RSM alongside the kinetic equations could be used to determine growth conditions under predefined temperature and pH in the fermentation process. Keywords: Lactobacillus bulgaricus, Richards model, Response surface methodology, Lactic acid production, Luedeking-Piret model

  1. Kinetic parameters of oscillating reaction of amino acid-BrO-3-Mn2+-H2SO4-acetone system

    Institute of Scientific and Technical Information of China (English)

    LI Zongxiao; YUAN Chunlan; NIE Fei

    2005-01-01

    The oscillating behavior of thirteen amino acids [leucine (Leu), threonine (Thr), arginine (Arg), lysine (Lys), histidine (His), alanine (Ala), glutamine (Glu), glycine (Gly), methionine (Met), cystine (Cys), tryptophan (Trp), serine (Ser) and tyrosine (Tyr)] in amino acid--Mn2+-H2SO4-acetone system is studied by using a potentiometric determination. With the help of the oscillatory induction period and oscillation period obtained by the oscillating wave, and Arrhenius equation, the kinetic parameters [the apparent activation energy (E) and pre-exponential constant (A)] and rate constant (k) of the above-mentioned oscillating reaction are estimated.

  2. Prediction of microbial growth rate versus biomass yield by a metabolic network with kinetic parameters.

    Science.gov (United States)

    Adadi, Roi; Volkmer, Benjamin; Milo, Ron; Heinemann, Matthias; Shlomi, Tomer

    2012-01-01

    Identifying the factors that determine microbial growth rate under various environmental and genetic conditions is a major challenge of systems biology. While current genome-scale metabolic modeling approaches enable us to successfully predict a variety of metabolic phenotypes, including maximal biomass yield, the prediction of actual growth rate is a long standing goal. This gap stems from strictly relying on data regarding reaction stoichiometry and directionality, without accounting for enzyme kinetic considerations. Here we present a novel metabolic network-based approach, MetabOlic Modeling with ENzyme kineTics (MOMENT), which predicts metabolic flux rate and growth rate by utilizing prior data on enzyme turnover rates and enzyme molecular weights, without requiring measurements of nutrient uptake rates. The method is based on an identified design principle of metabolism in which enzymes catalyzing high flux reactions across different media tend to be more efficient in terms of having higher turnover numbers. Extending upon previous attempts to utilize kinetic data in genome-scale metabolic modeling, our approach takes into account the requirement for specific enzyme concentrations for catalyzing predicted metabolic flux rates, considering isozymes, protein complexes, and multi-functional enzymes. MOMENT is shown to significantly improve the prediction accuracy of various metabolic phenotypes in E. coli, including intracellular flux rates and changes in gene expression levels under different growth rates. Most importantly, MOMENT is shown to predict growth rates of E. coli under a diverse set of media that are correlated with experimental measurements, markedly improving upon existing state-of-the art stoichiometric modeling approaches. These results support the view that a physiological bound on cellular enzyme concentrations is a key factor that determines microbial growth rate.

  3. Using the computerized glow curve deconvolution method and the R package tgcd to determination of thermoluminescence kinetic parameters of chilli powder samples by GOK model and OTOR one

    Science.gov (United States)

    Sang, Nguyen Duy; Van Hung, Nguyen; Van Hung, Tran; Hien, Nguyen Quoc

    2017-03-01

    The kinetic parameters of thermoluminescence (TL) glow peaks of chilli powder irradiated by gamma rays with the different doses of 0, 4 and 8 kGy have been calculated and estimate by computerized glow curve deconvolution (CGCD) method and the R package tgcd by using the TL glow curve data. The kinetic parameters of TL glow peaks (i.e. activation energies (E), order of kinetics (b), trapping and recombination probability coefficients (R) and frequency factors (s)) are fitted by modeled general-orders of kinetics (GOK) and one trap-one recombination (OTOR). The kinetic parameters of the chilli powder are different toward the difference of the sample time-storage, radiation doses, GOK model and OTOR one. The samples spending the shorter period of storage time have the smaller the kinetic parameters values than the samples spending the longer period of storage. The results obtained as comparing the kinetic parameters values of the three samples show that the value of non-irradiated samples are lowest whereas the 4 kGy irradiated-samples' value are greater than the 8 kGy irradiated-samples' one time.

  4. Influence of donor substrate on kinetic parameters of thiamine diphosphate binding to transketolase.

    Science.gov (United States)

    Ospanov, R V; Kochetov, G A; Kurganov, B I

    2007-01-01

    The two-step mechanism of interaction of thiamine diphosphate (ThDP) with transketolase (TK) has been studied: TK + ThDP TK...ThDP TK*-ThDP. The scheme involves the formation of inactive intermediate complex TK...ThDP followed by its transformation into catalytically active holoenzyme, TK*-ThDP. The dissociation and kinetic constants for individual stages of this process have been determined. The values of forward and backward rate constants change in the presence of the donor substrate hydroxypyruvate. This finally leads to an increase in the overall affinity of the coenzyme to TK.

  5. Study of reaction parameters and kinetics of esterification of lauric acid with butanol by immobilized Candida antarctica lipase.

    Science.gov (United States)

    Shankar, Sini; Agarwal, Madhu; Chaurasia, S P

    2013-12-01

    Esterification of lauric acid with n-butanol, catalyzed by immobilized Candida antarctica lipase (CAL) in aqueous-organic biphasic solvent system was studied. Effects of various reaction parameters on esterification were investigated, such as type and amount of solvent, amount of buffer, pH, temperature, speed of agitation, amount of enzyme, butanol and lauric acid. The most suitable reaction conditions for esterification were observed at 50 degrees C and pH 7.0 using 5000 micromoles of lauric acid, 7000 pmoles of butanol, 0.25 ml phosphate buffer, 1 ml of isooctane as the solvent and 50 mg of immobilized enzyme in the reaction medium at agitation speed of 150 rpm. Maximum esterification of 96.36% was acheived in 600 min of reaction time at n-butanol to lauric acid molar ratio of 1: 0.7. Kinetic study for the esterification of lauric acid with n-butanol using immobilized CAL was carried out and the kinetic constants were estimated by using non-linear regression method. The estimated value of Michaelis kinetic constants for butanol (KmBt) and acid (KmAc) were 451.56 (M) and 4.7 x 10(-7)(M), respectively and the value of dissociation constant (KBt) of the butanol-lipase complex was 9.41 x 10(7)(M). The estimated constants agreed fairly well with literature data.

  6. Degradation of carbofuran in aqueous solution by ultrasound and Fenton processes: Effect of system parameters and kinetic study.

    Science.gov (United States)

    Ma, Ying-Shih; Sung, Chi-Fanga; Lin, Jih-Gaw

    2010-06-15

    To establish an efficient oxidation process for carbofuran degradation, the effects of some operating parameters such as dosages of H(2)O(2), Fe(2+) and initial carbofuran concentrations were observed during carbofuran degradation by the ultrasound process, Fenton process and a combined ultrasound/Fenton process. The degradation kinetics of carbofuran was also examined based on the experimental data. The results show that more than 99% of the carbofuran was degraded by the ultrasound/Fenton process within short reaction time periods. Increased dosages of H(2)O(2) and Fe(2+) enhanced the degradation of carbofuran in the ultrasound and Fenton oxidation processes, but initial carbofuran concentrations decreased carbofuran degradation in both the Fenton and ultrasound/Fenton processes. The degradation kinetics of carbofuran by the three oxidation processes was found to be in accordance with first-order reaction kinetics. The results provide fundamental information about the treatment of carbofuran wastewater and/or other pesticides by the ultrasound/Fenton oxidation process.

  7. Kinetic approach and estimation of the parameters of cellular interaction between the immunity system and a tumor.

    Science.gov (United States)

    Kuznetsov, V A; Zhivoglyadov, V P; Stepanova, L A

    1993-01-01

    A method is suggested to estimate multi component dynamic systems, which permits, with the help of the computer-calculated kinetic curves, to obtain information about the possible mechanisms of the system component interaction. The method is based on the structural and parametrical identification of mathematical models presented in the form of a system of nonlinear differential equations, using a multi-criterial approach. Using experimental data of studies on growth kinetics and regression of multicellular tumor EMT6 line spheroids in the mouse allogenic system and the immune system cell accumulation in spheroids a mathematical model has been developed of the cellular interaction process in a spheroid. It has been stated that the rate of macrophage and neutrophil accumulation in a spheroid depends on the amount of tumor cells and is determined by the hyperbolic law (as analogous to the Michaelis-Menthen kinetics), while the accumulation of immune lymphocytes in a tumor is determined besides that by the three-cellular cooperation of lymphocytes, macrophages and tumor cells. According to the model, the inhibition of the process of neutrophil and lymphocyte (but not of macrophages) accumulation is realized through the auto-suppression mechanism. The numerical values of the process parameters, which characterise the rates of accumulation, cellular death in a tumor and of local cellular interactions intensity are obtained.

  8. The influence of estimated body segment parameters on predicted joint kinetics during diplegic cerebral palsy gait.

    Science.gov (United States)

    Kiernan, D; Walsh, M; O'Sullivan, R; O'Brien, T; Simms, C K

    2014-01-01

    Inverse Dynamic calculations are routinely used in joint moment and power estimates during gait with anthropometric data often taken from published sources. Many biomechanical analyses have highlighted the need to obtain subject-specific anthropometric data (e.g. Mass, Centre of Mass, Moments of Inertia) yet the types of imaging techniques required to achieve this are not always available in the clinical setting. Differences in anthropometric sets have been shown to affect the reactive force and moment calculations in normal subjects but the effect on a paediatric diplegic cerebral palsy group has not been investigated. The aim of this study was to investigate the effect of using different anthropometric sets on predicted sagittal plane moments during normal and diplegic cerebral palsy gait. Three published anthropometric sets were applied to the reactive force and moment calculations of 14 Cerebral Palsy and 14 Control subjects. Statistically significant differences were found when comparing the different anthropometric sets but variability in the resulting sagittal plane moment calculations between sets was low (0.01-0.07 Nm/kg). In addition, the GDI-Kinetic, used as an outcome variable to assess whether differences were clinically meaningful, indicated no clinically meaningful difference between sets. The results suggest that the effects of using different anthropometric sets on the kinetic profiles of normal and diplegic cerebral palsy subjects are clinically insignificant.

  9. Determination of the kinetic parameters of K{sub 2}YF{sub 5}:Tb from isothermal decay of thermoluminescence

    Energy Technology Data Exchange (ETDEWEB)

    Azorin, J. [Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada-IPN, Legaria 694 Col. Irrigacion, Mexico D.F. 11500 (Mexico); Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco, 186 Col. Vicentina, Mexico D.F. 09340 (Mexico)], E-mail: azorin@xanum.uam.mx; Gallegos, A.; Rivera, T.; Azorin, J.C. [Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada-IPN, Legaria 694 Col. Irrigacion, Mexico D.F. 11500 (Mexico); Khaidukov, N. [Institute of General and Inorganic Chemistry, Lenin SK 11 Prospect 31, Moscow 117907 (Russian Federation)

    2007-09-21

    Most of the existing methods for obtaining the frequency factors make use of the trap depth (activation energy) making assumptions about the order of the kinetics. This leads to inconsistencies in the reported values of trapping parameters as the values of the activation energy obtained by different methods differ appreciably among them. Then, it is necessary to employ a method independent of the trap depth as it is the case of the method that makes use of the isothermal decay of the thermoluminescence (TL). In this paper, the isothermal decay of TL was used to determine the trapping parameters of K{sub 2}YF{sub 5}:Tb. The results obtained by applying this method are in good agreement with those obtained using the glow curve shape method except in the value of the frequency factor.

  10. Estimation of biological kinetic parameters from an analysis of the BOD curve of waste waters - effects of a chemical preoxidation

    Energy Technology Data Exchange (ETDEWEB)

    Berlan, F.J.; Garcia-Araya, J.F.; Alvarez, P. [Universidad de Extremadura, Badajoz (Spain). Dept. de Ingenieria Quimica y Energetica

    1997-12-31

    Urban waste waters were treated with pure ozone or combinations of ozone, hydrogen peroxide and/or UV radiation to study the course of resulting BOD (biological oxygen demand)-time profiles and to propose a kinetic model. BOD-time profiles of chemically treated waste waters show an initial lag period that first order kinetic models cannot describe. A second order kinetic model is then proposed that satisfactorily fits experimental BOD-time profiles, except when hydrogen peroxide has been used. In these cases, BOD-time profiles present the highest lag periods observed. By applying this model, three parameters are determined: the biokinetic constant (k) which is an index of the biological removal rate; the potential amount of biodegradable matter (BOD{sub T}), and the measure of the size of inocula and microbial activities of microorganisms ({lambda}). The model was checked with experimental results of BOD-time profiles corresponding to both untreated and chemically ozonated urban waste waters. Ozonated waste waters showed the highest values of k and BOD{sub T}, which implies an improvement of waste water biodegradability after ozonation. However, values of {lambda} corrsponding to ozonated waste waters presented lower values than those of untreated waste waters. This was due to the lag period observed in the BOD-time profile, which was a consequence of a lack of micro-organism acclimation to ozonated waste waters. The effect of the ozone dose, pH and carbonates during oxonation on COD (chemical oxygen demand) and the above indicated parameters was also studies. The results suggest that ozonolysis, the direct molecular ozone way of reaction, due to its selective character, increases the biodegradability of waste water more than other chemically advancec oxidation processes based on hydroxyl radical reactions. (orig./SR)

  11. Adsorption of a cationic dye (Yellow Basic 28 ontothe calcined mussel shells: Kinetics, Isotherm and Thermodynamic Parameters

    Directory of Open Access Journals (Sweden)

    Imane EL Ouahabi

    2015-11-01

    Full Text Available The aim of this study is to valorise the mussel shells and evaluate the adsorption capacity of calcined mussel shells for the cationic dyes.  The adsorbent was characterized by DRX, FTIR, BET and SEM, respectively. The adsorption of Yellow Basic28 on calcined mussel shells was investigated using the parameters such as concentrations (10-50mg/L, pH (3-10, ionic strength (0-2 mol / L and temperature (288 - 318 °C.  The adsorption rate data were analysed according to the first and second-order kinetic models.  The adsorption kinetics was found to be best represented by the pseudo-second-order kinetic model.  The experimental isotherm data were analyzed using Langmuir, Freundlich, Temkin, Elovich and Dubinin–Radushkevich isotherm equations on the dye-adsorbent system. The experimental data yielded excellent fits with Freundlich isotherm equation (R² = 0.966. It was indicative of the heterogeneity of the adsorption sites on the CMS particles.  Various thermodynamic parameters such as enthalpy of adsorption ΔH°, free energy change ΔG°and entropy ΔS° were estimated.  The positive value of ΔH°(30.321 kJ/mol and negative values of ΔG° (from -5.392 to -2.873 kJ/mol show the process is endothermic and spontaneous.  The negative value of entropy ΔS° (-87.172 J/mol K suggest the decreased randomness at the solid-liquid interface during the adsorption of dyes onto calcined mussel shells.

  12. A benchmark on the calculation of kinetic parameters based on reactivity effect experiments in the CROCUS reactor

    Energy Technology Data Exchange (ETDEWEB)

    Paratte, J.M. [Laboratory for Reactor Physics and Systems Behaviour (LRS), Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland); Frueh, R. [Ecole Polytechnique Federale de Lausanne (EPFL), CH-1015 Lausanne (Switzerland); Kasemeyer, U. [Laboratory for Reactor Physics and Systems Behaviour (LRS), Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland); Kalugin, M.A. [Kurchatov Institute, 123182 Moscow (Russian Federation); Timm, W. [Framatome-ANP, D-91050 Erlangen (Germany); Chawla, R. [Laboratory for Reactor Physics and Systems Behaviour (LRS), Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland); Ecole Polytechnique Federale de Lausanne (EPFL), CH-1015 Lausanne (Switzerland)

    2006-05-15

    Measurements in the CROCUS reactor at EPFL, Lausanne, are reported for the critical water level and the inverse reactor period for several different sets of delayed supercritical conditions. The experimental configurations were also calculated by four different calculation methods. For each of the supercritical configurations, the absolute reactivity value has been determined in two different ways, viz.: (i) through direct comparison of the multiplication factor obtained employing a given calculation method with the corresponding value for the critical case (calculated reactivity: {rho} {sub calc}); (ii) by application of the inhour equation using the kinetic parameters obtained for the critical configuration and the measured inverse reactor period (measured reactivity: {rho} {sub meas}). The calculated multiplication factors for the reference critical configuration, as well as {rho} {sub calc} for the supercritical cases, are found to be in good agreement. However, the values of {rho} {sub meas} produced by two of the applied calculation methods differ appreciably from the corresponding {rho} {sub calc} values, clearly indicating deficiencies in the kinetic parameters obtained from these methods.

  13. [Molecular-kinetic parameters of thiamine enzymes and the mechanism of antivitamin action of hydroxythiamine in animal organisms].

    Science.gov (United States)

    Ostrovskiĭ KuM; Voskoboev, A I; Gorenshtenĭn, B I; Dosta, G A

    1979-09-01

    The molecula-kinetic parameters (Km, Ki) of three thiamine enzymes, e. g. thiamine pyrophosphokinase (EC 2.7.6.2), pyruvate dehydrogenase (EC 1.2.4.1) and transketolase (EC 2.2.1.1) with respect to the effects of the thiamine antimetabolite hydroxythiamine in the whole animal organism have been compared. It has been shown that only the first two enzymes, which interact competitively with the vitamin, antivitamin or their pyrophosphate ethers, obey the kinetic parameters obtained for the purified enzymes in vitro. The anticoenzymic effect of hydroxythiamine pyrophosphate with respect to transketolase is not observed in vivo at maximal concentration of the anticoenzyme in tissues due to the absence of competitive interactions with thiamine pyrophosphate. The incorporation of the true and false coenzymes into transketolase occurs only during de novo transketolase synthesis (the apoform is absent in tissues, with the exception of erythrocytes) and proceeds slowly with a half-life time equal to 24--30 hrs. After a single injection of hydroxythiamine at a large dose (70--400 mg/kg) the maximal inhibition of the transketolase activity in tissues (liver, heart, kidney, muscle, spleen, lungs adrenal grands) manifests itself by the 48th--72nd hour, when the concentration of free hydroxythiamine and its pyrophosphate is minimal and the whole anticoenzyme is tightly bound to the protein, forming the false holoenzyme. The use of hydroxythiamine for inhibition of pyruvate dehydrogenase or transketolase in animal organism is discussed.

  14. Temperature effects on kinetic parameters and substrate affinity of Cel7A cellobiohydrolases

    DEFF Research Database (Denmark)

    Sørensen, Trine Holst; Cruys-Bagger, Nicolaj; Windahl, Michael Skovbo

    2015-01-01

    Hypocrea jecorina and thermophilic Rasamsonia emersonii and two variants of these enzymes designed to elucidate the role of the carbohydrate binding module (CBM). We consistently found that the maximal rate increased strongly with temperature, whereas the affinity for the insoluble substrate decreased......We measured hydrolytic rates of four purified cellulases in small increments of temperature (10–50 °C) and substrate loads (0–100 g/liter) and analyzed the data by a steady state kinetic model that accounts for the processive mechanism. We used wild type cellobiohydrolases (Cel7A) from mesophilic......, and as a result, the effect of temperature depended strongly on the substrate load. Thus, temperature had little or no effect on the hydrolytic rate in dilute substrate suspensions, whereas strong temperature activation (Q10 values up to 2.6) was observed at saturating substrate loads. The CBM had a dual effect...

  15. DETERMINATION OF THERMODYNAMIC AND KINETIC PARAMETERS OF LARGE SCALE CHROMATOGRAPHIC SEPARATION OF SUGAR AND REDUCING SUGAR

    Institute of Scientific and Technical Information of China (English)

    LiZhong; ShuWenli; 等

    1996-01-01

    The parameter identification model of large scale chromatography separation process is proposed.The phase equilibrium constants and lumped mass transfer coefficients of sugar and reducing sugar adsorption on D1,D2 and D3 resins as well as the axial dispersion coefficients of the fluid through packed columns are determined by means of the pulse-response experiment technique with an inert substance as a tracer and the chromatography measuring technique.The elution curve calculated from these parameters is good agreement with the experimental elution curve.The sensitivity analysis of these parameters is carried out ,and the result shows that the elution curves of chromatography separation are more sensitive to the variations of the phase equilibrium relationship than to the variation of the axial dispersion as well as the lumped mass transfer coefficients.

  16. Sensitivity analysis of large system of chemical kinetic parameters for engine combustion simulation

    Energy Technology Data Exchange (ETDEWEB)

    Hsieh, H; Sanz-Argent, J; Petitpas, G; Havstad, M; Flowers, D

    2012-04-19

    In this study, the authors applied the state-of-the art sensitivity methods to downselect system parameters from 4000+ to 8, (23000+ -> 4000+ -> 84 -> 8). This analysis procedure paves the way for future works: (1) calibrate the system response using existed experimental observations, and (2) predict future experiment results, using the calibrated system.

  17. Treatment of biodiesel wastewater by adsorption with commercial chitosan flakes: parameter optimization and process kinetics.

    Science.gov (United States)

    Pitakpoolsil, Wipawan; Hunsom, Mali

    2014-01-15

    The possibility of using commercial chitosan flakes as an adsorbent for the removal of pollutants from biodiesel wastewater was evaluated. The effect of varying the adsorption time (0.5-5 h), initial wastewater pH (2-8), adsorbent dose (0.5-5.5 g/L) and mixing rate (120-350 rpm) on the efficiency of pollutant removal was explored by univariate analysis. Under the derived optimal conditions, greater than 59.3%, 87.9% and 66.2% of the biological oxygen demand (BOD), chemical oxygen demand (COD) and oil & grease, respectively, was removed by a single adsorption. Nevertheless, the remaining BOD, COD and oil & grease were still higher than the acceptable Thai government limits for discharge into the environment. When the treatment was repeated, a greater than 93.6%, 97.6% and 95.8% removal of the BOD, COD and oil & grease, respectively, was obtained. The reusability of commercial chitosan following NaOH washing (0.05-0.2 M) was not suitable, with less than 40% efficiency after just one recycling and declining rapidly thereafter. The adsorption kinetics of all pollutant types by the commercial chitosan flakes was controlled by a mixed process of diffusion and adsorption of the pollutants during the early treatment period (0-1.5 h) and then solely controlled by adsorption after 2 h. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. Kinetic Parameters Estimation of MgO-C Refractory by Shrinking Core Model

    Institute of Scientific and Technical Information of China (English)

    B.Hashemi; Z.A.Nemati; S.K. Sadrnezhaad; Z.A.Moghimi

    2006-01-01

    Kinetics of oxidation of MgO-C refractories was investigated by shrinking core modeling of the gas-solid reactions taking place during heating the porous materials to the high temperatures. Samples containing 4.5~17 wt pct graphite were isothermally oxidized at 1000~1350℃. Weight loss data was compared with predictions of the model. A mixed 2-stage mechanism comprised of pore diffusion plus boundary layer gas transfer was shown to generally control the oxidation rate. Pore diffusion was however more effective, especially at graphite contents lower than 10 wt pct under forced convection blowing of the air. Model calculations showed that effective gas diffusion coefficients were in the range of 0.08 to 0.55 cm2/s. These values can be utilized to determine the corresponding tortuosity factors of 6.85 to 2.22. Activation energies related to the pore diffusion mechanism appeared to be around (46.4±2)kJ/mol. The estimated intermolecular diffusion coefficients were shown to be independent of the graphite content, when the percentage of the graphite exceeded a marginal value of 10.

  19. Immobilization of denatured DNA to macroporous supports: II. Steric and kinetic parameters of heterogeneous hybridization reactions.

    Science.gov (United States)

    Bünemann, H

    1982-11-25

    The accessibility of immobilized DNA has been shown to depend more crucially on the method of immobilization than on the type of support used for fixation. When sonicated denatured DNA is coupled via diazotization or via cyanogen bromide reaction to solid Sephadex G-25 and Cellex 410 or to macroporous Sephacryl S-500 and Sepharose C1-6B its accessibility varies from 100 to 24 percent. Generally the loss of accessibility is linked to a depression of the melting temperature of DNA helices formed on the support. This correlation shows a characteristic course for a particular coupling method. DNA coupled under denaturing conditions may become totally inaccessible when only 3 percent of its bases are involved in the covalent linkage. Kinetic experiments with sonicated E.coli DNA have shown that the rate constants for renaturation or hybridization reactions are very similar for DNA immobilized by different methods to solid or macroporous supports. Generally the second order rate constant for a heterogeneous reaction (between mobile and immobilized DNA) is about one order of magnitude smaller than that of the analogous homogeneous reaction (in solution).

  20. Ethylene vinyl acetate based radiation grafted hydrophilic matrices: Process parameter standardization, grafting kinetics and characterization

    Science.gov (United States)

    Chaudhari, C. V.; Mondal, R. K.; Dubey, K. A.; Grover, V.; Panicker, L.; Bhardwaj, Y. K.; Varshney, L.

    2016-08-01

    A transparent, elastomeric, grafted matrix for several potential applications was synthesized by single-step simultaneous radiation grafting of methacrylic acid onto ethylene vinyl acetate (EVA). CuSO4 was found to be the most suitable homo-polymerization inhibitor among different inhibitors tried. The grafting kinetics was found to be a strong function of dose rate (D) and monomer content (M) and an equation relating grafting rate Rg=Kg [M]1.13D0.23 was deduced. Crystallinity of the grafted matrices as assessed from XRD and DSC measurements indicated decrease in crystalline content with increase in grafting yield, suggesting crystalline domain of EVA get disrupted on grafting. Elastic modulus increased linearly with the increase in grafting yield, though elongation at break decreased precipitously from 900% to 30% at even ~9% grafting. Thermo-gravimetric analysis showed three step weight loss of the grafted EVA matrix. The grafting of MAA resulted in increase in surface energy mainly due to enhanced polar component.

  1. Visualization and Curve-Parameter Estimation Strategies for Efficient Exploration of Phenotype Microarray Kinetics

    Science.gov (United States)

    Vaas, Lea A. I.; Sikorski, Johannes; Michael, Victoria; Göker, Markus; Klenk, Hans-Peter

    2012-01-01

    Background The Phenotype MicroArray (OmniLog® PM) system is able to simultaneously capture a large number of phenotypes by recording an organism's respiration over time on distinct substrates. This technique targets the object of natural selection itself, the phenotype, whereas previously addressed ‘-omics’ techniques merely study components that finally contribute to it. The recording of respiration over time, however, adds a longitudinal dimension to the data. To optimally exploit this information, it must be extracted from the shapes of the recorded curves and displayed in analogy to conventional growth curves. Methodology The free software environment R was explored for both visualizing and fitting of PM respiration curves. Approaches using either a model fit (and commonly applied growth models) or a smoothing spline were evaluated. Their reliability in inferring curve parameters and confidence intervals was compared to the native OmniLog® PM analysis software. We consider the post-processing of the estimated parameters, the optimal classification of curve shapes and the detection of significant differences between them, as well as practically relevant questions such as detecting the impact of cultivation times and the minimum required number of experimental repeats. Conclusions We provide a comprehensive framework for data visualization and parameter estimation according to user choices. A flexible graphical representation strategy for displaying the results is proposed, including 95% confidence intervals for the estimated parameters. The spline approach is less prone to irregular curve shapes than fitting any of the considered models or using the native PM software for calculating both point estimates and confidence intervals. These can serve as a starting point for the automated post-processing of PM data, providing much more information than the strict dichotomization into positive and negative reactions. Our results form the basis for a freely

  2. Visualization and curve-parameter estimation strategies for efficient exploration of phenotype microarray kinetics.

    Directory of Open Access Journals (Sweden)

    Lea A I Vaas

    Full Text Available BACKGROUND: The Phenotype MicroArray (OmniLog® PM system is able to simultaneously capture a large number of phenotypes by recording an organism's respiration over time on distinct substrates. This technique targets the object of natural selection itself, the phenotype, whereas previously addressed '-omics' techniques merely study components that finally contribute to it. The recording of respiration over time, however, adds a longitudinal dimension to the data. To optimally exploit this information, it must be extracted from the shapes of the recorded curves and displayed in analogy to conventional growth curves. METHODOLOGY: The free software environment R was explored for both visualizing and fitting of PM respiration curves. Approaches using either a model fit (and commonly applied growth models or a smoothing spline were evaluated. Their reliability in inferring curve parameters and confidence intervals was compared to the native OmniLog® PM analysis software. We consider the post-processing of the estimated parameters, the optimal classification of curve shapes and the detection of significant differences between them, as well as practically relevant questions such as detecting the impact of cultivation times and the minimum required number of experimental repeats. CONCLUSIONS: We provide a comprehensive framework for data visualization and parameter estimation according to user choices. A flexible graphical representation strategy for displaying the results is proposed, including 95% confidence intervals for the estimated parameters. The spline approach is less prone to irregular curve shapes than fitting any of the considered models or using the native PM software for calculating both point estimates and confidence intervals. These can serve as a starting point for the automated post-processing of PM data, providing much more information than the strict dichotomization into positive and negative reactions. Our results form the basis

  3. Real time kinetic flow cytometry measurements of cellular parameter changes evoked by nanosecond pulsed electric field.

    Science.gov (United States)

    Orbán, Csaba; Pérez-García, Esther; Bajnok, Anna; McBean, Gethin; Toldi, Gergely; Blanco-Fernandez, Alfonso

    2016-05-01

    Nanosecond pulsed electric field (nsPEF) is a novel method to increase cell proliferation rate. The phenomenon is based on the microporation of cellular organelles and membranes. However, we have limited information on the effects of nsPEF on cell physiology. Several studies have attempted to describe the effects of this process, however no real time measurements have been conducted to date. In this study we designed a model system which allows the measurement of cellular processes before, during and after nsPEF treatment in real time. The system employs a Vabrema Mitoplicator(TM) nsPEF field generating instrument connected to a BD Accuri C6 cytometer with a silicon tube led through a peristaltic pump. This model system was applied to observe the effects of nsPEF in mammalian C6 glioblastoma (C6 glioma) and HEK-293 cell lines. Viability (using DRAQ7 dye), intracellular calcium levels (using Fluo-4 dye) and scatter characteristics were measured in a kinetic manner. Data were analyzed using the FACSKin software. The viability and morphology of the investigated cells was not altered upon nsPEF treatment. The response of HEK-293 cells to ionomycin as positive control was significantly lower in the nsPEF treated samples compared to non-treated cells. This difference was not observed in C6 cells. FSC and SSC values were not altered significantly by the nsPEF treatment. Our results indicate that this model system is capable of reliably investigating the effects of nsPEF on cellular processes in real time. © 2016 International Society for Advancement of Cytometry.

  4. Evaluation of Kinetic and Thermodynamic Parameters of 1, 1’-Dibenzoylferrocene in Methanol by Cyclic Voltammetry

    Directory of Open Access Journals (Sweden)

    1I. I. Naqvi

    2012-12-01

    Full Text Available The electrochemical Kinetic study of 1, 1′- Dibenzoylferrocene (DBF at a platinum working electrode in 0.1 mol dm-3 NaClO4 non aqueous medium has been studied by Cyclicvoltammetry. The heterogeneous electron transfer rate constants (ks and the diffusion coefficients (Do of DBF were estimated at various temperatures (283 – 323 K and at different scan rates (0.05 – 0.5 V s-1. A calibration curve, linear over the range of 1x10-3 – 9x10-3 mol dm-3, was plotted at the scan rate of 0.25 Vs-1. This plot can be used to analyze an unknown sample of the compound. The kinetic data was also used to evaluate the Activation energy (Ea. The thermodynamic parameters such as enthalpy change of activation (ΔH*, Entropy change (ΔS* and Gibbs free energy change (ΔG* were also investigated during the study.

  5. Removal of Anionic Dyes from Water by Potash Alum Doped Polyaniline: Investigation of Kinetics and Thermodynamic Parameters of Adsorption.

    Science.gov (United States)

    Patra, Braja N; Majhi, Deola

    2015-06-25

    Polyaniline was synthesized by the oxidative polymerization method by using ammonium persulfate as an oxidant. The positive charge in the backbone of the polymer was generated by using Potash alum as a dopant. Scanning electron microscopy (SEM), Fourier transform infrared (FTIR), X-ray fluorescence (XRF), and X-ray diffraction (XRD) techniques were used for characterization of doped polyaniline. The doped polyaniline can be used for selective adsorption of various dyes (selectively sulfonated dyes) from aqueous solution. Adsorption studies regarding the effect of contact time, initial dye concentration, pH, doses of adsorbent, and temperature on adsorption kinetics were investigated. The influence of other anions like Cl(-), NO3(-), and SO4(2-) on the adsorption density of dyes onto doped polyaniline was also explored. Langmuir isotherm and pseudo-second-order kinetics were found to be the most appropriate models to describe the removal of anionic dyes from water through adsorption. Thermodynamic parameters such as free energy (ΔG(0)), enthalpy (ΔH(0)), and entropy (ΔS(0)) changes were also evaluated. The interaction of dyes with doped polyaniline was also investigated by FTIR and UV spectroscopy.

  6. Oxidation pathways for ozonation of azo dyes in a semi-batch reactor: a kinetic parameters approach.

    Science.gov (United States)

    Lopez, A; Benbelkacem, H; Pic, J S; Debellefontaine, H

    2004-03-01

    In this study ozone and the H2O2/O3 oxidation system are used to decolorize aqueous solutions of Orange II (Or-II) and Acid Red 27 (AR-27). Investigations are carried out in a semi-batch bubble column reactor. A system of series-parallel reactions is proposed to describe the mechanism of dye oxidation. The stoichiometric ratio for the first reaction is found to be 1 mol dye per mol O3, while the overall ozone demand for both reactions one and two is found to be 5 and 6 moles for Or-II and AR-27 respectively. Molecular and radical kinetics are compared: a radical scavenger, t-butanol, can be added to ensure only the molecular reaction of ozone, or hydrogen peroxide can be supplied through a peristaltic pump, to initiate radical reactivity. Results reveal that colour removal is ensured by direct ozone attack. For both dyes, TOC removal efficiencies of 50 - 60 % are obtained by the action of the hydroxyl free radical. However, this is not improved by addition of H2O2, thus demonstrating that organic species alone ensure HO degrees radical production during ozonation. Both the mass transfer and the ozone reactivity with the dyes are considered to evaluate the kinetic parameters for the molecular pathway.

  7. Determination of kinetic and thermodynamic parameters that describe isothermal seed germination: A student research project

    Science.gov (United States)

    Hageseth, Gaylord T.

    1982-02-01

    Students under the supervision of a faculty member can collect data and fit the data to the theoretical mathematical model that describes the rate of isothermal seed germination. The best-fit parameters are interpreted as an initial substrate concentration, product concentration, and the autocatalytic reaction rate. The thermodynamic model enables one to calculate the activation energy for the substrate and product, the activation energy for the autocatalytic reaction, and changes in enthalpy, entropy, and the Gibb's free energy. Turnip, lettuce, soybean, and radish seeds have been investigated. All data fit the proposed model.

  8. Optimizing the modified microdosimetric kinetic model input parameters for proton and 4He ion beam therapy application

    Science.gov (United States)

    Mairani, A.; Magro, G.; Tessonnier, T.; Böhlen, T. T.; Molinelli, S.; Ferrari, A.; Parodi, K.; Debus, J.; Haberer, T.

    2017-06-01

    Models able to predict relative biological effectiveness (RBE) values are necessary for an accurate determination of the biological effect with proton and 4He ion beams. This is particularly important when including RBE calculations in treatment planning studies comparing biologically optimized proton and 4He ion beam plans. In this work, we have tailored the predictions of the modified microdosimetric kinetic model (MKM), which is clinically applied for carbon ion beam therapy in Japan, to reproduce RBE with proton and 4He ion beams. We have tuned the input parameters of the MKM, i.e. the domain and nucleus radii, reproducing an experimental database of initial RBE data for proton and He ion beams. The modified MKM, with the best fit parameters obtained, has been used to reproduce in vitro cell survival data in clinically-relevant scenarios. A satisfactory agreement has been found for the studied cell lines, A549 and RENCA, with the mean absolute survival variation between the data and predictions within 2% and 5% for proton and 4He ion beams, respectively. Moreover, a sensitivity study has been performed varying the domain and nucleus radii and the quadratic parameter of the photon response curve. The promising agreement found in this work for the studied clinical-like scenarios supports the usage of the modified MKM for treatment planning studies in proton and 4He ion beam therapy.

  9. Application of artificial neural networks and DFT-based parameters for prediction of reaction kinetics of ethylbenzene dehydrogenase

    Science.gov (United States)

    Szaleniec, Maciej; Witko, Małgorzata; Tadeusiewicz, Ryszard; Goclon, Jakub

    2006-03-01

    Artificial neural networks (ANNs) are used for classification and prediction of enzymatic activity of ethylbenzene dehydrogenase from EbN1 Azoarcus sp. bacterium. Ethylbenzene dehydrogenase (EBDH) catalyzes stereo-specific oxidation of ethylbenzene and its derivates to alcohols, which find its application as building blocks in pharmaceutical industry. ANN systems are trained based on theoretical variables derived from Density Functional Theory (DFT) modeling, topological descriptors, and kinetic parameters measured with developed spectrophotometric assay. Obtained models exhibit high degree of accuracy (100% of correct classifications, correlation between predicted and experimental values of reaction rates on the 0.97 level). The applicability of ANNs is demonstrated as useful tool for the prediction of biochemical enzyme activity of new substrates basing only on quantum chemical calculations and simple structural characteristics. Multi Linear Regression and Molecular Field Analysis (MFA) are used in order to compare robustness of ANN and both classical and 3D-quantitative structure-activity relationship (QSAR) approaches.

  10. Biodegradation of malathion and evaluation of kinetic parameters using three bacterial species

    Directory of Open Access Journals (Sweden)

    S.R. Geed

    2016-12-01

    Full Text Available Efficacy of three different bacterial species for biodegradation of malathion and its secondary products have been investigated. The concentration range of malathion under investigation was 25–200 mg⋅L−1. It has been observed that Pseudomonas putida was found to be most efficient for degradation of malathion. The removal of malathion was 72% at its concentration of 125 mg⋅L−1. The optimum parameters were studied for all three bacterial species in batch mode. The average values of Ks and μmax were obtained for all these species for degradation of malathion. Results indicate that P. putida has high degradation potential than Rhodoccocus rhodochrous and Sphingomonas sp. The degradation of P. putida was maximum at concentration of 125 mg⋅L−1, pH and temperature at 7 ± 0.2, 80 °C respectively. Metabolites were obtained using GCMS analysis.

  11. Estimation of Hoffman-Lauritzen parameters from nonisothermal crystallization kinetics of PET/MWCNT nanocomposites

    Science.gov (United States)

    Gaonkar, Amita; Murudkar, Vrishali; Deshpande, V. D.

    2016-05-01

    Polyethylene terephthalate (PET) and Nucleated PET/ multi-walled carbon nanotubes (MWCNTs) nanocomposites with different MWCNTs loadings were prepared by melt compounding. The influence of the addition of MWCNTs and precipitated PET (p-PET) on the morphology and thermal properties of the nanocomposites was investigated. From Transmission Electronic Microscopy (TEM) and Wide angle X-Ray diffraction (WAXD) study, it can be clearly seen that nanocomposites with low MWCNTs contents (0.1 wt. %) get better MWCNTs dispersion than higher MWCNT loading. Comparing with PET, nucleated PET nanocomposite with 0.1% MWCNT loading shows higher value of Lauritzen-Hoffman parameters U* and Kg evaluated using the differential isoconversional method. Crystallization regime transition temperature range shifts to higher temperature (208°C - 215°C) for nanocomposites. The presence of p-PET in addition of MWCNT, which act as good nucleating agent, enhanced the crystallization of PET through heterogeneous nucleation.

  12. Dosimetric and kinetic parameters of lithium cadmium borate glasses doped with rare earth ions

    Directory of Open Access Journals (Sweden)

    J. Anjaiah

    2014-10-01

    Full Text Available Thermoluminescence (TL characteristics of X-ray irradiated pure and doped with four different rare earth ions (viz., Pr3+, Nd3+, Sm3+ and Eu3+ Li2O–Cdo–B2O3 glasses have been studied in the temperature range 303–573 K; the pure glass has exhibited single TL peak at 466 K. When this glass is doped with different rare earth ions no additional peaks are observed but the glow peak temperature of the existing glow peak shifted gradually towards higher temperatures with gain in intensity of TL light output. The area under the glow curve is found to be maximum for Eu3+ doped glasses. The trap depth parameters associated with the observed TL peaks have been evaluated using Chen's formulae. The possible use of these glasses in radiation dosimetry has been described. The result clearly showed that europium doped cadmium borate glass has a potential to be considered as the thermoluminescence dosimeter.

  13. Magnetic Properties and Kinetics Parameters of Electroless Magnetic Loss CoFeB Films

    Institute of Scientific and Technical Information of China (English)

    LIU Chang-hui; HE Hua-hui; SHEN Xiang; LI Hai-hua

    2008-01-01

    Electroless CoFeB films with good soft magnetic properties were fabricated on polyester plastic substrate from sodium tartarate as a complexing agent. The plating rate of electroless CoFeB films is a function of concentration of sodium tetrahydroborate, pH of the plating bath, plating temperature and the metallic ratio. The estimated regression coefficient b0-b3 confidence interval, residual error r and confidence interval rint were confirmed by a computer program. The optimal composition of the plating bath was obtained and the dynamic electromagnetic parameters of films were measured in the 2-10 GHz range. At 2 GHz, the μ′, μ″ of the electroless CoFeB films were 304 and 76.6, respectively, as the concentration of reducer is 1 g/L. Magnetic hysteresis loop of the deposited CoFeB films show a remanence close to the saturation magnetization and coercivity of about 55.7-127.4 A/m. The loops along the hard axis display low anisotropic field Hk of 2 388-3 582 A/m.

  14. Degradation of atenolol by UV/peroxymonosulfate: kinetics, effect of operational parameters and mechanism.

    Science.gov (United States)

    Liu, Xiaowei; Zhang, Tuqiao; Zhou, Yongchao; Fang, Lei; Shao, Yu

    2013-11-01

    Photoactivation of peroxymonosulfate (PMS) with UV (254nm) irradiation was used to generate the SO4(-)-based advanced oxidation process, which was adopted to degrade atenolol (ATL) in water. The second-order reaction rate constants of ATL with HO and SO4(-) were determined, and the effects of operational parameters (dose of PMS, solution pH, HCO3(-), humic acids (HA), and N2 bubbling) were evaluated as well. Finally the main transformation intermediates were identified and possible degradation pathways were proposed. The results showed that there was a linear positive correlation between the degradation rate of ATL and specific dose of PMS (1-16M PMS/M ATL). Increasing solution pH from 3 to 9 promoted elimination of ATL due to the pH-dependent effect of PMS photodecomposition, while further pH increase from 9 to 11 caused slowing down of degradation because of apparent conversion of HO to SO4(-). 1-8mM HCO3(-) exerted no more than 5.3% inhibition effect on ATL destruction, suggesting HCO3(-) was a weak inhibitor. Absorption (or complexation) and photosensitized oxidation induced by HA improved ATL degradation during the first minute of degradation process, whereas photon competition and radical scavenging effects became the leading role afterward. Bubbling with nitrogen enhanced the degradation rate due to the stripping of dissolved oxygen. Hydroxylation of aromatic ring, cleavage of ether bond, oxidation of primary and secondary amine moieties, and dimerization were involved in the degradation mechanism of ATL by UV/PMS.

  15. Estimation of turbulent kinetic energy using 4D phase-contrast MRI: Effect of scan parameters and target vessel size.

    Science.gov (United States)

    Ha, Hojin; Hwang, Dongha; Kim, Guk Bae; Kweon, Jihoon; Lee, Sang Joon; Baek, Jehyun; Kim, Young-Hak; Kim, Namkug; Yang, Dong Hyun

    2016-07-01

    Quantifying turbulence velocity fluctuation is important because it indicates the fluid energy dissipation of the blood flow, which is closely related to the pressure drop along the blood vessel. This study aims to evaluate the effects of scan parameters and the target vessel size of 4D phase-contrast (PC)-MRI on quantification of turbulent kinetic energy (TKE). Comprehensive 4D PC-MRI measurements with various velocity-encoding (VENC), echo time (TE), and voxel size values were carried out to estimate TKE distribution in stenotic flow. The total TKE (TKEsum), maximum TKE (TKEmax), and background noise level (TKEnoise) were compared for each scan parameter. The feasibility of TKE estimation in small vessels was also investigated. Results show that the optimum VENC for stenotic flow with a peak velocity of 125cm/s was 70cm/s. Higher VENC values overestimated the TKEsum by up to six-fold due to increased TKEnoise, whereas lower VENC values (30cm/s) underestimated it by 57.1%. TE and voxel size did not significantly influence the TKEsum and TKEnoise, although the TKEmax significantly increased as the voxel size increased. TKE quantification in small-sized vessels (3-5-mm diameter) was feasible unless high-velocity turbulence caused severe phase dispersion in the reference image. Copyright © 2016 Elsevier Inc. All rights reserved.

  16. Contribution of counterions and degree of ionization for birefringence creation and relaxation kinetics parameters of PAH/PAZO films

    Energy Technology Data Exchange (ETDEWEB)

    Raposo, Maria, E-mail: mfr@fct.unl.pt; Monteiro Timóteo, Ana Rita; Ribeiro, Paulo A. [CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, UNL, Campus de Caparica, 2829-516 Caparica (Portugal); Ferreira, Quirina [CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, UNL, Campus de Caparica, 2829-516 Caparica (Portugal); Instituto de Telecomunicações, Instituto Superior Técnico, University of Lisbon, Av. Rovisco Pais, P-1049-001 Lisboa (Portugal); Botelho do Rego, Ana Maria [Centro de Química-Física Molecular and IN, Complexo Interdisciplinar, Instituto Superior Técnico, University of Lisbon, 1049-001 Lisboa (Portugal)

    2015-09-21

    Photo induced birefringent materials can be used to develop optical and conversion energy devices, and consequently, the study of the variables that influences the creation and relaxation of birefringence should be carefully analyzed. In this work, the parameters of birefringence creation and relaxation kinetics curves obtained on layer-by-layer (LBL) films, prepared from azo-polyectrolyte poly[1-[4-(3-carboxy-4 hydroxyphenylazo) benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) and poly(allylamine hydrochloride)(PAH), are related with the presence of counterions and the degree of ionization of the polyelectrolytes. Those kinetics curves obtained on PAH/PAZO LBL films, prepared from PAH solutions with different pHs and maintaining the pH of PAZO solution constant at pH = 9, were analyzed taking into account the films composition which was characterized by X-ray photoelectron spectroscopy. The creation and relaxation birefringence curves are justified by two processes: one associated to local mobility of the azobenzene with a characteristic time 30 s and intensity constant and other associated with polymeric chains mobility with the characteristic time and intensity decreasing with pH. These results allow us to conclude that the birefringence creation process, associated to local mobility of azobenzenes is independent of the degree of ionization and of number of counterions or co-ions present while the birefringence creation process associated to mobility of chains have its characteristic time and intensity dependent of both degree of ionization and number of counterions. The birefringence relaxation processes are dependent of the degree of ionization. The analysis of the films composition revealed, in addition, the presence of a protonated secondary or tertiary amine revealing that PAZO may have positive charges and consequently a zwitterionic behavior.

  17. Final Report for NFE-07-00912: Development of Model Fuels Experimental Engine Data Base & Kinetic Modeling Parameter Sets

    Energy Technology Data Exchange (ETDEWEB)

    Bunting, Bruce G [ORNL

    2012-10-01

    The automotive and engine industries are in a period of very rapid change being driven by new emission standards, new types of after treatment, new combustion strategies, the introduction of new fuels, and drive for increased fuel economy and efficiency. The rapid pace of these changes has put more pressure on the need for modeling of engine combustion and performance, in order to shorten product design and introduction cycles. New combustion strategies include homogeneous charge compression ignition (HCCI), partial-premixed combustion compression ignition (PCCI), and dilute low temperature combustion which are being developed for lower emissions and improved fuel economy. New fuels include bio-fuels such as ethanol or bio-diesel, drop-in bio-derived fuels and those derived from new crude oil sources such as gas-to-liquids, coal-to-liquids, oil sands, oil shale, and wet natural gas. Kinetic modeling of the combustion process for these new combustion regimes and fuels is necessary in order to allow modeling and performance assessment for engine design purposes. In this research covered by this CRADA, ORNL developed and supplied experimental data related to engine performance with new fuels and new combustion strategies along with interpretation and analysis of such data and consulting to Reaction Design, Inc. (RD). RD performed additional analysis of this data in order to extract important parameters and to confirm engine and kinetic models. The data generated was generally published to make it available to the engine and automotive design communities and also to the Reaction Design Model Fuels Consortium (MFC).

  18. TU-C-12A-11: Comparisons Between Cu-ATSM PET and DCE-CT Kinetic Parameters in Canine Sinonasal Tumors

    Energy Technology Data Exchange (ETDEWEB)

    La Fontaine, M; Bradshaw, T [University of Wisconsin, Madison, Wisconsin (United States); Kubicek, L [University of Florida, Gainesville, Florida (United States); Forrest, L [University of Wisconsin-Madison, Madison, Wisconsin (United States); Jeraj, R [University of Wisconsin, Madison, WI (United States)

    2014-06-15

    Purpose: Regions of poor perfusion within tumors may be associated with higher hypoxic levels. This study aimed to test this hypothesis by comparing measurements of hypoxia from Cu-ATSM PET to vasculature kinetic parameters from DCE-CT kinetic analysis. Methods: Ten canine patients with sinonasal tumors received one Cu-ATSM PET/CT scan and three DCE-CT scans prior to treatment. Cu-ATSM PET/CT and DCE-CT scans were registered and resampled to matching voxel dimensions. Kinetic analysis was performed on DCE-CT scans and for each patient, the resulting kinetic parameter values from the three DCE-CT scans were averaged together. Cu-ATSM SUVs were spatially correlated (r{sub spatial}) on a voxel-to-voxel basis against the following DCE-CT kinetic parameters: transit time (t{sub 1}), blood flow (F), vasculature fraction (v{sub 1}), and permeability (PS). In addition, whole-tumor comparisons were performed by correlating (r{sub ROI}) the mean Cu-ATSM SUV (SUV{sub mean}) with median kinetic parameter values. Results: The spatial correlations (r{sub spatial}) were poor and ranged from -0.04 to 0.21 for all kinetic parameters. These low spatial correlations may be due to high variability in the DCE-CT kinetic parameter voxel values between scans. In our hypothesis, t{sub 1} was expected to have a positive correlation, while F was expected to have a negative correlation to hypoxia. However, in wholetumor analysis the opposite was found for both t{sub 1} (r{sub ROI} = -0.25) and F (r{sub ROI} = 0.56). PS and v{sub 1} may depict angiogenic responses to hypoxia and found positive correlations to Cu-ATSM SUV for PS (r{sub ROI} = 0.41), and v{sub 1} (r{sub ROI} = 0.57). Conclusion: Low spatial correlations were found between Cu-ATSM uptake and DCE-CT vasculature parameters, implying that poor perfusion is not associated with higher hypoxic regions. Across patients, the most hypoxic tumors tended to have higher blood flow values, which is contrary to our initial hypothesis. Funding

  19. Kinetic parameters study based on burn-up for improving the performance of research reactor equilibrium core

    Directory of Open Access Journals (Sweden)

    Muhammad Atta

    2014-01-01

    Full Text Available In this study kinetic parameters, effective delayed neutron fraction and prompt neutron generation time have been investigated at different burn-up stages for research reactor's equilibrium core utilizing low enriched uranium high density fuel (U3Si2-Al fuel with 4.8 g/cm3 of uranium. Results have been compared with reference operating core of Pakistan research Reactor-1. It was observed that by increasing fuel burn-up, effective delayed neutron fraction is decreased while prompt neutron generation time is increased. However, over all ratio beff/L is decreased with increasing burn-up. Prompt neutron generation time L in the understudy core is lower than reference operating core of reactor at all burn-up steps due to hard spectrum. It is observed that beff is larger in the understudy core than reference operating core of due to smaller size. Calculations were performed with the help of computer codes WIMSD/4 and CITATION.

  20. Comparison of dual-echo DSC-MRI- and DCE-MRI-derived contrast agent kinetic parameters.

    Science.gov (United States)

    Quarles, C Chad; Gore, John C; Xu, Lei; Yankeelov, Thomas E

    2012-09-01

    The application of dynamic susceptibility contrast (DSC) MRI methods to assess brain tumors is often confounded by the extravasation of contrast agent (CA). Disruption of the blood-brain barrier allows CA to leak out of the vasculature leading to additional T(1), T(2) and T(2) relaxation effects in the extravascular space, thereby affecting the signal intensity time course in a complex manner. The goal of this study was to validate a dual-echo DSC-MRI approach that separates and quantifies the T(1) and T(2) contributions to the acquired signal and enables the estimation of the volume transfer constant, K(trans), and the volume fraction of the extravascular extracellular space, v(e). To test the validity of this approach, DSC-MRI- and dynamic contrast enhanced (DCE) MRI-derived K(trans) and v(e) estimates were spatially compared in both 9L and C6 rat brain tumor models. A high degree of correlation (concordance correlation coefficients >0.83, Pearson's r>0.84) and agreement was found between the DSC-MRI- and DCE-MRI-derived measurements. These results indicate that dual-echo DSC-MRI can be used to simultaneously extract reliable DCE-MRI kinetic parameters in brain tumors in addition to conventional blood volume and blood flow metrics.

  1. Evaluation of the kinetic and thermodynamic parameters of oxidation reaction in biodiesel from a quaternary mixture of raw material

    Directory of Open Access Journals (Sweden)

    Karina Gomes Angilelli

    2017-05-01

    Full Text Available A mixture of vegetable oil and animal fat as raw materials was optimized by simplex-centroid mixture design to produce a type of biodiesel with good oxidative stability, flow properties and reaction yield. Further, kinetic and thermodynamic parameters of oxidation reaction were determined by the accelerated method at different temperatures. Biodiesel produced with sodium methoxide as catalyst presented 6.5°C of cloud point, 2.0°C of pour point, and oxidative stability at 110°C equal to 8.98h, with a reaction yield of 96.04%. Activation energy of the oxidation reaction was 81.03 kJ mol-1 for biodiesel produced with sodium hydroxide and 90.51 kJ mol-1 for sodium methoxide. The positive values for DH‡ and DG‡ indicate that the oxidation process is endothermic and endergonic. The less negative DS‡ for biodiesel produced with sodium methoxide (-28.87 JK-1 mol-1 showed that the process of degradation of this biofuel was slower than that produced with NaOH. The mixture of raw materials proposed, transesterified with the methoxide catalyst, resulted in a biofuel that resisted oxidation for longer periods, making unnecessary the addition of antioxidant

  2. A New General Method for Simultaneous Fitting of Temperature- and Concentration-Dependence of Reaction Rates Yields Kinetic and Thermodynamic Parameters for HIV Reverse Transcriptase Specificity.

    Science.gov (United States)

    Li, An; Ziehr, Jessica L; Johnson, Kenneth A

    2017-03-02

    Recent studies have demonstrated the dominant role of induced-fit in enzyme specificity of HIV reverse transcriptase and many other enzymes. However, relevant thermodynamic parameters are lacking and equilibrium thermodynamic methods are of no avail because the key parameters can only determined by kinetic measurement. By modifying KinTek Explorer software, we present a new general method for globally fitting data collected over a range of substrate concentrations and temperatures and apply it to HIV reverse transcriptase. Fluorescence stopped-flow methods were used to record the kinetics of enzyme conformational changes that monitor nucleotide binding and incorporation. The nucleotide concentration dependence was measured at temperatures ranging from 5 to 37C and the raw data were fit globally to derive a single set of rate constants at 37C and a set of activation enthalpy terms to account for the kinetics at all other temperatures. This comprehensive analysis afforded thermodynamic parameters for nucleotide binding (Kd, ΔG, ΔH, ΔS at 37C), and kinetic parameters for enzyme conformational changes and chemistry (rate constants and activation enthalpy). Comparisons between wild-type enzyme and a mutant resistant to nucleoside analogs used to treat HIV infections reveal that the ground state binding is weaker and the activation enthalpy for the conformational change step is significantly larger for the mutant. Further studies to explore the structural underpinnings of the observed thermodynamics and kinetics of the conformational change step may help to design better analogs to treat HIV infections and other diseases. Our new method is generally applicable to enzyme and chemical kinetics.

  3. Monin-Obukhov Similarity Functions of the Structure Parameter of Temperature and Turbulent Kinetic Energy Dissipation Rate in the Stable Boundary Layer

    NARCIS (Netherlands)

    Hartogensis, O.K.; Debruin, H.A.R.

    2005-01-01

    The Monin-Obukhov similarity theory (MOST) functions fepsi; and fT, of the dissipation rate of turbulent kinetic energy (TKE), ¿, and the structure parameter of temperature, CT2, were determined for the stable atmospheric surface layer using data gathered in the context of CASES-99. These data cover

  4. Study on thermal decomposition kinetic parameters of GAP-TPE%GAP-TPE热分解动力学研究

    Institute of Scientific and Technical Information of China (English)

    左海丽; 肖乐勤; 周伟良; 徐复铭

    2011-01-01

    利用热量(TG)及微商热重(DTG),研究了GAP基含能热塑性弹性体(GAP-TPE)在氢气气氛、不同升温速率的热分解反应过程.根据GAP-TPE热解DTG曲线特点,把GAP-TPE热解过程分为3个阶段,用Kissinger法计算3个阶段的动力学参数,其活化能分别是223、235、57kJ/mol,lnA分别是52.73、49.39、8.28.用Ozawa法求得各阶段的平均活化能与Kinger法计算结果基本一致,并采用Coats-Redfen法求算了GAP-TPE热分解3个阶段可能遵循的动力学机理方程式分别为[ - ln(1 -α)]1/3、-ln(1-α)和-ln(1-α).%Based on the thermal analysis kinetics,thermogravimetric analysis(TG)and derivative thermogravimetry( DTG) were employed to evaluate the thermal decomposition behaviors of CAP-TPE in Ar atmosphere. A peak separation was performed to separate the thermal decomposition of CAP-TPE into three stages according to the characteristic of the experimental differential mass loss curve,and the kinetic parameters such as activation energy and pre-exponential were calculated and analyzed with Kissinger method. The activation energy of three stages were 223 kJ/mol ,233 kJ/mol and 57 kJ/mol, the hv4 were 52.73,49.39 and 8.28, respectively. The average activation energy was calculated with Ozawa methods in each decomposition stage is consistent with the result of Kissinger method. In addition,the mechanism functions of the three stage using the methods of Coats-Redfen were[ - ln( 1 -a) ]1/3, -ln(1-α) and - ln(1-α),respectively.

  5. Enzyme Kinetics Experiment with the Multienzyme Complex Viscozyme L and Two Substrates for the Accurate Determination of Michaelian Parameters

    Science.gov (United States)

    Guerra, Nelson Pérez

    2017-01-01

    A laboratory experiment in which students study the kinetics of the Viscozyme-L-catalyzed hydrolysis of cellulose and starch comparatively was designed for an upper-division biochemistry laboratory. The main objective of this experiment was to provide an opportunity to perform enhanced enzyme kinetics data analysis using appropriate informatics…

  6. Estimation of kinetic parameters of the passive state of carbon steel in mildly alkaline solutions from electrochemical impedance spectroscopic and X-ray photoelectron spectroscopic data

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, X.; Wren, J.C. [Department of Chemistry, University of Western Ontario, 1151 Richmond St, London, Ontario, N6A 5B7 (Canada); Betova, I. [Department of Chemistry, Technical University of Sofia, 1000 Sofia (Bulgaria); Bojinov, M., E-mail: martin@uctm.edu [Department of Physical Chemistry, University of Chemical Technology and Metallurgy, 1756 Sofia (Bulgaria)

    2011-07-01

    Highlights: > The passive state of carbon steel is described using the Mixed-Conduction Model for oxide films. > Kinetic parameters are estimated by comparison of the model to EIS and XPS data. > The passive film is intermediate between magnetite and maghemite. > Relevance of film growth and dissolution reactions for corrosion is discussed. - Abstract: The unambiguous interpretation of electrochemical impedance spectra of complex systems such as passive metals and alloys in terms of an unique kinetic model is often hampered by the large number of adjustable modeling parameters. In this paper, a combination of in situ electrochemical data and ex situ surface analytical information is employed to validate the estimates of kinetic and transport parameters of the passive state of carbon steel. For the purpose, electrochemical impedance spectroscopic and X-ray photoelectron spectroscopic data for the oxidation of carbon steel in mildly alkaline solutions are quantitatively compared with the predictions of the Mixed-Conduction Model for oxide films that represent the passive oxide as an intermediate phase between magnetite and maghemite. Estimates of the kinetic rate constants at the film interfaces, as well as the diffusion coefficients and field strength in the film are obtained and their relevance for the corrosion mechanism of carbon steel is discussed.

  7. Testing of the Effect of Reaction Parameters on the Enzyme Immobilization by Adsorption and Cross-Linking Processes with Kinetic Desorption Method

    Directory of Open Access Journals (Sweden)

    Dániel Radva

    2011-01-01

    Full Text Available The activity of enzymes after the immobilization by weak interactions such as adsorption or adsorption followed by a cross-linking reaction can change easily not only during further application but during the activity measured via desorption and/or inactivation of enzymes. The changes in activity could be a consequence of the interactions between the enzyme and support. In this work a quick and efficient method is developed that permits studying of the strength and properties of the forces between the enzymes and support by examining the kinetics of desorption and/or inactivation. Applying this new cyclic kinetic desorption method, the effect of reaction parameters on immobilization could also be studied. The efficiency of this method was tested for optimizing the parameters for immobilization of β-glucosidase on Amberlite IRA 900 anion exchange resin by an adsorption followed by a cross-linking with glutaraldehyde to form potential preparation for food industry. The following parameters were chosen: concentration (0.10 M of the buffer (sodium acetate, pH=5.5 and the ratio of carrier to enzyme (10:1 for the adsorption step, then the time of treatment (1 min and concentration (0.25, by mass per volume of glutaraldehyde for the cross-linking by using the kinetic desorption method. The activity of this preparation was 57 μmol/(min·g in respect of dry resin. It was established that the effect of different parameters on this enzyme immobilization could be characterized by the new cyclic kinetic desorption method in a quick and efficient way; furthermore, it permitted separate testing of the effect of parameters on the adsorption and cross-linking processes.

  8. Kinetic Parameters during Bis-GMA and TEGDMA Monomer Polymerization by ATR-FTIR: The Influence of Photoinitiator and Light Curing Source

    Directory of Open Access Journals (Sweden)

    Aline B. Denis

    2016-01-01

    Full Text Available This study aimed to analyze the kinetic parameters of two monomers using attenuated total reflectance Fourier transform infrared (ATR-FTIR: 2,2-bis-[4-(2-hydroxy-3-methacryloxypropyl-1-oxy-phenyl] propane (Bis-GMA and triethylene glycol dimethacrylate (TEGDMA. The following were calculated to evaluate the kinetic parameters: maximum conversion rate (Rpmax, time at the maximum polymerization rate (tmax, conversion at Rpmax, and total conversion recorded at the maximum conversion point after 300 s. Camphorquinone (CQ and phenyl propanedione (PPD were used in this study as photoinitiators, whereas N,N-dimethyl-p-toluidine (DMPT amine was used as a coinitiator. LED apparatus and halogen lamp were used in turn to evaluate the effect that light source had on the monomer kinetics. The mass concentration ratio for the three resin preparations was 0.7 : 0.3 for Bis-GMA and TEGDMA: R1 (CQ + DMPT, R2 (PPD + DMPT, and R3 (PPD + CQ + DMPT. The PPD association with the CQ photoinitiator altered the polymerization kinetics compared to a resin containing only the CQ photoinitiator. The light sources exhibited no significant differences for tmax of R1 and R3. Resins containing only the PPD initiator exhibited a higher tmax than those containing only CQ. However, the Rpmax decreased for resins containing the PPD photoinitiator.

  9. The comparison of the estimation of enzyme kinetic parameters by fitting reaction curve to the integrated Michaelis-Menten rate equations of different predictor variables.

    Science.gov (United States)

    Liao, Fei; Zhu, Xiao-Yun; Wang, Yong-Mei; Zuo, Yu-Ping

    2005-01-31

    The estimation of enzyme kinetic parameters by nonlinear fitting reaction curve to the integrated Michaelis-Menten rate equation ln(S(0)/S)+(S(0)-S)/K(m)=(V(m)/K(m))xt was investigated and compared to that by fitting to (S(0)-S)/t=V(m)-K(m)x[ln(S(0)/S)/t] (Atkins GL, Nimmo IA. The reliability of Michaelis-Menten constants and maximum velocities estimated by using the integrated Michaelis-Menten equation. Biochem J 1973;135:779-84) with uricase as the model. Uricase reaction curve was simulated with random absorbance error of 0.001 at 0.075 mmol/l uric acid. Experimental reaction curve was monitored by absorbance at 293 nm. For both CV and deviation kinetic parameters and applicable for the characterization of enzyme inhibitors.

  10. KINETIC PARAMETERS AND CYTOTOXIC ACTIVITY OF RECOMBINANT METHIONINE γ-LYASE FROM CLOSTRIDIUM TETANI, CLOSTRIDIUM SPOROGENES, PORPHYROMONAS GINGIVALIS AND CITROBACTER FREUNDII

    OpenAIRE

    Morozova, E.; Kulikova, V.; Yashin, D.; Anufrieva, N.; Anisimova, N.; Revtovich, S.; Kotlov, M.; Belyi, Y.; Pokrovsky, V.; Demidkina, T.

    2013-01-01

    The steady-state kinetic parameters of pyridoxal 5’-phosphate-dependent recombinant methionine γ -lyase from three pathogenic bacteria, Clostridium tetani, Clostridium sporogenes, and Porphyromonas gingivalis, were determined in β- and γ-elimination reactions. The enzyme from C. sporogenes is characterized by the highest catalytic efficiency in the γ-elimination reaction of L-methionine. It was demonstrated that the enzyme from these three sources exists as a tetramer. The N-terminal poly-his...

  11. Thermoluminescent kinetic parameters of the perovskite, KMgF{sub 3}, activated with lanthanum; Parametros cineticos termoluminiscentes de la perovskita, KMgF{sub 3}, activada con lantano

    Energy Technology Data Exchange (ETDEWEB)

    Sepulveda M, F. [ESFM-IPN, 07738 Mexico D.F. (Mexico); Azorin N, J.; Rivera M, T. [UAM-I, 09340 Mexico D.F. (Mexico); Furetta, C.; Sanipoli, C. [Physics Department, Universita di Roma ' ' La Sapienza' ' , Piazzale A. Moro 2, 00185 Roma (Italy)

    2004-07-01

    The thermoluminescent curves induced by the beta radiation in the perovskite KMgF{sub 3} were investigated activated with lanthanum. The classic methods were used to determine the kinetic parameters (the kinetic order b, the activation energy E and the frequency of escape intent s) associated with the peaks of the thermoluminescent curve (Tl) in the KMgF{sub 3} activated with lanthanum after the irradiation with beta rays. The method is based on the position of the thermoluminescent peaks, obtained of the temperature change of the peak in the maximum emission caused by the change in the heating rapidity to which the samples were measured. In this work, the samples in form of pellets were re cooked previously at 400 C during one hour before irradiating them with beta particles. The Tl measures were made with a Tl reader system using three different heating rapidities and storing the glow curves. To calculate the depth of the E traps and the frequency factor s, the parameters of the glow curve were determined experimentally of the shame of the glow curve by means of the mensuration of the shame of the maximum temperature of the peak, T{sub M} like a function of the heating rapidity. The results indicate that the values of the kinetic parameters are very near among if when they are obtained indistinctly of anyone of the different methods. (Author)

  12. Displacement cascades and defect annealing in tungsten, Part III: The sensitivity of cascade annealing in tungsten to the values of kinetic parameters

    Energy Technology Data Exchange (ETDEWEB)

    Nandipati, Giridhar; Setyawan, Wahyu; Heinisch, Howard L.; Roche, Kenneth J.; Kurtz, Richard J.; Wirth, Brian D.

    2015-07-01

    Object kinetic Monte Carlo (OKMC) simulations have been performed to investigate various aspects of cascade aging in bulk tungsten and to determine the sensitivity of the results to the kinetic parameters. The primary focus is on how the kinetic parameters affect the initial recombination of defects in the first few ns of a simulation. The simulations were carried out using the object kinetic Monte Carlo (OKMC) code KSOME (kinetic simulations of microstructure evolution), using a database of cascades obtained from results of molecular dynamics (MD) simulations at various primary knock-on atom (PKA) energies and directions at temperatures of 300, 1025 and 2050 K. The OKMC model was parameterized using defect migration barriers and binding energies from ab initio calculations. Results indicate that, due to the disparate mobilities of SIA and vacancy clusters in tungsten, annealing is dominated by SIA migration even at temperatures as high as 2050 K. For 100 keV cascades initiated at 300 K recombination is dominated by annihilation of large defect clusters. But for all other PKA energies and temperatures most of the recombination is due to the migration and rotation of small SIA clusters, while all the large SIA clusters escape the cubic simulation cell. The inverse U-shape behavior exhibited by the annealing efficiency as a function of temperature curve, especially for cascades of large PKA energies, is due to asymmetry in SIA and vacancy clustering assisted by the large difference in mobilities of SIAs and vacancies. This annealing behavior is unaffected by the dimensionality of SIA migration persists over a broad range of relative mobilities of SIAs and vacancies.

  13. Assessment of metabolic properties and kinetic parameters of methanogenic sludge by on-line methane production rate measurements

    NARCIS (Netherlands)

    Gonzalez-Gil, G.; Kleerebezem, R.; Lettinga, G.

    2002-01-01

    This report presents a new approach to studying the metabolic and kinetic properties of anaerobic sludge from single batch experiments. The two main features of the method are that the methane production is measured on-line with a relatively cheap system, and that the methane production data can be

  14. Displacement cascades and defect annealing in tungsten, Part III: The sensitivity of cascade annealing in tungsten to the values of kinetic parameters

    Energy Technology Data Exchange (ETDEWEB)

    Nandipati, Giridhar, E-mail: giridhar.nandipati@pnnl.gov [Pacific Northwest National Laboratory, Richland, WA (United States); Setyawan, Wahyu; Heinisch, Howard L. [Pacific Northwest National Laboratory, Richland, WA (United States); Roche, Kenneth J. [Pacific Northwest National Laboratory, Richland, WA (United States); Department of Physics, University of Washington, Seattle, WA 98195 (United States); Kurtz, Richard J. [Pacific Northwest National Laboratory, Richland, WA (United States); Wirth, Brian D. [University of Tennessee, Knoxville, TN (United States)

    2015-07-15

    A study has been performed using object kinetic Monte Carlo (OKMC) simulations to investigate various aspects of cascade aging in bulk tungsten (W) and to determine its sensitivity to the kinetic parameters. The primary focus is on how the kinetic parameters affect the intracascade recombination of defects. Results indicate that, due to the disparate mobilities of SIA and vacancy clusters, annealing is dominated by SIA migration even at 2050 K. It was found that for 100 keV cascades initiated at 300 K, recombination is dominated by the annihilation of large defect clusters, while for all the other primary knock-on atom (PKA) energies and temperatures, recombination is primarily due to the migration and rotation of small SIA clusters, while the large SIA clusters escape the simulation cell. The annealing efficiency exhibits an inverse U-shaped curve behavior with increasing temperature, especially at large PKA energies, caused by the asymmetry in SIA and vacancy clustering assisted by the large differences in their mobilities. This behavior is unaffected by the dimensionality of SIA migration, and it persists over a broad range of relative mobilities of SIAs and vacancies.

  15. GROWTH KINETIC PARAMETERS AND BIOSYNTHESIS OF POLYHYDROXY-BUTYRATE IN Cupriavidus necator DSMZ 545 ON SELECTED SUBSTRATES

    Directory of Open Access Journals (Sweden)

    M. KHODABANDEH

    2011-03-01

    Full Text Available A kinetic model for Cupriavidus necator in batch culture using glucose, fructose and molasses as carbon sources was obtained. The experimental data was also fitted with the modified logistic equation that can provide adequate description for PHB synthesized by C. necator. The Lineweaver-Burk plot defined biokinetic coefficients which were described by a simplified Monod’s rate model. The specific growth rates, μmax and the Monod constants, Ks, for various substrates such as glucose, fructose and molasses were 0.18, 1.25, 0.42 h-1 and 107.53, 30.342 and 188.16 g/l, respectively. The kinetic constants were evaluated on the basis of non-linear regression solved using MATLAB soft¬ware. Good agreement was found between the experimental and the predicted values, which indicated that the model with differential equations would describe fermentation process for the PHB formation.

  16. Evaluation of kinetic parameters of exothermic gas/solid-reactions by the ignition point method; Bestimmung kinetischer Parameter exothermer Gas/Feststoff-Reaktionen mit der Zuendpunktsmethode

    Energy Technology Data Exchange (ETDEWEB)

    Hein, O.; Jess, A. [Technische Hochschule Aachen (Germany). Inst. fuer Technische Chemie und Makromolekulare Chemie

    2000-01-01

    The determination of kinetic constants of heterogeneous reactions is usually performed in tubular flow reactors under isothermal and stationary reaction conditions. This is often time-consuming and difficult. For example, in case of strong exothermic reactions, temperature gradients up to the ignition of the fixed-bed are hard to avoid, and therefore expensive reactors with internal or external gas recycle are needed. The effect of ignition can also be used to characterize the reactivity of solid fuels and the activity of catalysts, respectively. A well-known method for a simple, fast and accurate determination of the ignition temperature in a lab-scale tubular flow reactor is already described in literature. Yet, the ignition point method is up to now only used as a qualitative measure for the (relative) reactivity of solid fuels and activity of catalysts. Therefore, an attempt was made to extend this method towards a quantitative characterization of the kinetics of exothermic heterogeneous reaction systems, i.e. for a determination of the activation energy and the preexponential factor. The basic idea is thereby to alter the ignition point by a defined variation of the operation conditions such as particle diameter, heating rate as well as of the composition and flow rate of the reacting gas mixture. The resulting data are then used to calculate the kinetic constants based on the theory of ignition of exothermic reactions. The combustion of different cokes as well as of carbon deposits on a Pt-catalyst were selected as model reactions for gas/solid-reactions. In addition, the oxidation of methane on a Pt-catalyst was investigated. The experiments on the influence of the operation conditions show that the gas composition - in case of combustion of coke the oxygen content - has the strongest influence on the ignition temperature. This method is therefore very suitable to determine kinetic constants. To prove the accuracy of this method, the kinetic data were also

  17. Comparison of adsorption equilibrium and kinetic models for a case study of pharmaceutical active ingredient adsorption from fermentation broths: parameter determination, simulation, sensitivity analysis and optimization

    Directory of Open Access Journals (Sweden)

    B. Likozar

    2012-09-01

    Full Text Available Mathematical models for a batch process were developed to predict concentration distributions for an active ingredient (vancomycin adsorption on a representative hydrophobic-molecule adsorbent, using differently diluted crude fermentation broth with cells as the feedstock. The kinetic parameters were estimated using the maximization of the coefficient of determination by a heuristic algorithm. The parameters were estimated for each fermentation broth concentration using four concentration distributions at initial vancomycin concentrations of 4.96, 1.17, 2.78, and 5.54 g l−¹. In sequence, the models and their parameters were validated for fermentation broth concentrations of 0, 20, 50, and 100% (v/v by calculating the coefficient of determination for each concentration distribution at the corresponding initial concentration. The applicability of the validated models for process optimization was investigated by using the models as process simulators to optimize the two process efficiencies.

  18. A New Method to Estimate Intrinsic Parameters in the Ping-pong Bisustrate Kinetic: Application to the Oxipolymerization of Phenol

    Directory of Open Access Journals (Sweden)

    José L. Gómez

    2005-01-01

    Full Text Available A new method for determining the intrinsic parameters of reaction in processes involving a high initial rate has been developed. The usefulness of this alternative, which consists of determining several sets of apparent parameters at different times and then extrapolating these to time zero, is demonstrated proved by the linear dependence obtained between the apparent parameters and the reaction time. The method permitted the values of the intrinsic parameters (enzyme specific activity and Michaelis-Menten constants of both substrates to be obtained for the system under study and was checked with experimental reaction rate data for the soybean peroxidase/phenol/hydrogen peroxide system.

  19. Determination of kinetic parameters of fermentation processes by a continuous unsteady-state method: Application to the alcoholic fermentation of D-xylose by Pichia stipitis

    Energy Technology Data Exchange (ETDEWEB)

    Dominguez, H.; Nunez, M.J.; Lema, J.M. (Avda. Ciencias s/n, Santiago (Spain)); Chamy, R. (Univ. Catolica de Valparaiso (Chile))

    1993-05-01

    A quick technique for determination of kinetic parameters of fermentation processes is proposed and applied to the transformation of D-xylose into ethanol by Pichi stipitis. The commonly used method to evaluate these parameters is based on achieving several steady states. In the proposed procedure, [mu][sub m] and K[sub S] can be determined from only one steady state, by provoking a disturbance over it, after allowing the system to return to the original conditions. The main difference between the steady and unsteady state methods is the required fermentation time; while the former method lasted 350 h, the latter required a period 25 times lower. Kinetic and stoichiometric parameters were determined with both methods under anoxic and limited oxygen concentration conditions. Results from the two methods were compared, giving only 2% and 4.5% differences in the values of K[sub S] and [mu][sub m], respectively, under anoxic conditions; 12.5% for K[sub S] and a little over 4% for [mu][sub m] were the deviations under the latter ones.

  20. Determination of Kinetic Parameters for Methane Oxidation over Pt/γ-Al2O3 in a Fixed-Bed Reactor

    Directory of Open Access Journals (Sweden)

    Vita Wonoputri

    2013-07-01

    Full Text Available This paper describes akinetic study for the determination of the kinetic parameters of lean methane emission oxidation over Pt/γ-Al2O3 in a dedicated laboratory scale fixed bed reactor. A model ofthemechanistic reaction kinetic parameters has been developed. The reaction rate model was determined using therate-limiting step method, which was integrated and optimized to find the most suitable model and parameters. Based on this study, the Langmuir-Hinshelwood reaction rate model with the best correlationis the one where the rate-limiting step is thesurface reaction between methane and one adsorbed oxygen atom. The pre-exponential factor and activation energy were 9.19 x 105 and 92.04 kJ/mol, while the methane and oxygen adsorption entropy and enthalpy were –17.46 J/mol.K, –2739.36 J/mol,–16.34 J/mol.K, and –6157.09 J/mol, respectively.

  1. Assessment and parameter identification of simplified models to describe the kinetics of semi-continuous biomethane production from anaerobic digestion of green and food waste.

    Science.gov (United States)

    Owhondah, Raymond O; Walker, Mark; Ma, Lin; Nimmo, Bill; Ingham, Derek B; Poggio, Davide; Pourkashanian, Mohamed

    2016-06-01

    Biochemical reactions occurring during anaerobic digestion have been modelled using reaction kinetic equations such as first-order, Contois and Monod which are then combined to form mechanistic models. This work considers models which include between one and three biochemical reactions to investigate if the choice of the reaction rate equation, complexity of the model structure as well as the inclusion of inhibition plays a key role in the ability of the model to describe the methane production from the semi-continuous anaerobic digestion of green waste (GW) and food waste (FW). A parameter estimation method was used to investigate the most important phenomena influencing the biogas production process. Experimental data were used to numerically estimate the model parameters and the quality of fit was quantified. Results obtained reveal that the model structure (i.e. number of reactions, inhibition) has a much stronger influence on the quality of fit compared with the choice of kinetic rate equations. In the case of GW there was only a marginal improvement when moving from a one to two reaction model, and none with inclusion of inhibition or three reactions. However, the behaviour of FW digestion was more complex and required either a two or three reaction model with inhibition functions for both ammonia and volatile fatty acids. Parameter values for the best fitting models are given for use by other authors.

  2. Estrone-1-sulphate (E1S) has impact on the kinetics parameters of transporter mediated taurine and glutamate influx in Caco-2 cells

    DEFF Research Database (Denmark)

    Steffansen, Bente; El-Sayed, F

    of membrane transporters. The aim was therefore to investigate if addition of E1S to the growth medium of Caco-2 cells before but not during the influx study, change the kinetic parameters of transporter-mediated influx of taurine and glutamate by respective TAUT and EAAT transporters. The results show that 4...... days pretreatment with E1S change the concentration dependent influx curves and Km for transporter mediated taurine and Km and Jmax for glutamate influx although the effects on Km and Jmax are not significant....

  3. Oxygen transfer coefficient and the kinetic parameters of exo-polygalacturonase production by Aspergillus flavipes FP-500 in shake flasks and bioreactor.

    Science.gov (United States)

    Gómez Sánchez, C E; Martínez-Trujillo, A; Aguilar Osorio, G

    2012-12-01

    To evaluate and compare the sensitivity of Exo-PG production and kinetic parameters of Aspergillus flavipes FP-500 to oxygen transfer condition in shake flasks and bioreactor. Aspergillus flavipes FP-500 was grown on pectin as carbon source in shake flasks and bioreactor at different oxygen transfer conditions. The volumetric coefficient of oxygen transfer (kLa) was modified by changing both, the flask size/medium volume ratio and the agitation speed. Higher biomass concentration, Exo-PG activity, maximum specific growth rate and yield coefficient were obtained in bioreactor at higher kLa value. A strong correlation was found between biomass, Exo-PG activity and growth-associated product coefficient to kLa in bioreactor but does not in shake flasks. The mathematical model provided a good description of growth, pectin consumption and Exo-PG production in submerged batch cultures carried out in bioreactor. Biomass concentration, Exo-PG activity and their kinetics of Aspergillus flavipes FP-500 were strongly influenced by oxygen transfer condition and cultivation system. Significance and Impact of Study The production of enzymes by fungal fermentation is strictly aerobic and understanding the influence of oxygen transfer condition on the production kinetic is of vital importance in order to design, optimize and translate bioprocesses to industrial scale. © 2012 The Society for Applied Microbiology.

  4. Is it possible to study the kinetic parameters of interaction between PNA and parallel and antiparallel DNA by stopped-flow fluorescence?

    Science.gov (United States)

    Barbero, N; Cauteruccio, S; Thakare, P; Licandro, E; Viscardi, G; Visentin, S

    2016-10-01

    Peptide nucleic acids (PNAs) are among the most interesting and versatile artificial structural mimics of nucleic acids and exhibit peculiar and important properties (i.e. high chemical stability, and a high resistance to cellular enzymes and nucleases). Despite their unnatural structure, they are able to recognize and bind DNA and RNA in a very high, specific and selective manner. One of the most popular, easy and reliable method to measure the stability of PNA-DNA hybrid systems is the melting temperature but the thermodynamic data are obtained using a big quantity of materials failing to provide information on the kinetics of the interaction. In the present work, the PNA decamer 6, with the TCACTAGATG sequence of nucleobases, and the corresponding fluorescent PNA-FITU (fluorescein isothiourea) decamer 8 were synthesized with standard manual Boc-based chemistry. The interaction of the PNA-FITU with parallel and antiparallel DNA has been studied by stopped-flow fluorescence, which is proposed as an alternative technique to obtain the kinetic parameters of the binding. The great advantage of using the stopped-flow technique is the possibility of studying the kinetics of the PNA-DNA duplex formation in a physiological environment. In particular, fluorescence stopped-flow technique has been exploited to compare the affinity of two PNA-DNA duplexes since it can discriminate between parallel and antiparallel DNA binding.

  5. Exact relativistic kinetic theory of an electron beam-plasma system: hierarchy of the competing modes in the system parameter space

    CERN Document Server

    Bret, A; Benisti, D; Lefebvre, E

    2008-01-01

    Besides being one of the most fundamental basic issues of plasma physics, the stability analysis of an electron beam-plasma system is of critical relevance in many areas of physics. Surprisingly, decades of extensive investigation had not yet resulted in a realistic unified picture of the multidimensional unstable spectrum within a fully relativistic and kinetic framework. All attempts made so far in this direction were indeed restricted to simplistic distribution functions and/or did not aim at a complete mapping of the beam-plasma parameter space. The present paper comprehensively tackles this problem by implementing an exact linear model. We show that three kinds of modes compete in the linear phase, which can be classified according to the direction of their wavenumber with respect to the beam. We then determine their respective domain of preponderance in a three-dimensional parameter space. All these results are supported by multidimensional particle-in-cell simulations.

  6. Errors in Sounding of the Atmosphere Using Broadband Emission Radiometry (SABER) Kinetic Temperature Caused by Non-Local Thermodynamic Equilibrium Model Parameters

    Science.gov (United States)

    Garcia-Comas, Maya; Lopez-Puertas, M.; Funke, B.; Bermejo-Pantaleon, D.; Marshall, Benjamin T.; Mertens, Christopher J.; Remsberg, Ellis E.; Mlynczak, Martin G.; Gordley, L. L.; Russell, James M.

    2008-01-01

    The vast set of near global and continuous atmospheric measurements made by the SABER instrument since 2002, including daytime and nighttime kinetic temperature (T(sub k)) from 20 to 105 km, is available to the scientific community. The temperature is retrieved from SABER measurements of the atmospheric 15 micron CO2 limb emission. This emission separates from local thermodynamic equilibrium (LTE) conditions in the rarefied mesosphere and thermosphere, making it necessary to consider the CO2 vibrational state non-LTE populations in the retrieval algorithm above 70 km. Those populations depend on kinetic parameters describing the rate at which energy exchange between atmospheric molecules take place, but some of these collisional rates are not well known. We consider current uncertainties in the rates of quenching of CO2 (v2 ) by N2 , O2 and O, and the CO2 (v2 ) vibrational-vibrational exchange to estimate their impact on SABER T(sub k) for different atmospheric conditions. The T(sub k) is more sensitive to the uncertainty in the latter two and their effects depend on altitude. The T(sub k) combined systematic error due to non-LTE kinetic parameters does not exceed +/- 1.5 K below 95 km and +/- 4-5 K at 100 km for most latitudes and seasons (except for polar summer) if the Tk profile does not have pronounced vertical structure. The error is +/- 3 K at 80 km, +/- 6 K at 84 km and +/- 18 K at 100 km under the less favourable polar summer conditions. For strong temperature inversion layers, the errors reach +/- 3 K at 82 km and +/- 8 K at 90 km. This particularly affects tide amplitude estimates, with errors of up to +/- 3 K.

  7. Kinetic modeling of light limitation and sulfur deprivation effects in the induction of hydrogen production with Chlamydomonas reinhardtii: Part I. Model development and parameter identification.

    Science.gov (United States)

    Fouchard, Swanny; Pruvost, Jérémy; Degrenne, Benoit; Titica, Mariana; Legrand, Jack

    2009-01-01

    Chlamydomonas reinhardtii is a green microalga capable of turning its metabolism towards H2 production under specific conditions. However this H2 production, narrowly linked to the photosynthetic process, results from complex metabolic reactions highly dependent on the environmental conditions of the cells. A kinetic model has been developed to relate culture evolution from standard photosynthetic growth to H2 producing cells. It represents transition in sulfur-deprived conditions, known to lead to H2 production in Chlamydomonas reinhardtii, and the two main processes then induced which are an over-accumulation of intracellular starch and a progressive reduction of PSII activity for anoxia achievement. Because these phenomena are directly linked to the photosynthetic growth, two kinetic models were associated, the first (one) introducing light dependency (Haldane type model associated to a radiative light transfer model), the second (one) making growth a function of available sulfur amount under extracellular and intracellular forms (Droop formulation). The model parameters identification was realized from experimental data obtained with especially designed experiments and a sensitivity analysis of the model to its parameters was also conducted. Model behavior was finally studied showing interdependency between light transfer conditions, photosynthetic growth, sulfate uptake, photosynthetic activity and O2 release, during transition from oxygenic growth to anoxic H2 production conditions.

  8. The effect of organic solvents on enzyme kinetic parameters of human CYP3A4 and CYP1A2 in vitro.

    Science.gov (United States)

    Rokitta, Dennis; Pfeiffer, Kay; Streich, Christina; Gerwin, Henrik; Fuhr, Uwe

    2013-10-01

    Abstract Enzyme kinetic parameters provide essential quantitative information about characterization of individual steps in drug metabolism. Such enzymes are located in a (partially) aqueous environment. For in vitro measurements potential lipophilic substrates regularly require organic solvents to achieve concentrations sufficient for access of the drug to the binding site of the enzyme. However, solvents may interact with the enzymes. In this study, we investigated the effects of methanol, ethanol, acetonitrile and dimethyl sulfoxide (1% to 4%) on the assessment of km, Vmax and Clint for the metabolism of midazolam via CYP3A4 to 1-hydroxymidazolam and the metabolism of caffeine to paraxanthine via CYP1A2 using expressed enzymes in vitro. The presence of acetonitrile proved the highest apparent Vmax value for paraxanthine formation but the lowest values for 1-hydroxymidazolam formation. The km value for midazolam showed no systematic effects of organic solvents, while for caffeine km was up to 8-fold lower for solvent free samples compared to solvent containing samples. The present example suggests that effects of solvents may considerably influence enzyme kinetic parameters beyond a mere change in apparent activity. These effects illustrate a difference for individual enzyme--substrate pairs, solvents, and solvent concentrations. What remains is the determination to which extent these effects compromise in vitro-in vivo extrapolations, and which solvents are most appropriate.

  9. Non-Isothermal Kinetics.

    Science.gov (United States)

    Brown, M. E.; Phillpotts, C. A. R.

    1978-01-01

    Discusses the principle of nonisothermal kinetics and some of the factors involved in such reactions, especially when considering the reliability of the kinetic parameters, compared to those of isothermal conditions. (GA)

  10. Evaluation of Tafel-Volmer kinetic parameters for the hydrogen oxidation reaction on Pt(1 1 0) electrodes

    Science.gov (United States)

    Mann, R. F.; Thurgood, C. P.

    2011-05-01

    Modelling of PEM fuel cells has long been an active research area to improve understanding of cell and stack operation, facilitate design improvements and support simulation studies. The prediction of activation polarization in most PEM models has concentrated on the cathode losses since anode losses are commonly much smaller and tend to be ignored. Further development of the anode activation polarization term is being undertaken to broaden the application and usefulness of PEM models in general. Published work on the kinetics of the hydrogen oxidation reaction (HOR) using Pt(h k l) electrodes in dilute H2SO4 has been recently reassessed and published. Correlations for diffusion-free exchange current densities were developed and empirical predictive equations for the anode activation polarization were proposed for the experimental conditions of the previously published work: Pt(1 0 0), Pt(1 1 0) and Pt(1 1 1) electrodes, pH2 of 1 atm, and temperatures of 1, 30 and 60 °C. It was concluded that the HOR on Pt(1 1 0) electrodes followed a Tafel-Volmer reaction sequence. The aim of the present paper is to generalize these Tafel-Volmer correlations, apply them to published data for Pt(1 1 0) electrodes and further develop the modelling of anode activation polarization over the range of operating conditions found in PEMFC operation.

  11. Kinetic parameters and monomeric conversion of different dental composites using standard and soft-start photoactivation modes

    Science.gov (United States)

    Denis, A. B.; Viana, R. B.; Plepis, A. M. G.

    2012-06-01

    This paper evaluates the photopolymerization kinetics and degree of conversion of different commercial dental composites when photoactivated by a LED curing unit using two different modes (standard and soft-start mode). The investigation was performed on with RelyX ARC (dual-cured), Filtek Z-350 (Nanocomposite), Filtek Z-250 (Hybrid), and Filtek Z-350flow (Flowable) resin composites. The analysis used was attenuated total reflection with a Fourier transform infrared (ATR-FTIR). The RelyX ARC resin demonstrated the highest degree of conversion with both LED photoactivation modes. For this resin a 28% decrease in maximum rate was observed and the time to reach its highest rate was almost 2.3 times higher than when the soft-start photoactivation light curing was used. Z-350flow resin recorder a higher maximum rate using the soft-start mode rather than the standard mode. In contrast, the Z-250 showed a higher value using the standard mode. Although Z-250 and Z-350 showed a higher total degree of conversion effectiveness using the soft-start mode, RelyX and Z-350flow achieved a higher value using the standard mode.

  12. Chemical modification and pH dependence of kinetic parameters to identify functional groups in a glucosyltransferase from Strep. Mutans

    Energy Technology Data Exchange (ETDEWEB)

    Bell, J.E.; Leone, A.; Bell, E.T.

    1986-05-01

    A glucosyltransferase, forming a predominantly al-6 linked glucan, was partially purified from the culture filtrate of S. mutans GS-5. The kinetic properties of the enzyme, assessed using the transfer of /sup 14/C glucose from sucrose into total glucan, were studied at pH values from pH 3.5 to 6.5. From the dependence of km on pH, a group with pKa = 5.5 must be protonated to maximize substrate binding. From plots of V/sub max/ vs pH two groups, with pKa's of 4.5 and 5.5 were indicated. The results suggest the involvement of either two carboxyl groups (one protonated, one unprotonated in the native enzyme) or a carboxyl group (unprotonated) and some other protonated group such as histidine, cysteine. Chemical modification studies showed that Diethylyrocarbonate (histidine specific) had no effect on enzyme activity while modification with p-phydroxy-mercuribenzoate or iodoacetic acid (sulfhydryl reactive) and carbodimide reagents (carboxyl specific) resulted in almost complete inactivation. Activity loss was dependent upon time of incubation and reagent concentration. The disaccharide lylose, (shown to be an inhibitor of the enzyme with similar affinity to sucrose) offers no protection against modification by the sulfhydryl reactive reagents.

  13. Quality changes of pasteurised orange juice during storage: A kinetic study of specific parameters and their relation to colour instability.

    Science.gov (United States)

    Wibowo, Scheling; Grauwet, Tara; Santiago, Jihan Santanina; Tomic, Jovana; Vervoort, Liesbeth; Hendrickx, Marc; Van Loey, Ann

    2015-11-15

    In view of understanding colour instability of pasteurised orange juice during storage, to the best of our knowledge, this study reports for the first time in a systematic and quantitative way on a range of changes in specific quality parameters as a function of time and as well as temperature (20-42 °C). A zero-order (°Brix, fructose, glucose), a first-order (vitamin C), a second-order (sucrose) and a fractional conversion model (oxygen) were selected to model the evolution of the parameters between parentheses. Activation energies ranged from 22 to 136 kJ mol(-1), HMF formation being the most temperature sensitive. High correlations were found between sugars, ascorbic acid, their degradation products (furfural and HMF) and total colour difference (ΔE(∗)). Based on PLS regression, the importance of the quality parameters for colour degradation was ranked relatively among each other: the acid-catalysed degradation of sugars and ascorbic acid degradation reactions appeared to be important for browning development in pasteurised orange juice during ambient storage.

  14. Global kinetic rate parameters for the formation of polycyclic aromatic hydrocarbons from the pyrolyis of catechol, a model compound representative of solid fuel moieties

    Energy Technology Data Exchange (ETDEWEB)

    E.B. Ledesma; N.D. Marsh; A.K. Sandrowitz; M.J. Wornat [Princeton University, Princeton, NJ (United States). Department of Mechanical and Aerospace Engineering

    2002-12-01

    To obtain kinetic parameters on PAH formation relevant to solid fuels combustion, pyrolysis experiments have been conducted with catechol, a model fuel representing entities in coal and biomass. Catechol pyrolysis experiments were performed in a tubular-flow reactor at temperatures of 500-1000{sup o}C and at a residence time of 0.4 s. PAH products were identified and quantified by high-pressure liquid chromatography with ultraviolet-visible diode-array detection and by gas chromatography with flame ionization and mass spectrometric detection. A pseudo-unimolecular reaction kinetic model was used to model the experimental yield/temperature data of 15 individual aromatics and of combinations of PAH grouped by structural class and ring-number. The modeling of the individual species' yields showed that the pseudo-unimolecular model agreed very well with the experimental data. E{sub a} values ranged from 50 to 110 kcal mol{sup -1}, generally increasing as the size of the aromatic product increased from one to five aromatic rings. The pseudo-unimolecular model also performed well in modeling the experimental yields of PAH grouped by structural class and ring number. The global kinetic analysis results for PAH grouped by ring number revealed that E{sub a} values increased in the following order: 2-ring {lt} 3-ring {lt} 4-ring {lt} 5-ring {lt} 6-ring. Their yields followed the reverse order: 2-ring {lt} 3-ring {lt} 4-ring {lt} 5-ring {lt} 6-ring. These trends of increasing E{sub a} and decreasing yield, as ring number is increased, are consistent with a mechanism for PAH growth involving successive ring buildup reactions. 39 refs., 6 figs., 3 tabs.

  15. Calculation of reactivities using ionization chamber currents with different sets of kinetic parameters for reduced scram system efficiency in the VVER-1000 of the third unit of the Kalinin nuclear power plant at the stage of physical start-up

    Energy Technology Data Exchange (ETDEWEB)

    Zizin, M. N., E-mail: zizin@adis.vver.kiae.ru [Russian Research Centre Kurchatov Institute (Russian Federation); Zizina, S. N.; Kryakvin, L. V.; Pitilimov, V. A.; Tereshonok, V. A. [JSC VNIIAES (Russian Federation)

    2011-12-15

    The effectiveness of the VVER-1000 reactor scram system is analyzed using ionization chamber currents with different sets of kinetic parameters with allowance for the isotopic composition in the calculation of these parameters. The most 'correct, aesthetically acceptable' results are obtained using the eight-group constants of the ROSFOND (BNAB-RF) library. The difference between the maximum and minimum values of the scram system effectiveness calculated with different sets of kinetic parameters slightly exceeds 2{beta}. The problems of introducing corrections due to spatial effects are not considered in this study.

  16. Influence of instrumental parameters on the kinetic energy of ions and plasma temperature for a hexapole collision/reaction-cell-based inductively coupled plasma quadrupole mass spectrometer.

    Science.gov (United States)

    Favre, Georges; Brennetot, René; Chartier, Frédéric; Tortajada, Jeanine

    2009-02-01

    Inductively coupled plasma mass spectrometry (ICP-MS) is widely used in inorganic analytical chemistry for element and/or isotope ratio measurements. The presence of interferences, which is one of the main limitations of this method, has been addressed in recent years with the introduction of collision/reaction cell devices on ICP-MS apparatus. The study of ion-molecule reactions in the gas phase then became of great importance for the development of new analytical strategies. Knowing the kinetic energy and the electronic states of the ions prior to their entrance into the cell, i.e., just before they react, thereby constitutes crucial information for the interpretation of the observed reactivities. Such studies on an ICP-MS commonly used for routine analyses require the determination of the influence of different instrumental parameters on the energy of the ions and on the plasma temperature from where ions are sampled. The kinetic energy of ions prior to their entrance into the cell has been connected to the voltage applied to the hexapole according to a linear relationship determined from measurements of ion energy losses due to collisions with neutral gas molecules. The effects of the plasma forward power, sampling depth, and the addition of a torch shield to the ICP source were then examined. A decrease of the plasma potential due to the torch shielding, already mentioned in the literature, has been quantified in this study at about 3 V.

  17. Photocatalytic parameters and kinetic study for degradation of dichlorophenol-indophenol (DCPIP) dye using highly active mesoporous TiO2 nanoparticles.

    Science.gov (United States)

    Hamad, H A; Sadik, W A; Abd El-Latif, M M; Kashyout, A B; Feteha, M Y

    2016-05-01

    Highly active mesoporous TiO2 of about 6nm crystal size and 280.7m(2)/g specific surface areas has been successfully synthesized via controlled hydrolysis of titanium butoxide at acidic medium. It was characterized by means of XRD (X-ray diffraction), SEM (scanning electron microscopy), TEM (transmission electron microscopy), FT-IR (Fourier transform infrared spectroscopy), TGA (thermogravimetric analysis), DSC (differential scanning calorimetry) and BET (Brunauer-Emmett-Teller) surface area. The degradation of dichlorophenol-indophenol (DCPIP) under ultraviolet (UV) light was studied to evaluate the photocatalytic activity of samples. The effects of different parameters and kinetics were investigated. Accordingly, a complete degradation of DCPIP dye was achieved by applying the optimal operational conditions of 1g/L of catalyst, 10mg/L of DCPIP, pH of 3 and the temperature at 25±3°C after 3min under UV irradiation. Meanwhile, the Langmuir-Hinshelwood kinetic model described the variations in pure photocatalytic branch in consistent with a first order power law model. The results proved that the prepared TiO2 nanoparticle has a photocatalytic activity significantly better than Degussa P-25.

  18. Plant-mediated biosynthesis of silver nanoparticles by leaf extracts of Lasienthra africanum and a study of the influence of kinetic parameters

    Indian Academy of Sciences (India)

    ELIAS E ELEMIKE; DAMIAN C ONWUDIWE; OLAYINKA ARIJEH; HENRY U NWANKWO

    2017-02-01

    Lasienthra africanum (LA) leaf extract was employed for nano-silver synthesis. The reducing effect of the plant extract was investigated at different times, pH, temperatures and concentrations. The effect of variouskinetic parameters was studied using UV–vis spectroscopy. Blue-shifted surface plasmon bands indicating smaller sized nanoparticles were obtained at neutral pH (6.8–7.0), temperature of 65$^{\\circ}$C and concentration ratio of 1:10 (leafextract: AgNO$_3$) with increasing reaction times under the reaction conditions. The kinetics of the reaction followed pseudo-first- and -second-order rate equations, and was thermodynamically favoured at higher time. Sphericallyshaped nanoparticles were obtained at different reaction conditions.

  19. Comparison of the electronic properties, and thermodynamic and kinetic parameters of the aquation of selected platinum(II) derivatives with their anticancer IC50 indexes.

    Science.gov (United States)

    Bradác, Ondrej; Zimmermann, Tomás; Burda, Jaroslav V

    2008-08-01

    Three potential anticancer agents {trans-[PtCl(2)(NH(3))(thiazole)], cis-[PtCl(2)(NH(3))(piperidine)], and PtCl(2)(NH(3))(cyclohexylamine) (JM118)} were explored and compared with cisplatin and the inactive [PtCl(dien)](+) complex. Basic electronic properties, bonding and stabilization energies were determined, and thermodynamic and kinetic parameters for the aquation reaction were estimated at the B3LYP/6-311++G(2df,2pd) level of theory. Since the aquation process represents activation of these agents, the obtained rate constants were compared with the experimental IC(50) values for several tumor cells. Despite the fact that the processes in which these drugs are involved and the way in which they affect cells are very complex, some correlations can be deduced.

  20. Calculation of Reactor Kinetic Parameters with Monte Carlo Method%反应堆动态参数的蒙特卡罗计算研究

    Institute of Scientific and Technical Information of China (English)

    王冠博; 刘汉刚; 王侃; 刘永康; 曾和荣; 杨鑫

    2012-01-01

    Basic conceptions of kinetic parameters, including effective delayed neutron fraction (βeff), effective neutron generation time (Aeff) and a eigenvalue, and Monte Carlo calculation methods for these values are systematically introduced in this paper. Βeff is obtained with a "Prompt Method". Perturbation method is chosen to obtain Aeff. And then a eigenvalue is obtained by two ways, (I) prompt neutron density attenuation, in other words "direct simulation of time evolvement", (ii) indirect method using the result of kp and neutron generation time. Linear fitting is used to get the critical ac eigenvalues which match well with experimental ones. And uncertainties of kinetic parameters with different methods using Monte Carlo method are also analyzed.%介绍缓发中子有效份额(βeff)、有效中子代时间(∧eff)和α本征值的概念及其蒙特卡罗程序计算方法.采用Prompt Method方法计算得到βeff;微扰法得到∧eff;采用瞬发中子密度衰减直接拟合法和间接求解法得到α本征值;将各种反应性状态下的α拟合得到临界α本征值,并与实验测量的α,值进行比对,结果符合很好;并对动态参数蒙特卡罗程序计算的各种方法进行不确定度分析.

  1. Assessment of the aerobic preparation and bottom ash addition as pretreatment steps before landfilling: impact on methanogenesis kinetics and leachate parameters.

    Science.gov (United States)

    Mansour, Alicia A; Motte, Antoine; Pallier, Virginie; Feuillade-Cathalifaud, Geneviève; Ponthieux, Arnaud

    2012-10-01

    This work focuses on assessing the impact of two types of waste pretreatment: addition of bottom ashes and aerobic pretreatment on both the onset and kinetics of methanogenesis and the evolution of different parameters in the leachate. It also studies the correlation between methane production and the different parameters measured in the leachate produced. A total of six 68-L pilots were thus used with fresh municipal solid waste (MSW) shredded to a 40-mm size. After 14 months of landfilling, the control has produced less than 10 NLkg(-1)DM, which corresponds to around 7% of its biochemical methane potential (BMP). Nevertheless, on one hand for aerobically pretreated waste, the lag phase before the onset of methanogenesis is significantly reduced to 0.9 month compared to more than 1 year for the control. In addition to that, on average 110 NLkg(-1)DM (90% of the BMP) is produced within around 6.5 months. On the other hand, the waste with added bottom ash shows a slight improvement of the lag phase over the control for one of the duplicate: 6.1 months of lag phase. At this stage, on average of 26 NLkg(-1)DM waste are detected (22% of the BMP) no final conclusion concerning the impact of bottom ashes could be made. The data obtained for the leachate parameters agrees with the observations on methane production. Statistical correlation study shows that the two components of the corrected PCA interpret 76% of the variability of the data: SUVA (specific UV absorbance at 254 nm) and HPI(*) (% of hydrophilic compounds) are identified as interesting parameters for following up the biodegradation in landfill conditions. Copyright © 2012 Elsevier Ltd. All rights reserved.

  2. Varietal differences in photosynthetic characters and chlorophyll fluorescence induction kinetics parameters among intergeneric progeny derived from Oryza×Sorghum, its parents, and hybrid rice

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A comparative study on the photosynthetic parameters among intergeneric progenies derived from Oryza sativa L.×Sorghum vulgare L., its maternal parent Gui 630 and commercial 3-line hybrid rice Shanyou 63 in pot experiment in greenhouse was conducted. The morphological and photosynthetic characters of canopy leaves and chlorophyll fluorescence kinetic parameters including Fv/Fm, Fv/F0, photochemical quenching coefficient and non-photochemical coefficient of canopy leaves of 3 varieties were measured. The results showed the progeny, Yuanyou 1, derived from an intergeneric cross of rice and sorghum possesses better canopy spatial architecture with thicker, heavier and bigger canopy leaf than its maternal parent Gui 630. Higher photosynthetic rate due to higher chlorophyll content, higher primary energy transformation efficiency, potential of PSII and non-photochemical quenching coefficient (qE) were also measured in Yuanyou 1. These explain partly why the intergeneric progeny has higher biomass production, and better tolerance to adverse conditions and higher field yields even under stress conditions.

  3. Insights into organogelation and its kinetics from Hansen solubility parameters. Toward a priori predictions of molecular gelation.

    Science.gov (United States)

    Diehn, Kevin K; Oh, Hyuntaek; Hashemipour, Reza; Weiss, Richard G; Raghavan, Srinivasa R

    2014-04-21

    Many small molecules can self-assemble by non-covalent interactions into fibrous networks and thereby induce gelation of organic liquids. However, no capability currently exists to predict whether a molecule in a given solvent will form a gel, a low-viscosity solution (sol), or an insoluble precipitate. Gelation has been recognized as a phenomenon that reflects a balance between solubility and insolubility; however, the distinction between these regimes has not been quantified in a systematic fashion. In this work, we focus on a well-known gelator, 1,3:2,4-dibenzylidene sorbitol (DBS), and study its self-assembly in various solvents. From these data, we build a framework for DBS gelation based on Hansen solubility parameters (HSPs). While the HSPs for DBS are not known a priori, the HSPs are available for each solvent and they quantify the solvent's ability to interact via dispersion, dipole-dipole, and hydrogen bonding interactions. Using the three HSPs, we construct three-dimensional plots showing regions of solubility (S), slow gelation (SG), instant gelation (IG), and insolubility (I) for DBS in the different solvents at a given temperature and concentration. Our principal finding is that the above regions radiate out as concentric shells: i.e., a central solubility (S) sphere, followed in order by spheres corresponding to SG, IG, and I regions. The distance (R0) from the origin of the central sphere quantifies the incompatibility between DBS and a solvent-the larger this distance, the more incompatible the pair. The elastic modulus of the final gel increases with R0, while the time required for a super-saturated sol to form a gel decreases with R0. Importantly, if R0 is too small, the gels are weak, but if R0 is too large, insolubility occurs-thus, strong gels fall within an optimal window of incompatibility between the gelator and the solvent. Our approach can be used to design organogels of desired strength and gelation time by judicious choice of a

  4. Kinetics and

    Directory of Open Access Journals (Sweden)

    Mojtaba Ahmadi

    2016-11-01

    Full Text Available The aqueous degradation of Reactive Yellow 84 (RY84 by potassium peroxydisulfate (K2S2O8 has been studied in laboratory scale experiments. The effect of the initial concentrations of potassium peroxydisulfate and RY84, pH and temperature on RY84 degradation were also examined. Experimental data were analyzed using first and second-order kinetics. The degradation kinetics of RY84 of the potassium peroxydisulfate process followed the second-order reaction kinetics. These rate constants have an extreme values similar to of 9.493 mM−1min−1 at a peroxydisulfate dose of 4 mmol/L. Thermodynamic parameters such as activation (Ea and Gibbs free energy (ΔG° were also evaluated. The negative value of ΔGo and Ea shows the spontaneous reaction natural conditions and exothermic nature.

  5. Kinetic parameters, collision rates, energy exchanges and transport coefficients of non-thermal electrons in premixed flames at sub-breakdown electric field strengths

    Science.gov (United States)

    Bisetti, Fabrizio; El Morsli, Mbark

    2014-01-01

    The effects of an electric field on the collision rates, energy exchanges and transport properties of electrons in premixed flames are investigated via solutions to the Boltzmann kinetic equation. The case of high electric field strength, which results in high-energy, non-thermal electrons, is analysed in detail at sub-breakdown conditions. The rates of inelastic collisions and the energy exchange between electrons and neutrals in the reaction zone of the flame are characterised quantitatively. The analysis includes attachment, ionisation, impact dissociation, and vibrational and electronic excitation processes. Our results suggest that Townsend breakdown occurs for E/N = 140 Td. Vibrational excitation is the dominant process up to breakdown, despite important rates of electronic excitation of CO, CO2 and N2 as well as impact dissociation of O2 being apparent from 50 Td onwards. Ohmic heating in the reaction zone is found to be negligible (less than 2% of peak heat release rate) up to breakdown field strengths for realistic electron densities equal to 1010 cm-3. The observed trends are largely independent of equivalence ratio. In the non-thermal regime, electron transport coefficients are insensitive to mixture composition and approximately constant across the flame, but are highly dependent on the electric field strength. In the thermal limit, kinetic parameters and transport coefficients vary substantially across the flame due to the spatially inhomogeneous concentration of water vapour. A practical approach for identifying the plasma regime (thermal versus non-thermal) in studies of electric field effects on flames is proposed.

  6. The influence of dose on the kinetic parameters and dosimetric features of the main thermoluminescence glow peak in α-Al2O3:C,Mg

    Science.gov (United States)

    Kalita, J. M.; Chithambo, M. L.

    2017-03-01

    The influence of dose (0.1-100 Gy) on the kinetic parameters and the dosimetric features of the main glow peak of α-Al2O3:C,Mg have been investigated. Thermoluminescence (TL) measured at 1 °C/s shows a very high intensity glow peak at 161 °C and six secondary peaks at 42, 72, 193, 279, 330, 370 °C respectively. Analysis shows that the main peak follows first order kinetics irrespective of the irradiation dose. The activation energy is found to be consistent at 1.37 eV and the frequency factor is of the order of 1014 s-1 for any dose between 0.1 and 100 Gy. Further, the analysis for thermal quenching of the main peak of 0.1 Gy irradiated sample shows that the activation energy for thermal quenching is (0.94 ± 0.04) eV. Regarding the dosimetric features of α-Al2O3:C,Mg, the dose response of the main peak is superlinear within 0.1 to 30 Gy of beta dose and then it becomes sublinear up to 100 Gy. Fading analysis shows that the intensity of the main peak drops to ∼22% of its initial value within 2400 s after irradiation and thereafter to ∼14% within 64,800 s. Analysis of the reproducibility shows that the coefficient of variation in the results for 10 identical TL measurements show that reproducibility improves with increase in dose.

  7. Time profiles and toxicokinetic parameters of key biomarkers of exposure to cypermethrin in orally exposed volunteers compared with previously available kinetic data following permethrin exposure.

    Science.gov (United States)

    Ratelle, Mylène; Coté, Jonathan; Bouchard, Michèle

    2015-12-01

    Biomonitoring of pyrethroid exposure is largely conducted but human toxicokinetics has not been fully documented. This is essential for a proper interpretation of biomonitoring data. Time profiles and toxicokinetic parameters of key biomarkers of exposure to cypermethrin in orally exposed volunteers have been documented and compared with previously available kinetic data following permethrin dosing. Six volunteers ingested 0.1 mg kg(-1) bodyweight of cypermethrin acutely. The same volunteers were exposed to permethrin earlier. Blood samples were taken over 72 h after treatment and complete timed urine voids were collected over 84 h postdosing. Cis- and trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acids (trans- and cis-DCCA) and 3-phenoxybenzoic acid (3-PBA) metabolites, common to both cypermethrin and permethrin, were quantified. Blood and urinary time courses of all three metabolites were similar following cypermethrin and permethrin exposure. Plasma levels of metabolites reached peak values on average ≈ 5-7 h post-dosing; the elimination phase showed mean apparent half-lives (t½ ) for trans-DCCA, cis-DCCA and 3-PBA of 5.1, 6.9 and 9.2 h, respectively, following cypermethrin treatment as compared to 7.1, 6.2 and 6.5 h after permethrin dosing. Corresponding mean values obtained from urinary rate time courses were peak values at ≈ 9 h post-dosing and apparent elimination t½ of 6.3, 6.4 and 6.4 h for trans-DCCA, cis-DCCA and 3-PBA, respectively, following cypermethrin treatment as compared to 5.4, 4.5 and 5.7 h after permethrin dosing. These data confirm that the kinetics of cypermethrin is similar to that of permethrin in humans and that their common biomarkers of exposure may be used for an overall assessment of exposure.

  8. Kinetic parameters, collision rates, energy exchanges and transport coefficients of non-thermal electrons in premixed flames at sub-breakdown electric field strengths

    KAUST Repository

    Bisetti, Fabrizio

    2014-01-02

    The effects of an electric field on the collision rates, energy exchanges and transport properties of electrons in premixed flames are investigated via solutions to the Boltzmann kinetic equation. The case of high electric field strength, which results in high-energy, non-thermal electrons, is analysed in detail at sub-breakdown conditions. The rates of inelastic collisions and the energy exchange between electrons and neutrals in the reaction zone of the flame are characterised quantitatively. The analysis includes attachment, ionisation, impact dissociation, and vibrational and electronic excitation processes. Our results suggest that Townsend breakdown occurs for E/N = 140 Td. Vibrational excitation is the dominant process up to breakdown, despite important rates of electronic excitation of CO, CO2 and N2 as well as impact dissociation of O2 being apparent from 50 Td onwards. Ohmic heating in the reaction zone is found to be negligible (less than 2% of peak heat release rate) up to breakdown field strengths for realistic electron densities equal to 1010 cm-3. The observed trends are largely independent of equivalence ratio. In the non-thermal regime, electron transport coefficients are insensitive to mixture composition and approximately constant across the flame, but are highly dependent on the electric field strength. In the thermal limit, kinetic parameters and transport coefficients vary substantially across the flame due to the spatially inhomogeneous concentration of water vapour. A practical approach for identifying the plasma regime (thermal versus non-thermal) in studies of electric field effects on flames is proposed. © 2014 Taylor & Francis.

  9. Sorption of Th(IV) onto ZnO nanoparticles and diatomite-supported ZnO nanocomposite. Kinetics, mechanism and activation parameters

    Energy Technology Data Exchange (ETDEWEB)

    Yusan, Sabriye; Aslani, Mahmut A.A.; Aytas, Sule [Ege Univ., Izmir (Turkey). Inst. of Nuclear Sciences; Bampaiti, Anastasia; Noli, Fotini [Aristotle University of Thessaloniki (Greece). Dept. of Chemistry; Erenturk, Sema [Istanbul Technical Univ., Ayazaga Campus, Maslak-Istanbul (Turkey). Energy Inst.

    2016-11-01

    In this study, for the first time ZnO nanoparticles and diatomite-supported ZnO nanocomposite have been utilized as adsorbent for the removal of Th(IV) ions from aqueous solutions under different experimental conditions. The Langmuir, Freundlich, Temkin and Dubinin- Radushkevich (D-R) isotherms were used to analyze the equilibrium data. The sorption equilibrium data were fitted well to the Langmuir isotherm with maximum sorption capacities values was found to be 1.105 mmol/g and 0.320 mmol/g for ZnO nanoparticles and diatomite supported ZnO nanocomposite, respectively. Pseudo-first and pseudo-second order equations, Intraparticle diffusion and Bangham's models were considered to evaluate the rate parameters and sorption mechanism. Sorption kinetics were better reproduced by the pseudo-second order model (R{sup 2} > 0.999), with an activation energy (E{sub a}) of +99.74 kJ/mol and +62.95 kJ/mol for ZnO nanoparticles and diatomite-supported ZnO nanocomposite, respectively. In order to specify the type of sorption reaction, thermodynamic parameters were also determined. The evaluated ΔG* and ΔH* indicate the non-spontaneous and endothermic nature of the reactions. The results of this work suggest that both of the used materials are fast and effective adsorbents for removing Th(IV) from aqueous solutions and chemical sorption plays a role in controlling the sorption rate.

  10. Perfusion and kinetic variations of left ventricle after primary PCI for acute myocardial infarction: correlation between clinico-angiographic and scintigraphic parameters

    Directory of Open Access Journals (Sweden)

    E Varani

    2007-11-01

    Full Text Available Background: The aim of the present study was to evaluate which of theclinico-angiographic parameters of acute ischemic extension and efficacy ofreperfusion in AMI treated with primary PCI are predictive of infarct size andone month left ventricular ejection fraction (LVEF.Patients and Method: Thirty-five patients with first AMI treated withprimary PCI underwent two rest 99mTc-sestamibi gated SPECT, 4-6 days and 30-40days after PCI. Clinical, electrocardiographic, angiographic and scintigraphicparameters for ischemic extent in acute phase, effective reperfusion,perfusional and kinetic outcome were collected.Results: There was a significant linear correlation among indices ofinitial ischemic extension and early perfusion defect and infarct size, whiletime to treatment (symptom onset to balloon correlated with reperfusion indices(ST resolution, corrected TIMI frame count cTFC, myocardial perfusion grade MPGand with late functional outcomes (smaller infarct size and better LVEF. A timeto treatment of <240 minutes was the most accurate predictor of effectivereperfusion and functional outcome. A late LVEF ≥50% was correlated with sum ofST elevation, ST resolution, time to treatment, CK-MB peak value, early LVEF,and early and late infarct size. An improvement in LVEF in 1 month was seen in60% of patients, who showed a shorter time to treatment and a lower cTFC.Conclusions: Improvements of perfusion and left ventricular function werefrequent one month after primary PCI in AMI. A total ischemic time ≤240 minutesand secondary ST resolution and angiographic parameters of effective reperfusionwere the best indicators of infarct size, late LVEF and improvement of LVEF.

  11. TG-FTIR pyrolysis of coal and secondary biomass fuels: Determination of pyrolysis kinetic parameters for main species and NOx precursors

    Energy Technology Data Exchange (ETDEWEB)

    W. de Jong; G. Di Nola; B.C.H. Venneker; H. Spliethoff; M.A. Wojtowicz [Delft University of Technology, Delft (Netherlands). Process and Energy Department, Energy Technology Section

    2007-10-15

    Co-firing of secondary biomass fuels with coal in coal-fired pulverized fuel boilers is facing increased application in large-scale power production. Fundamental knowledge on the thermochemical behavior of biomass and waste fuels is still lacking, especially regarding the release of the fuel bound nitrogen. Characterization of chicken litter (CL), biomass mix (BM) and meat and bone meal (MBM) and an HV coal blend was performed using TG-FTIR analysis. Three heating rate profiles were applied (10, 30 and 100{sup o}C/min), with a final temperature of 900 {sup o}C. NH{sub 3} was found to be the major gaseous N-product, while HCN and HNCO were also released in substantial amounts. Kinetic parameters for the pyrolysis of biomass fuels were obtained using a model based on parallel first-order reactions with a Gaussian distribution of activation energies. Input files for the coal FG-DVC (functional group-devolatilization, vaporization, cross-linking) and FG-BioMass pyrolysis models were prepared. The fit of model parameters to TG-FTIR product-evolution data was found to be generally good, but the model-predicted yields for some species did not fit experimental data at all heating rates equally well. This problem can be overcome by improvements in the FG-BioMass model. The results of this study can be used to have an improved input of initial pyrolysis in CFD modeling of co-fired boilers. 45 refs., 5 figs., 8 tabs.

  12. Activity, stability and kinetic parameters for -chymotrypsin catalysed reactions in AOT/isooctane reverse micelles with nonionic and zwitterionic mixed surfactants

    Indian Academy of Sciences (India)

    Santosh Kumar Verma; Kallol K Ghosh

    2013-07-01

    Reverse micelles (RMs) of sodium 1,4-bis(2-ethylhexyl)sulphosuccinate (AOT) in nonpolar organic solvents are widely known to have very high solubilization power for water. The method is applied to the hydrolysis of -nitrophenyl acetate (PNPA) catalysed by -chymotrypsin (-CT) in AOT/isooctane/buffer RMs. The increase in -CT activity and stability was an optimum at wo ([H2O]/[AOT]) = 10, z [Isooctane]/[AOT]) = 5. Three typical surfactants were selected based on their head group charges: a non-ionic surfactant Triton-X 100 and two zwitterionic sulphobetaine surfactants of the type CH2+1N+Me2 (CH2)3 SO$^{−}_{3}$ (n = 10; SB3-10, n = 16; SB3-16). The kinetic parameters (such as cat and M) of the -CT at 27°C were determined and compared in the absence and presence of three surfactants. The effect of chain length of zwitterionic surfactant (SB3-10 and SB3-16) on the enzymatic efficacy of -CT as a function of mixed surfactant addition has been investigated in AOT/isooctane RMs at pH 7.75.

  13. A critical study of the Miura-Maki integral method for the estimation of the kinetic parameters of the distributed activation energy model.

    Science.gov (United States)

    Cai, Junmeng; Li, Tao; Liu, Ronghou

    2011-02-01

    Using some theoretically simulated data constructed from known sets of the activation energy distribution f(E) (assumed to follow the Gaussian distribution [Formula in text] where E is the activation energy, E(0) is the mean value of the activation energy distribution, and σ is the standard deviation of the activation energy distribution) and the frequency factor k(0), a critical study of the use of the Miura-Maki integral method for the estimation of the kinetic parameters of the distributed activation energy model has been performed from three cases. For all cases, the use of the Miura-Maki integral method leads to important errors in the estimation of k(0). There are some differences between the assumed and calculated activation energy distributions and the differences decrease with increasing the assumed k(0) values (for Case 1), with increasing the assumed σ values (for Case 2), and with decreasing the b values (for Case 3). Crown Copyright © 2010. Published by Elsevier Ltd. All rights reserved.

  14. Adsorption of iron(III), cobalt(II), and nickel(II) on activated carbon derived from Xanthoceras Sorbifolia Bunge hull: mechanisms, kinetics and influencing parameters.

    Science.gov (United States)

    Zhang, Xiaotao; Hao, Yinan; Wang, Ximing; Chen, Zhangjing

    2017-04-01

    Xanthoceras Sorbifolia Bunge hull activated carbon (XSA) was prepared and characterized by Brunauer-Emmett-Teller analysis, scanning electron microscopy and energy dispersive X-ray (EDX) spectroscopy. The ability of XSA as an adsorbent was investigated for the removal of the iron group ions Fe(III), Co(II), and Ni(II) from aqueous solution. Optimum adsorption parameters were determined based on the initial concentrations of the iron group ions, pH, adsorption temperature, and adsorption time in adsorption studies. The maximum monolayer adsorption capacities were 241.13 mg/g for Fe(III), 126.05 mg/g for Co(II), and 187.96 mg/g for Ni(II), respectively. Adsorption kinetics and isotherms showed that the adsorption process best fitted the nonlinear pseudo-second-order and Langmuir models, and the affinity of the ions for XSA decreased as follows: Fe(III) > Ni(II) > Co(II). Regeneration studies indicated that XSA could be used after several consecutive adsorption/desorption cycles using HNO3. Fourier transform infrared and EDX spectra revealed the chemical adsorption value of XSA as an adsorbent for removing iron group ions from aqueous solutions.

  15. Varietal differences in photosynthetic characters and chlorophyll fluorescence induction kinetics parameters among intergeneric progeny derived from Oryza×Sorghum, its parents, and hybrid rice

    Institute of Scientific and Technical Information of China (English)

    KatsuyoshiShimizu; 唐建军; 陈欣

    2002-01-01

    A comparative study on the photosynthetic parameters among intergeneric progenies derived from Oryza sativa L.× Sorghum vulgare L. , its maternal parent Gui 630 and commercial 3-line hybrid rice Shanyou 63 in pot experiment in greenhouse was conducted. The morphological and photosynthetic characters of canopy leaves and chlorophyll fluorescence kinetic pm'mneters including Fv/Fm, Fv/F0, photochemical quenching coefficient and non-photochemical coefficient of canopy leaves of 3 varieties were measured. The results showed the progeny, Yuanyou 1, derived from an intergeneric cross of rice and sorghum possesses better canopy spatial architecture with thicker, heavier and bigger canopy leaf than its maternal parent Gui 630.Higher photosynthetic rate due to higher chlorophyll content, higher primary energy transformation efficiency,potential of PSII and non-photochemieal quenching coefficient (qE) were also measured in Yuanyou 1. These explain partly why the intergeneric progeny has higher biomass production, and better tolerance to adverse conditions and higher field yields even under stress conditions.

  16. Determination of the kinetic parameters during continuous cultivation of the lipase-producing thermophile Bacillus sp. IHI-91 on olive oil.

    Science.gov (United States)

    Becker, P; Abu-Reesh, I; Markossian, S; Antranikian, G; Märkl, H

    1997-08-01

    A thermostable lipase was produced in continuous cultivation of a newly isolated thermophilic Bacillus sp. strain IHI-91 growing optimally at 65 degrees C. Lipase activity decreased with increasing dilution rate while lipase productivity showed a maximum of 340 U l-1 h-1 at a condition rate of 0.4 h-1. Lipase productivity was increased by 50% compared to data from batch fermentations. Up to 70% of the total lipase activity measured was associated to cells and by-products or residual substrate. Kinetic and stoichiometric parameters for the utilisation of olive oil were determined. The maximal biomass output method led to a saturation constant Ks of 0.88 g/l. Both batch growth data and a washout experiment yielded a maximal specific growth rate, mu max, of 1.0 h-1. Oxygen uptake rates of up to 2.9 g l-1 h-1 were calculated and the yield coefficient, Y X/O, was determined to be 0.29 g dry cell weight/g O2. From an overall material balance the yield coefficient, Y X/S, was estimated to be 0.60 g dry cell weight/g olive oil.

  17. VC对土壤亚硝酸还原酶动力学参数的影响%Effect of VC on Soil Nitrite Reductase Kinetic Parameters

    Institute of Scientific and Technical Information of China (English)

    许明惠; 李昌满

    2012-01-01

    采用rpиcc试剂比色法,研究了VC对灰棕紫泥土亚硝酸还原酶动力学参数的影响.结果表明,VC的加入降低了V0、Km和Vmax值,表明VC对土壤亚硝酸还原酶的作用类型表现为反竞争性抑制作用,但低浓度VC会减弱亚硝酸还原酶与底物亲和力,而加快产物与酶的分离.由于VC具有抗氧化作用,对土壤具有良好作用,作为安全、有效的反硝化抑制剂使用.%The article researched the effect of Vc treatment on the nitrite reductase kinetic parameter of gray-brown purple clay soil by rpHCC reagent colorimetric method. The result showed that Vc treatment reduced the values of V0, Km and Vmax, the effect type of Vc on soil nitrite reductase was uncompetitive inhibition. Low concentration Vc reduced the affinity of nitrite reductase with substrate, and accelerated the separation of products and enzyme. Vc has antioxidant effect, and is good for to soil, it could be the safe and functional nitrification inhibitors.

  18. Kinetic Parameters and Cytotoxic Activity of Recombinant Methionine γ-Lyase from Clostridium tetani, Clostridium sporogenes, Porphyromonas gingivalis and Citrobacter freundii.

    Science.gov (United States)

    Morozova, E A; Kulikova, V V; Yashin, D V; Anufrieva, N V; Anisimova, N Y; Revtovich, S V; Kotlov, M I; Belyi, Y F; Pokrovsky, V S; Demidkina, T V

    2013-07-01

    The steady-state kinetic parameters of pyridoxal 5'-phosphate-dependent recombinant methionine γ -lyase from three pathogenic bacteria, Clostridium tetani, Clostridium sporogenes, and Porphyromonas gingivalis, were determined in β- and γ-elimination reactions. The enzyme from C. sporogenes is characterized by the highest catalytic efficiency in the γ-elimination reaction of L-methionine. It was demonstrated that the enzyme from these three sources exists as a tetramer. The N-terminal poly-histidine fragment of three recombinant enzymes influences their catalytic activity and facilitates the aggregation of monomers to yield dimeric forms under denaturing conditions. The cytotoxicity of methionine γ-lyase from C. sporogenes and C. tetani in comparison with Citrobacter freundii was evaluated using K562, PC-3, LnCap, MCF7, SKOV-3, and L5178y tumor cell lines. K562 (IC50=0.4-1.3 U/ml), PC-3 (IC50=0.1-0.4 U/ml), and MCF7 (IC50=0.04-3.2 U/ml) turned out to be the most sensitive cell lines.

  19. Magnetic isotope effect on kinetic parameters and quantum beats of radical pairs in micellar solution studied by optically detected esr using pulsed microwave.

    Science.gov (United States)

    Kitahama, Yasutaka; Sakaguchi, Yoshio

    2008-01-17

    We investigated the quantum beats, the oscillation between singlet and triplet states of radical pairs induced by the microwave field resonant to one of the component radicals. They were observed as the alternation of the yields of the component radicals by a nanosecond time-resolved optical absorption with the X-band (9.15 GHz) resonant microwave pulse. This technique was applied to the photochemical reaction of benzophenone, benzophenone-d(10), and benzophenone-carbonyl-(13)C in a sodium dodecylsulfate micellar solution with a step-by-step increase of the resonant microwave pulse width. The yields of the component radicals showed alternation with an increase of the microwave pulse width. This indicates that the radical pair retains spin coherence in the micellar solution. The magnetic isotope effect on the amplitude of the quantum beat was observed. The MW effect on the quantum beat of BP-(13)C decreases from 80% to 60% of that of BP by irradiation of the pi-pulse MW due to spin-locking. The kinetic parameters were also determined using the X- or Ku-band (17.44 GHz) region. They are almost similar to each other except for the intersystem recombination rate in the system of BP-(13)C, which may be slightly higher than those in other systems.

  20. Kinetic parameters of the GUINEVERE reference configuration in VENUS-F reactor obtained from a pile noise experiment using Rossi and Feynman methods

    Energy Technology Data Exchange (ETDEWEB)

    Geslot, Benoit; Pepino, Alexandra; Blaise, Patrick; Mellier, Frederic [CEA, DEN, DER/SPEx, Cadarache, F-13108 St Paul Lez Durance (France); Lecouey, Jean-Luc [LPC Caen, ENSICAEN, Universite de Caen, CNRS/IN2P3, 6 Bd. Marechal Juin 14050 Caen cedex (France); Carta, Mario [ENEA, UTFISST-REANUC, C.R. Casaccia, S.P.040 via Anguillarese 301, 00123 S. Maria Di Galeria, Roma (Italy); Kochetkov, Anatoly; Vittiglio, Guido [SCK.CEN, Belgian Nuclear Research Centre, Boeretang 200, BE-2400, Mol (Belgium); Billebaud, Annick [LPSC, CNRS, IN2P3/UJF/INPG, 53 Avenue des Martyrs, 38026 Grenoble cedex (France)

    2015-07-01

    A pile noise measurement campaign has been conducted by the CEA in the VENUS-F reactor (SCK-CEN, Mol Belgium) in April 2011 in the reference critical configuration of the GUINEVERE experimental program. The experimental setup made it possible to estimate the core kinetic parameters: the prompt neutron decay constant, the delayed neutron fraction and the generation time. A precise assessment of these constants is of prime importance. In particular, the effective delayed neutron fraction is used to normalize and compare calculated reactivities of different subcritical configurations, obtained by modifying either the core layout or the control rods position, with experimental ones deduced from the analysis of measurements. This paper presents results obtained with a CEA-developed time stamping acquisition system. Data were analyzed using Rossi-α and Feynman-α methods. Results were normalized to reactor power using a calibrated fission chamber with a deposit of Np-237. Calculated factors were necessary to the analysis: the Diven factor was computed by the ENEA (Italy) and the power calibration factor by the CNRS/IN2P3/LPC Caen. Results deduced with both methods are consistent with respect to calculated quantities. Recommended values are given by the Rossi-α estimator, that was found to be the most robust. The neutron generation time was found equal to 0.438 ± 0.009 μs and the effective delayed neutron fraction is 765 ± 8 pcm. Discrepancies with the calculated value (722 pcm, calculation from ENEA) are satisfactory: -5.6% for the Rossi-α estimate and -2.7% for the Feynman-α estimate. (authors)

  1. A coupled transport and solid mechanics formulation with improved reaction kinetics parameters for modeling oxidation and decomposition in a uranium hydride bed.

    Energy Technology Data Exchange (ETDEWEB)

    Salloum, Maher N.; Shugard, Andrew D.; Kanouff, Michael P.; Gharagozloo, Patricia E.

    2013-03-01

    Modeling of reacting flows in porous media has become particularly important with the increased interest in hydrogen solid-storage beds. An advanced type of storage bed has been proposed that utilizes oxidation of uranium hydride to heat and decompose the hydride, releasing the hydrogen. To reduce the cost and time required to develop these systems experimentally, a valid computational model is required that simulates the reaction of uranium hydride and oxygen gas in a hydrogen storage bed using multiphysics finite element modeling. This SAND report discusses the advancements made in FY12 (since our last SAND report SAND2011-6939) to the model developed as a part of an ASC-P&EM project to address the shortcomings of the previous model. The model considers chemical reactions, heat transport, and mass transport within a hydride bed. Previously, the time-varying permeability and porosity were considered uniform. This led to discrepancies between the simulated results and experimental measurements. In this work, the effects of non-uniform changes in permeability and porosity due to phase and thermal expansion are accounted for. These expansions result in mechanical stresses that lead to bed deformation. To describe this, a simplified solid mechanics model for the local variation of permeability and porosity as a function of the local bed deformation is developed. By using this solid mechanics model, the agreement between our reacting bed model and the experimental data is improved. Additionally, more accurate uranium hydride oxidation kinetics parameters are obtained by fitting the experimental results from a pure uranium hydride oxidation measurement to the ones obtained from the coupled transport-solid mechanics model. Finally, the coupled transport-solid mechanics model governing equations and boundary conditions are summarized and recommendations are made for further development of ARIA and other Sandia codes in order for them to sufficiently implement the model.

  2. Parameter Estimation

    DEFF Research Database (Denmark)

    2011-01-01

    of optimisation techniques coupled with dynamic solution of the underlying model. Linear and nonlinear approaches to parameter estimation are investigated. There is also the application of maximum likelihood principles in the estimation of parameters, as well as the use of orthogonal collocation to generate a set......In this chapter the importance of parameter estimation in model development is illustrated through various applications related to reaction systems. In particular, rate constants in a reaction system are obtained through parameter estimation methods. These approaches often require the application...... of algebraic equations as the basis for parameter estimation.These approaches are illustrated using estimations of kinetic constants from reaction system models....

  3. Study on Kinetic Parameters of Degradating Phenol by Photosynthetic Bacteria%光合细菌降解苯酚的动力学参数研究

    Institute of Scientific and Technical Information of China (English)

    刘宏芳

    2011-01-01

    苯酚是炼焦(油)、塑料、化工等行业生产过程中的主要污染物。随着经济的快速发展,各类含酚废水已经严重威胁着人类的生存环境。利用微生物处理含酚废水是一种经济有效且无二次污染的方法。本文主要研究了光合细菌-沼泽红假单胞菌降解含酚废水的动力学参数。实验结果表明,沼泽红假单胞菌对含酚废水具有很好的降解性能,正常状态下,该菌最大比生长速率μmax为8.00 mg/g.h,半速率常数Ks为247.92 mg/L,产率系数Y为5.88 mg/mg,内源呼吸系数Kd为0.29 d-1。%Phenol is the significant raw material or midst substance of coking plant,oil refining,plastic and medicine composing etc.More and more waste water containing phenol without treatment is threatening the environment heavily with the rapid development of economy.The method of microorganism biodegradation is economic and effective to treat with phenol waste water without second pollution.The kinetic parameters of the degradation of the phenol were studied with Rhodopseudomonas palustri.The experimental results show that Rhodopseudomonas palustris had excellent biodegradability for phenol wastewater.Under normal conditions,μmax is 8.00 mg/g·h,Ks is 247.92 mg/L,Y is 5.88 mg/mg and Kd is 0.29 d-1.

  4. Determination of the kinetic parameters of K{sub 2}Y F{sub 5}: Tb; Determinacion de los parametros cineticos de K{sub 2}Y F{sub 5}: Tb

    Energy Technology Data Exchange (ETDEWEB)

    Gallegos, A.A. [CICATA-IPN, Legaria 694, Col. Irrigacion, 11500 Mexico D.F. (Mexico); Khaidukov, N.M. [Kurnakov Institute of General and Inorganic Chemistry, Moscow (Russian Federation); Azorin, J. [UAM-I, 09340 Mexico D.F. (Mexico)

    2005-07-01

    In this work the K{sub 2}Y doped materials with percentages of 0.01 and 0.2 of F{sub 5} and, 0.8 and 0.99 of Tb{sup 3+} were studied to determine the kinetic parameters (activation energy and frequency factor) of TL peaks with the purpose of comparing those sensitive qualities of the materials at the doping with TR and their candidacy for tests of TL dosimetry (linearity of the response with the absorbed dose and the reproducibility of the measures of the dose). The samples were irradiated with a beta source of {sup 90} Sr/{sup 90} Y, to ambient temperature, giving its a dose of 236.6 mGy, later the kinetic parameters with different experimental procedures were determined: isothermal decay to ambient temperature and erased of peaks not desired to greater temperature than the ambient. The glow curves (TL curves) were obtained with an TL analyzer Harshaw 4000, with interface to CPU for the handling of the data of the curves, which were treated with the curve form method and the models of: Chen first approach and Chen modified, corrected Lushchik approach and Grossweiner approach, to calculate the kinetic parameters of the sample. (Author)

  5. Application of the exact distribution pj{sub k} in the determination of kinetic parameters in a reactor; Aplicacion de la distribucion exacta p{sub k} a la determinacion de parametros cineticos de un reactor

    Energy Technology Data Exchange (ETDEWEB)

    Alca Ruiz, F.

    1982-07-01

    In this report one distribution of neutron counts obtained by a detector placed in a reactor is studied in order to be used in the determination of reactor kinetic parameters such as {beta}/{lambda} and reactivities. The parameters accuracy from this new method is compared with the Feynman and Mogilner method, based too in Reactor Neutron Noise Analysis. These three methods have been applied to JEN-2 reactor and the better accuracy and faster collection of experimental data give some interest to the new method which only requires a good footing code. (Author) 68 refs.

  6. Kinetic and thermodynamic parameters of hydrogen release during the heterogeneous catalytic dehydrogenation of cis- and trans-isomers of perhydro-m-terphenyl

    Science.gov (United States)

    Kalenchuk, A. N.; Bogorodskii, S. E.; Bogdan, V. I.

    2016-10-01

    Comparative studies on the temperature dependence of the dehydrogenation of cis- and trans-isomers of perhydro- m-terphenyl are performed in a flow catalytic reactor. Rate constants and equilibrium constants of all elementary acts of this reaction are calculated on basis of experimental data using the KINET 0.8 program for the mathematical modeling of the kinetics of complex reactions. The resulting data indicate that perhydro- m-terphenyl cis- and trans-isomers structural differences have no appreciable effect on dehydrogenation.

  7. Spin-orbit coupling and paramagnetic relaxation in micellized triplet radical pairs. Determination of relaxation parameters from magnetic field dependences of the decay kinetics

    Science.gov (United States)

    Levin, P. P.; Kuzmin, V. A.

    1990-01-01

    The geminate recombination kinetics of the radical pairs produced by quenching of triplet benzophenone or 4-bromobenzophenone by 4-phenylphenol and 4-phenylaniline in aqueous micellar solutions of sodium dodecyl sulfate has been examined using the laser flash technique. Application of an external magnetic field results in the retardation of geminate recombination up to 20 times. The magnetic field dependences are considered in terms of a simple kinetic scheme, which includes the singlet-triplet evolution in the separated states of a pair due to hyperfine coupling and relaxation mechanisms as well as intersystem recombination process due to the spin-orbit coupling in the contact states of a pair.

  8. Effect of the Hamiltonian parameters on the hysteresis properties of the kinetic mixed spin (1/2, 1) Ising ferrimagnetic model on a hexagonal lattice

    Energy Technology Data Exchange (ETDEWEB)

    Batı, Mehmet, E-mail: mehmet.bati@erdogan.edu.tr [Department of Physics, Recep Tayyip Erdoğan University, 53100 Rize (Turkey); Ertaş, Mehmet [Department of Physics, Erciyes University, 38039 Kayseri (Turkey)

    2017-05-15

    The hysteresis properties of a kinetic mixed spin (1/2, 1) Ising ferrimagnetic system on a hexagonal lattice are studied by means of the dynamic mean field theory. In the present study, the effects of the nearest-neighbor interaction, temperature, frequency of oscillating magnetic field and the exchange anisotropy on the hysteresis properties of the kinetic system are discussed in detail. A number of interesting phenomena such as the shape of hysteresis loops with one, two, three and inverted-hysteresis/proteresis (butterfly shape hysteresis) have been obtained. Finally, the obtained results are compared with some experimental and theoretical results and a qualitatively good agreement is found.

  9. Decolorization Kinetics of Acid Azo Dye and Basic Thiazine Dye in Aqueous Solution by UV/H2O2 and UV/Fenton: Effects of Operational Parameters

    Directory of Open Access Journals (Sweden)

    Baffoun Ayda

    2017-03-01

    Full Text Available The photochemical decolorization of two dyes, namely Acid Yellow 54 and Basic Blue 9, was studied using the UV/H2O2 and UV/Fenton processes. The effects of the amount of H2O2 and FeSO4 as well as the initial pH solution on decolorization kinetics of both the dyes were investigated. The pseudo-first order kinetic model was applied to predict the decolorization of the selected dyes at the different operational conditions and results showed that this model fitted very well with the experimental data. The obtained results also showed the efficiency of UV/Fenton process to quickly degrade aqueous effluents polluted by Acid Yellow 54 and Basic Blue 9 compared to the UV/H2O2 process.

  10. Mathematical determination of kinetic parameters for assessing the effect of the organic solvent on the selectivity of peptide synthesis with immobilized α-chymotrypsin.

    Science.gov (United States)

    Bahamondes, Carola; Wilson, Lorena; Guzmán, Fanny; Illanes, Andrés

    2017-08-25

    The synthesis of the dipeptide N-benzoyl-l-tyrosine-l-argininamide (BTAA) was conducted under kinetic control with N-benzoyl-l-tyrosine ethyl ester as acyl donor and argininamide as nucleophile using immobilized α-chymotrypsin as catalyst. Using a mathematical procedure, the kinetic constants corresponding to the proposed mechanism of peptide synthesis were determined in three different cosolvent media, namely, ethanol, diglyme and acetonitrile. These constants were used for evaluating the selectivity of glyoxyl-agarose immobilized α-chymotrypsin in the synthesis of BTAA by determining the ratios of synthesis to hydrolysis rates. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  11. Exact relativistic kinetic theory of an electron beam-plasma system: hierarchy of the competing modes in the system parameter space

    OpenAIRE

    Bret, A.; Gremillet, L; Benisti, D.; Lefebvre, E.

    2008-01-01

    Besides being one of the most fundamental basic issues of plasma physics, the stability analysis of an electron beam-plasma system is of critical relevance in many areas of physics. Surprisingly, decades of extensive investigation had not yet resulted in a realistic unified picture of the multidimensional unstable spectrum within a fully relativistic and kinetic framework. All attempts made so far in this direction were indeed restricted to simplistic distribution functions and/or did not aim...

  12. Kinetics, reactivity, initial-transition state analysis and thermodynamic parameters of base-catalyzed hydrolysis of coumalic acid in solvents with different polarities

    Directory of Open Access Journals (Sweden)

    Ezz A. Abu-Gharib

    2017-02-01

    Full Text Available Base-catalyzed hydrolysis of coumalic acid (COU in binary aqueous-methanol and aqueous-acetone mixtures has been studied kinetically at a temperature range from 283 to 313 K. Moreover, the change in the activation energy barrier of COU from water to water–methanol and water–acetone mixtures is estimated from the kinetic data. Solvent effects on reactivity trends have been analyzed into initial and transition state components by using transfer chemical potentials of the reactants and kinetic data. The transfer chemical potentials δmμθ for COU− anion are derived from solubility data from its calcium, cerium and lanthanum salts. The decrease in rate constant of the base hydrolysis reaction of COU as the percentage of methanol or acetone increases is dominated by transition state (TS. The base hydrolysis reaction of COU follows a rate law with kobs = k2[OH−] and the reaction mechanism was suggested. The high negative values of entropy of activation support the proposal mechanism, i.e. the investigated reaction takes place via the formation of an intermediate complex. Thus, the ring opening of the intermediate complex would be the rate controlling step.

  13. Non-isothermal decomposition kinetics of magnesite

    OpenAIRE

    Maitra, S; Mukherjee, S.; Saha, N; Pramanik, J

    2007-01-01

    Kinetics of thermal decomposition of Indian magnesite was studied by thermo-gravimetric analysis under non-isothermal condition. Coats and Redfern Integral approximation method was used to determine the kinetic parameters. Using the kinetic parameters different kinetic functions were analyzed with the experimental data to ascertain the decomposition mechanism of magnesium carbonate and it was observed that the decomposition reaction followed a contracting sphere kinetic mechanism.

  14. Modelling and dynamic simulation of a pilot-scale moving bed bioreactor for the treatment of municipal wastewater: model concepts and the use of respirometry for the estimation of kinetic parameters.

    Science.gov (United States)

    Plattes, M; Fiorelli, D; Gillé, S; Girard, C; Henry, E; Minette, F; O'Nagy, O; Schosseler, P M

    2007-01-01

    A model for the simulation of a moving bed bioreactor (MBBR) used for the treatment of municipal wastewater is proposed. The model includes attachment of particulates to the biofilm and detachment of biofilm into the bulk liquid. The growth kinetics are modelled with the activated sludge model no. 1 (ASM1). Respirometry was used for the estimation of kinetic parameters. The resulting respirograms featured the typical endogenous and exogenous respiration phases and the respirogram shapes were as expected from analogous respirometry with activated sludge. The estimated parameter set was used for modelling and simulation of the pilot-scale MBBR. The main proportion of biomass in the MBBR was found to be attached as biofilm on the carrier elements (4.1 -4.6 g dm-3) and only a small amount was suspended in the bulk liquid (0.15gdm(-3)). Attachment and detachment rates were estimated to be 4.8-7.5g m(-2) d(-1) 1for attachment and 6.5-7.5g m(-2) d(-1) for detachment. The biofilm age was estimated to be 1.8-2.7d. The model was used to predict effluent quality parameters and a good fit of the simulated data to the measured data originating from a four-days-long measurement campaign was obtained.

  15. The study of lithium ion de-insertion/insertion in LiMn{sub 2}O{sub 4} and determination of kinetic parameters in aqueous Li{sub 2}SO{sub 4} solution using electrochemical impedance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Manjunatha, H.; Mahesh, K.C. [Chemistry Research Centre, S.S.M.R.V. Degree College, Jayanagar, Bangalore 560041 (India); Suresh, G.S., E-mail: sureshssmrv@yahoo.co.i [Chemistry Research Centre, S.S.M.R.V. Degree College, Jayanagar, Bangalore 560041 (India); Venkatesha, T.V. [Department of Chemistry, Kuvempu University, Jnanasahyadri, Shankaraghatta 577451 Shimoga (India)

    2011-01-01

    In this work, we report a basic study on the mechanism of lithium ion de-insertion/insertion process from/into LiMn{sub 2}O{sub 4} cathode material in aqueous Li{sub 2}SO{sub 4} solution using electrochemical impedance spectroscopy (EIS). An equivalent circuit distinguishing the kinetic parameters of lithium ion de-insertion/insertion is used to simulate the experimental impedance data. The fitting results are in good agreement with the experimental results and the parameters of the kinetic process of Li{sup +} de-insertion and insertion in LiMn{sub 2}O{sub 4} at different potentials during charge and discharge are obtained using the same circuit. The results indicate that the de-insertion/insertion behavior of lithium ions at LiMn{sub 2}O{sub 4} cathode in Li{sub 2}SO{sub 4} aqueous solution is similar to that reported in the organic electrolytes. The charge transfer resistance (R{sub ct}), warburg resistance, double layer capacitance and chemical diffusion coefficient (D{sub Li}{sup +}) vary with potentials during de-insertion/insertion processes. R{sub ct} is lowest at the CV peak potentials and the important kinetic parameter, D{sub Li}{sup +} exhibits two distinct minima at potentials corresponding to CV peaks during de-insertion-insertion and it was found to be between 10{sup -8} and 10{sup -10} cm{sup 2} s{sup -1}during lithium de-insertion/insertion processes.

  16. Correlation between [{sup 18}F]FLT kinetic parameters and in vitro immunohistochemical analysis results in a mouse model with human epithelial carcinoma (A431) and lewis lung carcinoma (LLC) cells

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Su Jin; Lee, Jae Sung; Im, Ki Chun; Kim, Seog Young; Park, Soo Ah; Lee, Dong Soo; Moon, Dae Hyuk [Seoul National Univ. College of Medicine, Seoul (Korea, Republic of)

    2007-07-01

    [18F]FLT is a thymidine analog for assessing the cellular proliferation. Quantitative analysis is particularly important for the in vivo characteristics of the drugs which modulate the cancer-associated alternations of cellular proliferation. We assessed the correlation between the quantitative parameters obtained by the PET kinetic analysis and Ki-67 immunohistochemical analysis results in a mouse model with different cells. The A431 derived from skin epidermoid carcinoma was injected subcutaneously into the shoulders of 9 Balb-c/nu mice at a dose of 7 x 106 cells/site. 9 C57BL/6 mice were inoculated with 1 x 106 LLC lung carcinoma cells in same region. PET scans were acquired for 2 hours after injection of 37MBq [18F]FLT when the tumors achieved diameters of 10 mm. Image-derived left ventricular time-activity curve was used as an input function for kinetic modeling. The time-activity curves of tumor and contra-lateral normal tissues were fitted to two-tissue compartment model with blood volume term. We examined the correlation between kinetic parameters and immunohistochemical results. Semi-quantitative parameters such as percentage injected dose per gram (%ID/g) and SUV was also examined. Metabolic flux of FLT (K{sub FLT}), total distribution volume (DV{sub tot}), distribution volume of FLT phosphorylated nucleotides (DV{sub m}), phosphorylation of FLT by TK1 (k{sub 3}). %ID/g and SUV were high in A431 tumor, whereas LLC tumor had low value. Discrimination of the types of tumor cell lines was possible based on these quantitative and semi-quantitative parameters. In correlation analysis, K{sub FLT} and k{sub 3} had most significant correlation with Ki-67(%). K{sub FLT} and k{sub 3} of [l8F]FLT kinetics were well correlated with in vitro measures of tumor proliferation in a mouse model with A431 and LLC cell line, and should be useful for the assessment of the cancer-associated alternations of cellular proliferation.

  17. Comparative study of diethyl phthalate degradation by UV/H2O2 and UV/TiO2: kinetics, mechanism, and effects of operational parameters.

    Science.gov (United States)

    Song, Chengjie; Wang, Liping; Ren, Jie; Lv, Bo; Sun, Zhonghao; Yan, Jing; Li, Xinying; Liu, Jingjing

    2016-02-01

    The photodegradation of diethyl phthalate (DEP) by UV/H2O2 and UV/TiO2 is studied. The DEP degradation kinetics and multiple crucial factors effecting the clearance of DEP are investigated, including initial DEP concentration ([DEP]0), initial pH values (pH0), UV light intensity, anions (Cl(-), NO(3-), SO4 (2-), HCO3 (-), and CO3 (2-)), cations (Mg(2+), Ca(2+), Mn(2+), and Fe(3+)), and humic acid (HA). Total organic carbon (TOC) removal is tested by two treatments. And, cytotoxicity evolution of DEP degradation intermediates is detected. The relationship between molar ratio ([H2O2]/[DEP] or [TiO2]/[DEP]) and degradation kinetic constant (K) is also studied. And, the cytotoxicity tests of DEP and its degradation intermediates in UV/H2O2 and UV/TiO2 treatments are researched. The DEP removal efficiency of UV/H2O2 treatment is higher than UV/TiO2 treatment. The DEP degradation fitted a pseudo-first-order kinetic pattern under experimental conditions. The K linearly related with molar ratio in UV/H2O2 treatment while nature exponential relationship is observed in the case of UV/TiO2. However, K fitted corresponding trends better in H2O2 treatment than in TiO2 treatment. The Cl(-) is in favor of the DEP degradation in UV/H2O2 treatment; in contrast, it is disadvantageous to the DEP degradation in UV/TiO2 treatment. Other anions are all disadvantageous to the DEP degradation in two treatments. Fe(3+) promotes the degradation rates significantly. And, all other cations in question inhibit the degradation of DEP. HA hinders DEP degradation in two treatments. The intermediates of DEP degradation in UV/TiO2 treatment are less toxic to biological cell than that in UV/H2O2 treatment.

  18. Estimation of Kinetic Parameters for Autocatalytic Oxidation of Cyclohexane Based on a Modified Adaptive Genetic Algorithm%基于一种改进的自适应遗传算法估算环己烷自催化氧化反应动力学参数

    Institute of Scientific and Technical Information of China (English)

    刘平乐; 邹丽珊; 罗和安; 王良芥; 郑金华

    2004-01-01

    A modified genetic algorithm of multiple selection strategies, crossover strategies and adaptive operator is constructed, and it is used to estimate the kinetic parameters in autocatalytic oxidation of cyclohexane. The influences of selection strategy, crossover strategy and mutation strategy on algorithm performance are discussed.This algorithm with a specially designed adaptive operator avoids the problem of local optimum usually associated with using standard genetic algorithm and simplex method. The kinetic parameters obtained from the modified genetic algorithm are credible and the calculation results using these parameters agree well with experimental data.Furthermore, a new kinetic model of cyclohexane autocatalytic oxidation is established and the kinetic parameters are estimated by using the modified genetic algorithm.

  19. Determination of kinetic parameters in Tl dosemeters of LiF: Mg, Cu, P + PTFE developed in the ININ; Determinacion de parametros cineticos en dosimetros Tl de LiF: Mg, Cu, P + PTFE desarrollados en el ININ

    Energy Technology Data Exchange (ETDEWEB)

    Basurto G, B.S

    2002-07-01

    The objective of this work, is the one of determining the kinetic parameters of the dosemeter of LiF: Mg, Cu, P + Ptfe; starting from the curves Tl obtained at being irradiated with alpha radiation ({alpha}), beta ({beta}) and gamma ({gamma}). As like to compare its sensitivity with each radiation type, considering the sensitivity of the TLD-100 as the unit. In the Chapter 1, the fundamental structure of the matter is described, making emphasis in the different radiation types, and their interaction with this. In the Chapter 2, the units are described but used in the dosimetry of the radiation. In the Chapter 3, the basic concepts of the phenomenon of Tl are described and those are explained characteristic of the deconvolution method to determine the kinetics of the one phenomenon. In the Chapter 4, the methodology is detailed that was used in the elaboration of this thesis work, describing the material Tl that were considered like reference, as well as the sources of ionizing radiation, with those that the dosemeters were irradiated and the equipment in the one that the curves Tl was obtained. Reference is made to the software used to carry out the deconvolution of the curves Tl that were obtained in the one experimental development. In the Chapter 5, the obtained results of this study are presented, showing the tables of homogenization of dosemeters and the reading of the same one; they are observed the curves Tl obtained to different radiation doses (alpha, beta and gamma), the intensity Tl in function of the dose. Also they are tabulated, the obtained results in the kinetic parameters of the three different study materials (TLD-100H, USA; TLD-100, USA and LiF: Mg, Cu, P + Ptfe developed in the l.N.l.N). They are analyzed shortly for each material Tl their sensitivity to the ionizing radiation as well as their kinetic parameters. The obtained results showed that the Tl dosemeters of LiF: Mg,Cu,P + Ptfe, they presented a bigger sensitivity that the TLD-100 when

  20. Electrophysiological approach to determine kinetic parameters of sucrose uptake by single sieve elements or phloem parenchyma cells in intact Vicia faba plants

    Directory of Open Access Journals (Sweden)

    Jens B. Hafke

    2013-07-01

    Full Text Available Apart from a few using cut aphid stylets, no attempts have been made thus far to measure in vivo sucrose-uptake properties of sieve elements. We investigated the kinetics of sucrose uptake by single sieve elements and phloem parenchyma cells in Vicia faba plants. To this end, microelectrodes were inserted into free-lying phloem cells in the main vein of the youngest fully-expanded leaf, half-way along the stem, in the transition zone between the autotrophic and heterotrophic part of the stem, and in the root axis. A top-to-bottom membrane potential gradient of sieve elements was observed along the stem (-130 mV to -110 mV, while the membrane potential of the phloem parenchyma cells was stable (approx. -100 mV. In roots, the membrane potential of sieve elements dropped abruptly to -55 mV. Bathing solutions having various sucrose concentrations were administered and sucrose/H+-induced depolarisations were recorded. Data analysis by nonlinear least-square data fittings as well as by linear Eadie-Hofstee (EH -transformations pointed at biphasic Michaelis-Menten kinetics (2 MM, EH: Km1 1.2-1.8 mM, Km2 6.6-9.0 mM of sucrose uptake by sieve elements. However, Akaike’s Information Criterion (AIC favoured single MM kinetics. Using single MM as the best-fitting model, Km values for sucrose uptake by sieve elements decreased along the plant axis from 1 to 7 mM. For phloem parenchyma cells, higher Km values (EH: Km1 10 mM, Km2 70 mM as compared to sieve elements were found. In preliminary patch-clamp experiments with sieve-element protoplasts, small sucrose-coupled proton currents (-0.1 to -0.3 pA/ pF were detected in the whole-cell mode. In conclusion (a Km values for sucrose uptake measured by electrophysiology are similar to those obtained with heterologous systems, (b electrophysiology provides a useful tool for in-situ determination of Km values, (c As yet, it remains unclear if one or two uptake systems are involved in sucrose uptake by sieve

  1. Kinetic Atom.

    Science.gov (United States)

    Wilson, David B.

    1981-01-01

    Surveys the research of scientists like Joule, Kelvin, Maxwell, Clausius, and Boltzmann as it comments on the basic conceptual issues involved in the development of a more precise kinetic theory and the idea of a kinetic atom. (Author/SK)

  2. The ratio of the kinetic inductance to the geometric inductance: a key parameter for the frequency tuning of the THz semiconductor split-ring resonator.

    Science.gov (United States)

    Cong, Jiawei; Yun, Binfeng; Cui, Yiping

    2013-08-26

    By introducing the frequency tuning sensitivity, an analytical model based on equivalent LC circuit is developed for the relative frequency tuning range of THz semiconductor split-ring resonator (SRR). And the model reveals that the relative tuning range is determined by the ratio of the kinetic inductance to the geometric inductance (RKG). The results show that under the same carrier density variation, a larger RKG results in a larger relative tuning range. Based on this model, a stacked SRR-dimer structure with larger RKG compared to the single SRR due to the inductive coupling is proposed, which improves the relative tuning range effectively. And the results obtained by the simple analytical model agree well with the numerical FDTD results. The presented analytical model is robust and can be used to analyze the relative frequency tuning of other tunable THz devices.

  3. THERMODYNAMIC AND KINETIC PARAMETERS OF MIXTURES DESULFURIZING THE MADE WITH CaO, MgO, SiO2 AND CaF2

    Directory of Open Access Journals (Sweden)

    Felipe Nylo de Aguiar

    2012-09-01

    Full Text Available This paper presents an analysis of the kinetics and thermodynamics of marble residue mixtures utilisation on desulfurization of pig iron. The desulfurization was carried out using lime, marble residue, fluorite and pig iron. Different mixtures of these materials were added into a bath of pig iron at 1,450°C. Metal samples were collected via vacuum samplers at times of 5, 10, 15, 20 and 30 minutes, in order to check the variation of sulfur content. Based on the results of chemical analysis of the metal and the desulfurizer mixture, the sulfide capacity of mixtures, the sulfur partition coefficient and the sulfur mass transport coefficient values were calculated.The results show the technical feasibility of using marble waste as desulfurizer agent.

  4. Kinetic Typography

    DEFF Research Database (Denmark)

    van Leeuwen, Theo; Djonov, Emilia

    2014-01-01

    After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images.......After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images....

  5. Investigation of MA Content Effect on Kinetic Parameter in ADS Core%MA 含量对 ADS 堆芯动力学参数的影响研究

    Institute of Scientific and Technical Information of China (English)

    罗润; 宋洪兵; 赵福宇

    2016-01-01

    The effective delayed neutron fraction (βef ),mean neutron generation time (Λ)and reactivity feedback coefficient (α)are the most important parameters in nuclear reactor kinetics.In this study,Monte Carlo method was applied to calculate the kinetic parameters of accelerator driven sub-critical system (ADS)cores,and the effect of mi-nor actinides (MA)content on these parameters was analyzed.The different contents of MA in the fuel were investigated to determine its effect on the kinetic parameters.The results show that when the content of MA reaches 5% in the fuel,theβef andΛ decrease by about 18% and 31%,respectively.With the increase of MA content from 0% to 5%,the average value of Doppler feedback coefficientαD varies from -0.56 pcm/K to-0.36 pcm/K,and the average value of coolant feedback coefficient αC varies from-2.1 1 pcm/K to -1.73 pcm/K.%有效缓发中子份额(βef )、平均中子代时间(Λ)和反应性反馈系数(α)是核反应堆动力学中至关重要的参数。本文采用蒙特卡罗方法计算了加速器驱动的次临界系统(ADS)堆芯的动力学参数,并分析了次锕系核素(MA)装载量对这些参数的影响。通过在燃料中添加不同含量的 MA,来研究其对 ADS堆芯动力学参数的影响。结果表明,当 MA 在燃料中的含量从0%增加到5%时,βef 和Λ的值分别降低了18%和31%,多普勒反馈系数平均值αD 由-0.56 pcm/K 变化到-0.36 pcm/K,冷却剂反馈系数平均值αC 由-2.11 pcm/K变化到-1.73 pcm/K。

  6. Density functional theory investigation of competitive free-radical processes during the thermal cracking of methylated polyaromatics: estimation of kinetic parameters.

    Science.gov (United States)

    Leininger, J-Philippe; Minot, Christian; Lorant, François; Behar, Françoise

    2007-04-26

    Density functional B3LYP and BH&HLYP calculations with the 6-31G** basis set have been performed to investigate elementary reactions playing an important role in the pyrolysis of 1-methylnaphthalene. The pathways describing the destiny of the main radicals, H, methyl, hydromethylnaphthyl and methylnaphthyl, have been studied. At low temperature, addition of H atoms on the aromatic ring is favored over hydrogen abstraction. Except at low temperature (below 400 K), the hydromethylnaphthyl radical undergoes preferentially a loss of hydrogen rather than a bimolecular hydrogen transfer with methylnaphthalene or addition reaction on methylnaphthalene forming a hydrogenated dimer. In the range 400-750 K, the formation of methane by hydrogen abstraction of methyl radical on methylnaphthalene is predominant compared to the formation of hydrodimethylnaphthalenes by addition reaction. Rate constants of reactions describing the formation of heavy products like methyldinaphthylmethanes or dimethylbinaphthalenes have been calculated and discussed. They are also compared to recombination reactions from the literature. Rate constants of these reactions have been computed using transition state theory and can be integrated in kinetic radical schemes of methylated polyaromatic compounds pyrolysis from geological to laboratory conditions.

  7. Electrowinning of Nickel from ammonical sulphate bath and effect of acetone on morphology of nickel deposit and its correlation with kinetic parameters

    Directory of Open Access Journals (Sweden)

    Borikar, D. K.

    2006-01-01

    Full Text Available The electrodeposition of nickel from nickel sulphate bath was studied in ammonia medium. The electrolytic conditions for nickel deposition was optimized at room temperature. The effect of acetone on current efficiency, morphology, stability and particle size of deposited nickel powder was studied. The effect of organic additive Tribenzyl ammonium chloride (TBAC on the morphology of nickel powder was also studied. The kinetics of electrodeposition was studied and the results were utilized in developing mathematical model. During electrodeposition the current efficiency was found to increase with increase in acetone concentration up to 15% V/V in bath solution. On further increase of acetone concentration in bath solution current efficiency decreases. The stability of the electrowon deposited nickel powder was found to be in the range of 85 to 89 %. Powder morphology was found to be dentritic, porous and irregular. The morphology was also found to be underdeveloped dentritic to rounded aggregate as the concentration of organic additive TBAC increases. The average particle size of the deposited powder was found to be decreasing as the concentration of the acetone increases. The average size of the particle is in the range of 13-16 m.

  8. Determination of the best-fit values of kinetic parameters of the Michaelis-Menten equation by the method of least squares with the Taylor expansion.

    Science.gov (United States)

    Sakoda, M; Hiromi, K

    1976-09-01

    The best-fit values of the Michaelis constant (Km) and the maximum velocity (V) in the Michaelis-Menten equation can be obtained by the method of least squares with the Taylor expansion for the sum of squares of the absolute residual, i.e., the difference between the observed velocity and the corresponding velocity by calculation. This method makes it possible to determine the values of Km and V not in a trial-and-error manner but in a deductive and unique manner after some iterative procedures starting from arbitrary approximate values of Km and V. These values can be said to be uniquely determined for a set of data as the finally converged values are no longer dependent upon the initial approximate values of Km and V. It is also very important to obtain initial approximate values of parameters for the application of the method described above. A simple method is proposed to estimate the approximate values of parameters involved in fractional functions. The method of rearrangement after canceling of denominator of a fractional function can be utilized to obtain approximate values, not only for cases of two unknown parameters such as the Michaelis-Menten equation, but also for cases with more than two unknowns.

  9. Dynamic contrast-enhanced CT of head and neck tumors: perfusion measurements using a distributed-parameter tracer kinetic model. Initial results and comparison with deconvolution-based analysis

    Science.gov (United States)

    Bisdas, Sotirios; Konstantinou, George N.; Sherng Lee, Puor; Thng, Choon Hua; Wagenblast, Jens; Baghi, Mehran; San Koh, Tong

    2007-10-01

    The objective of this work was to evaluate the feasibility of a two-compartment distributed-parameter (DP) tracer kinetic model to generate functional images of several physiologic parameters from dynamic contrast-enhanced CT data obtained of patients with extracranial head and neck tumors and to compare the DP functional images to those obtained by deconvolution-based DCE-CT data analysis. We performed post-processing of DCE-CT studies, obtained from 15 patients with benign and malignant head and neck cancer. We introduced a DP model of the impulse residue function for a capillary-tissue exchange unit, which accounts for the processes of convective transport and capillary-tissue exchange. The calculated parametric maps represented blood flow (F), intravascular blood volume (v1), extravascular extracellular blood volume (v2), vascular transit time (t1), permeability-surface area product (PS), transfer ratios k12 and k21, and the fraction of extracted tracer (E). Based on the same regions of interest (ROI) analysis, we calculated the tumor blood flow (BF), blood volume (BV) and mean transit time (MTT) by using a modified deconvolution-based analysis taking into account the extravasation of the contrast agent for PS imaging. We compared the corresponding values by using Bland-Altman plot analysis. We outlined 73 ROIs including tumor sites, lymph nodes and normal tissue. The Bland-Altman plot analysis revealed that the two methods showed an accepted degree of agreement for blood flow, and, thus, can be used interchangeably for measuring this parameter. Slightly worse agreement was observed between v1 in the DP model and BV but even here the two tracer kinetic analyses can be used interchangeably. Under consideration of whether both techniques may be used interchangeably was the case of t1 and MTT, as well as for measurements of the PS values. The application of the proposed DP model is feasible in the clinical routine and it can be used interchangeably for measuring

  10. Dynamic contrast-enhanced CT of head and neck tumors: perfusion measurements using a distributed-parameter tracer kinetic model. Initial results and comparison with deconvolution-based analysis

    Energy Technology Data Exchange (ETDEWEB)

    Bisdas, Sotirios [Department of Diagnostic and Interventional Radiology, Johann Wolfgang GoeUniversity Hospital, 60590 Frankfurt (Germany); Konstantinou, George N [401 General Military Hospital, Athens (Greece); Lee, Puor Sherng [Department of Oncologic Imaging National Cancer Centre, 169610 Singapore (Singapore); Thng, Choon Hua [Department of Oncologic Imaging National Cancer Centre, 169610 Singapore (Singapore); Wagenblast, Jens [Department of Otorhinolaryngology, Johann Wolfgang GoeUniversity Hospital, 60590 Frankfurt (Germany); Baghi, Mehran [Department of Otorhinolaryngology, Johann Wolfgang GoeUniversity Hospital, 60590 Frankfurt (Germany); Koh, Tong San [Center for Modeling and Control of Complex Systems, Nanyang Technological University, 639798 Singapore (Singapore)

    2007-10-21

    The objective of this work was to evaluate the feasibility of a two-compartment distributed-parameter (DP) tracer kinetic model to generate functional images of several physiologic parameters from dynamic contrast-enhanced CT data obtained of patients with extracranial head and neck tumors and to compare the DP functional images to those obtained by deconvolution-based DCE-CT data analysis. We performed post-processing of DCE-CT studies, obtained from 15 patients with benign and malignant head and neck cancer. We introduced a DP model of the impulse residue function for a capillary-tissue exchange unit, which accounts for the processes of convective transport and capillary-tissue exchange. The calculated parametric maps represented blood flow (F), intravascular blood volume (v{sub 1}), extravascular extracellular blood volume (v{sub 2}), vascular transit time (t{sub 1}), permeability-surface area product (PS), transfer ratios k{sub 12} and k{sub 21}, and the fraction of extracted tracer (E). Based on the same regions of interest (ROI) analysis, we calculated the tumor blood flow (BF), blood volume (BV) and mean transit time (MTT) by using a modified deconvolution-based analysis taking into account the extravasation of the contrast agent for PS imaging. We compared the corresponding values by using Bland-Altman plot analysis. We outlined 73 ROIs including tumor sites, lymph nodes and normal tissue. The Bland-Altman plot analysis revealed that the two methods showed an accepted degree of agreement for blood flow, and, thus, can be used interchangeably for measuring this parameter. Slightly worse agreement was observed between v{sub 1} in the DP model and BV but even here the two tracer kinetic analyses can be used interchangeably. Under consideration of whether both techniques may be used interchangeably was the case of t{sub 1} and MTT, as well as for measurements of the PS values. The application of the proposed DP model is feasible in the clinical routine and it

  11. Degradation of dibutyl phthalate (DBP) by UV-254 nm/H2O2 photochemical oxidation: kinetics and influence of various process parameters.

    Science.gov (United States)

    Wang, Dong; Duan, Xiaodi; He, Xuexiang; Dionysiou, Dionysios D

    2016-12-01

    Degradation of dibuytl phthalate (DBP), a plasticizer and also a widely distributed endocrine disruptor, by UV-254 nm/H2O2 advanced oxidation process (AOP) was investigated in this study. A significant DBP removal of 77.1 % at an initial concentration of 1.0 μM was achieved at UV fluence of 160 mJ/cm(2), initial H2O2 dosage of 1.0 mM, and pH of 7.6 ± 0.1. The DBP degradation exhibited a pseudo-first-order reaction kinetic pattern, with the rate constants linearly increasing with increasing H2O2 dosage while decreasing with increasing initial DBP concentration and pH value in a specific range. DBP destruction was significantly inhibited in the presence of alkalinity and natural organic matter (NOM), two known factors that should be taken a serious consideration of in the research and design of UV/H2O2-based AOPs. Presence of common inorganic anions (i.e., Cl(-), SO4(2-), and NO3(-)) and metal cations (i.e., Fe(3+) and Zn(2+)) had a slight impact on the degradation of DBP, although Cu(2+) could improve the degradation efficiency even at a concentration as low as 0.01 mg/L, suggesting a strong potential of applying UV/H2O2 for the removal of DBP with an environmental relevant level of copper.

  12. Enhancing toxic protein expression in Escherichia coli fed-batch culture using kinetic parameters: Human granulocyte-macrophage colony-stimulating factor as a model system.

    Science.gov (United States)

    Khasa, Yogender Pal; Khushoo, Amardeep; Mukherjee, Krishna Jyoti

    2013-03-01

    The kinetics of recombinant human granulocyte-macrophage colony-stimulating factor (hGM-CSF) expression was studied under the strong T7 promoter in continuous culture of Escherichia coli using complex medium to design an optimum feeding strategy for high cell density cultivation. Continuous culture studies were done at different dilution rates and the growth and product formation profiles were monitored post-induction. Recombinant protein expression was in the form of inclusion bodies with a maximum specific product formation rate (q(p)) of 63.5 mg g(-1) DCW h(-1) at a dilution rate (D) of 0.3 h(-1). The maximum volumetric product concentration achieved at this dilution rate was 474 mg l(-1), which translated a ~1.4 and ~1.75 folds increase than the values obtained at dilution rates of 0.2 h(-1) and 0.4 h(-1) respectively. The specific product yield (Y(P/x)) peaked at 138 mg g(-1) DCW, demonstrating a ~1.6 folds increase in the values obtained at other dilution rates. A drop in q(p) was observed within 5-6 h of induction at all the dilution rates, possibly due to protein toxicity and metabolic stress associated with protein expression. The data from the continuous culture studies allowed us to design an optimal feeding strategy and induction time in fed-batch cultures which resulted in a maximum product concentration of 3.95 g l(-1) with a specific hGM-CSF yield (Y(P/x)) of 107 mg g(-1) DCW.

  13. 基于加速度计的汽车动力学参数采集平台设计%Data Acquisition Platform for Automobile Kinetic Parameters Based on Accelerometer ADXL330

    Institute of Scientific and Technical Information of China (English)

    陈泽军

    2011-01-01

    为了方便采集汽车运动中的动力学数据,设计了一种基于加速度计ADXL330的汽车动力学参数采集平台.采用集成CAN协议模块的MC9S12DJ256单片机作为控制器,可以及时、准确地对汽车运动的相关信息进行数据采集、分析和计算.在此平台基础上进行二次开发,可应用于汽车自动变速器、汽车安全气囊(Airbag)、ABS防抱死刹车系统、电子稳定程序(ESP)等方面.%In order to obtain the kinetic data in automobile motion, a data acquisition platform for automobile kinetic parameters based on accelerometer ADXL330 is designed.The platform uses MC9S12DJ256 of integrated CAN protocol module as a controller to collect, analyze and compute the vehicle movement's information timely and accurately.The data acquisition platform-based secondary development can be applied to The automatic transmission, safe airbag, anti-locked braking system, electronic stability program(ESP)and so on.

  14. Modelling the anaerobic digestion of solid organic waste - Substrate characterisation method for ADM1 using a combined biochemical and kinetic parameter estimation approach.

    Science.gov (United States)

    Poggio, D; Walker, M; Nimmo, W; Ma, L; Pourkashanian, M

    2016-07-01

    This work proposes a novel and rigorous substrate characterisation methodology to be used with ADM1 to simulate the anaerobic digestion of solid organic waste. The proposed method uses data from both direct substrate analysis and the methane production from laboratory scale anaerobic digestion experiments and involves assessment of four substrate fractionation models. The models partition the organic matter into a mixture of particulate and soluble fractions with the decision on the most suitable model being made on quality of fit between experimental and simulated data and the uncertainty of the calibrated parameters. The method was tested using samples of domestic green and food waste and using experimental data from both short batch tests and longer semi-continuous trials. The results showed that in general an increased fractionation model complexity led to better fit but with increased uncertainty. When using batch test data the most suitable model for green waste included one particulate and one soluble fraction, whereas for food waste two particulate fractions were needed. With richer semi-continuous datasets, the parameter estimation resulted in less uncertainty therefore allowing the description of the substrate with a more complex model. The resulting substrate characterisations and fractionation models obtained from batch test data, for both waste samples, were used to validate the method using semi-continuous experimental data and showed good prediction of methane production, biogas composition, total and volatile solids, ammonia and alkalinity.

  15. Kinetic parameters as determinants of vertical jump performance. DOI: 10.5007/1980-0037.2012v14n1p41

    Directory of Open Access Journals (Sweden)

    Saray Giovana dos Santos

    2012-01-01

    Full Text Available The aim of this study was to identify force and velocity parameters related to vertical jump performance in counter movement jump (CMJ and squat jump (SJ, and to compare these parameters between sprint runners and volleyball players. Twenty-four male athletes (12 regional/national-level sprint runners and 12 national-level volleyball players participated in this study. The athletes performed CMJ and SJ on a force platform. The following variables were analyzed: jump performance (jump height and power, peak velocity (PV, absolute and relative maximum force (Fmax, rate of force development (RFD, and time to reach maximum force (TFmax. In CMJ, jump height was correlated with PV (r=0.97 and normalized Fmax (r=0.47, whereas jump power was significantly correlated with all variables, except for Fmax (r=0.12. In SJ, PV and normalized Fmax were significantly correlated with jump height (r=0.95 and r=0.51, respectively and power (r=0.80 and r=0.87, respectively. In addition, TFmax was inversely correlated with power (r=-0.49. Runners presented higher performance variables (height and power, normalized Fmax and PV than volleyball players in both CMJ and SJ. In conclusion, velocity and maximum force were the main determinants of height and power in the two types of vertical jump. However, explosive force (RFD and TFmax was also important for power production in vertical jumps. Finally, runners presented a better vertical jump performance than volleyball players.

  16. Enhanced luminescence of ZnO:RE{sup 3+} (RE=Eu, Tb) nanorods by Li{sup +} doping and calculations of kinetic parameters

    Energy Technology Data Exchange (ETDEWEB)

    Pal, Partha P., E-mail: phys.ppal@gmail.com; Manam, J.

    2014-01-15

    Lithium co-doped ZnO:Eu{sup 3+} and ZnO:Tb{sup 3+} nanophosphors were prepared by co-precipitation method and the effect of Li{sup +} co-doping was systematically studied by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), UV-Vis-NIR reflectance, Photoluminescence (PL) spectroscopy and Thermoluminescence (TL) studies. XRD pattern shows typical peak pattern for hexagonal wurtzite structure and matches JCPDS card no. 79-0206. A shift of the (1 0 1) peak towards the lower angle in Li{sup +} co-doped samples can be observed showing the increase of lattice constant for the incorporation of Li{sup +} ions in the lattice sites. The present samples are found to be consisting of nanorods of diameter 60–90 nm as revealed by the SEM image. The FTIR pattern shows the enhancement of peak intensity for the ZnO in the Li{sup +} co-doped samples. The diffuse reflectance study shows red shift of the absorption edges in Li{sup +} co-doped ZnO:Eu{sup 3+} and Li{sup +} co-doped ZnO:Tb{sup 3+}. PL study reveals that a very small amount of Li{sup +} is very effective for charge compensation and for producing lattice defect to enhance the rare-earth related emissions, whereas a little excess of Li{sup +} brings oxygen vacancies, which leads to luminescence quenching. The prominent peaks of the TL glow curves of Li{sup +} co-doped ZnO:RE{sup 3+} samples are found to be increased than that of ordinary ZnO:RE{sup 3+} samples. The peaks are also shifted towards the lower temperature from the peaks of ZnO:RE{sup 3+} due to the Li{sup +} co-doping. The TL glow curves of the Li{sup +} co-doped ZnO:RE{sup 3+} samples are found to obey first order kinetics. The samples are found to be very useful in thermoluminescence dosimetry. -- Highlights: • Effect of Li{sup +} co-doping on ZnO:RE{sup 3+}(RE=Eu,Tb) nanorods were studied. • Formation of nanorods confirmed by SEM and TEM image. • No major change in XRD peak pattern on Li

  17. Fluorescent intercalator displacement replacement (FIDR) assay: determination of relative thermodynamic and kinetic parameters in triplex formation--a case study using triplex-forming LNAs.

    Science.gov (United States)

    Sau, Sujay P; Kumar, Pawan; Sharma, Pawan K; Hrdlicka, Patrick J

    2012-11-01

    Triplex forming oligonucleotides (TFOs) are the most commonly used approach for site-specific targeting of double stranded DNA (dsDNA). Important parameters describing triplex formation include equilibrium binding constants (K(eq)) and association/dissociation rate constants (k(on) and k(off)). The 'fluorescent intercalator displacement replacement' (FIDR) assay is introduced herein as an operationally simple approach toward determination of these parameters for triplexes involving TC-motif TFOs. Briefly described, relative rate constants are determined from fluorescence intensity changes upon: (i) TFO-mediated displacement of pre-intercalated and fluorescent ethidium from dsDNA targets (triplex association) and (ii) Watson-Crick complement-mediated displacement of the TFO and replacement with ethidium (triplex dissociation). The assay is used to characterize triplexes between purine-rich dsDNA targets and TC-motif TFOs modified with six different locked nucleic acid (LNA) monomers, i.e. conventional and C5-alkynyl-functionalized LNA and α-L-LNA pyrimidine monomers. All of the studied monomers increase triplex stability by decreasing the triplex dissociation rate. LNA-modified TFOs form more stable triplexes than α-L-LNA-modified counterparts owing to slower triplex dissociation. Triplexes modified with C5-(3-aminopropyn-1-yl)-LNA-U monomer Z are particularly stable. The study demonstrates that three affinity-enhancing features can be combined into one high-affinity TFO monomer: conformational restriction of the sugar ring, expansion of the pyrimidine π-stacking surface and introduction of an exocyclic amine.

  18. 新的单参数动态再结晶动力学建模及晶粒尺寸预测%A NEW ONE-PARAMETER KINETICS MODEL OF DYNAMIC RECRYSTALLIZATION AND GRAIN SIZE PREDICATION

    Institute of Scientific and Technical Information of China (English)

    刘娟; 李居强; 崔振山; 阮立群

    2012-01-01

    通过引入动态再结晶的演化速率,分析了基于Avrami方程的经典动态再结晶动力学模型的不足,提出了一种新的具有单参数的动态再结晶动力学模型,反映了动态再结晶过程缓慢 快速-缓慢的特点.采用Gleeble-1500热模拟试验机,对典型的具有动态再结晶特性的材料镁合金AZ31B进行了热压缩实验,通过进行参数回归得到了其动态再结晶动力学模型,并与实验结果相对比,验证了该模型的正确性.进一步将稳态变形条件下获得的微观组织演化模型改写成分步叠加形式,与动态再结晶晶粒尺寸模型相结合,应用到非稳态条件的晶粒预测,模拟与实验的对比表明计算结果和定量金相法所获得的结果基本一致,说明了非稳态变形过晶粒的叠加预测方法的合理性.%Dynamic recrystallization (DRX) is considered as one of the most important mi-crostructural evolution mechanisms to obtain fine metallurgical structures, eliminate defects and improve mechanical properties of products. Although the DRX kinetics models proposed by researchers have some differences in parameters and forms, they are all based on the Avrami function describing the relationship between dynamically recrystallized volume fraction and strain or time. Avrami equation is in the form of exponential function and the kinetics curve of DRX exhibits different when the exponent is assumed to be different (between 1 and 2). Under these conditions, however, the exponential function cannot exactly describe the "slow-rapid-slow" property of the development speed of DRX process. By introducing the velocity of development of DRX process, which is referred to as the variation of the dynamically recrystallized volume fraction with strain, namely, the first partial derivative of the dynamically recrystallized volume fraction to strain, a new kinetics model of DRX was proposed in comparison with the classical kinetics model of DRX. The new model

  19. The influence of dose on the kinetic parameters and dosimetric features of the main thermoluminescence glow peak in α-Al{sub 2}O{sub 3}:C,Mg

    Energy Technology Data Exchange (ETDEWEB)

    Kalita, J.M.; Chithambo, M.L., E-mail: m.chithambo@ru.ac.za

    2017-03-01

    Highlights: • Influence of dose on thermoluminescence features of α-Al{sub 2}O{sub 3}:C,Mg have been studied. • Kinetic parameters of the main peak are independent of dose (0.1–100 Gy). • Dose response of the main peak: 0.1–30 Gy, superlinear; 30–100 Gy, sublinear. • Fading of the main peak: ∼22% within 2400 s. • Reproducibility: coefficient of variation in the results of 10 re-cycles: >0.071%. - Abstract: The influence of dose (0.1–100 Gy) on the kinetic parameters and the dosimetric features of the main glow peak of α-Al{sub 2}O{sub 3}:C,Mg have been investigated. Thermoluminescence (TL) measured at 1 °C/s shows a very high intensity glow peak at 161 °C and six secondary peaks at 42, 72, 193, 279, 330, 370 °C respectively. Analysis shows that the main peak follows first order kinetics irrespective of the irradiation dose. The activation energy is found to be consistent at 1.37 eV and the frequency factor is of the order of 10{sup 14} s{sup −1} for any dose between 0.1 and 100 Gy. Further, the analysis for thermal quenching of the main peak of 0.1 Gy irradiated sample shows that the activation energy for thermal quenching is (0.94 ± 0.04) eV. Regarding the dosimetric features of α-Al{sub 2}O{sub 3}:C,Mg, the dose response of the main peak is superlinear within 0.1 to 30 Gy of beta dose and then it becomes sublinear up to 100 Gy. Fading analysis shows that the intensity of the main peak drops to ∼22% of its initial value within 2400 s after irradiation and thereafter to ∼14% within 64,800 s. Analysis of the reproducibility shows that the coefficient of variation in the results for 10 identical TL measurements show that reproducibility improves with increase in dose.

  20. Intestinal transporters for endogenic and pharmaceutical organic anions: the challenges of deriving in-vitro kinetic parameters for the prediction of clinically relevant drug-drug interactions.

    Science.gov (United States)

    Grandvuinet, Anne Sophie; Vestergaard, Henrik Tang; Rapin, Nicolas; Steffansen, Bente

    2012-11-01

    This review provides an overview of intestinal human transporters for organic anions and stresses the need for standardization of the various in-vitro methods presently employed in drug-drug interaction (DDI) investigations. Current knowledge on the intestinal expression of the apical sodium-dependent bile acid transporter (ASBT), the breast cancer resistance protein (BCRP), the monocarboxylate transporters (MCT) 1, MCT3-5, the multidrug resistance associated proteins (MRP) 1-6, the organic anion transporting polypetides (OATP) 2B1, 1A2, 3A1 and 4A1, and the organic solute transporter α/β (OSTα/β) has been covered along with an overview of their substrates and inhibitors. Furthermore, the many challenges in predicting clinically relevant DDIs from in-vitro studies have been discussed with focus on intestinal transporters and the various methods for deducting in-vitro parameters for transporters (K(m) /K(i) /IC50, efflux ratio). The applicability of using a cut-off value (estimated based on the intestinal drug concentration divided by the K(i) or IC50) has also been considered. A re-evaluation of the current approaches for the prediction of DDIs is necessary when considering the involvement of other transporters than P-glycoprotein. Moreover, the interplay between various processes that a drug is subject to in-vivo such as translocation by several transporters and dissolution should be considered. © 2012 The Authors. JPP © 2012 Royal Pharmaceutical Society.

  1. Studies on the effect of different operational parameters on the crystallization kinetics of α-lactose monohydrate single crystals in aqueous solution

    Science.gov (United States)

    Parimaladevi, P.; Srinivasan, K.

    2014-09-01

    Supersaturation dependent nucleation, size and morphology of alpha-lactose monohydrate (α-LM) crystals from aqueous solution were investigated by adopting two different crystallization methods, slow evaporation and fast evaporation, in the supersaturation range between σ=0.05 and 1.30. The induction period of nucleation is comparatively long in case of slow evaporation and is very short in case of fast evaporation process as the interconversion between α-L and β-L is uncontrollable in the former and is under control in the latter case. Moreover α-LM crystals with tomahawk morphology were obtained throughout the supersaturation range by slow evaporation method whereas crystals with tomahawk, triangular and needle-like morphologies were obtained in supersaturation ranges σ=0.05-0.5, σ=0.5-0.9 and σ=0.9-1.30 respectively by fast evaporation method. Experimentally observed nucleation parameters were verified with theoretically deuced values. It is realized that the fast evaporation method employed in the present study is found to be highly efficient in controlling the interconversion between α-L and β-L as well as in suppressing the inhibitory activity of β molecule on the nucleation and growth of α-LM crystals when compared to conventional slow evaporation method and is successful in producing the industrially preferred needle-like crystals at high supersaturation ranges.

  2. Development of a chemical kinetic model for a biosolids fluidized-bed gasifier and the effects of operating parameters on syngas quality.

    Science.gov (United States)

    Champion, Wyatt M; Cooper, C David; Mackie, Kevin R; Cairney, Paul

    2014-02-01

    In an effort to decrease the land disposal of sewage sludge biosolids and to recover energy, gasification has become a viable option for the treatment of waste biosolids. The process of gasification involves the drying and devolatilization and partial oxidation of biosolids, followed closely by the reduction of the organic gases and char in a single vessel. The products of gasification include a gaseous fuel composed largely of N2, H2O, CO2, CO, H2, CH4, and tars, as well as ash and unburned solid carbon. A mathematical model was developed using published devolatilization, oxidation, and reduction reactions, and calibrated using data from three different experimental studies of laboratory-scale fluidized-bed sewage sludge gasifiers reported in the literature. The model predicts syngas production rate, composition, and temperature as functions of the biosolids composition and feed rate, the air input rate, and gasifier bottom temperature. Several data sets from the three independent literature sources were reserved for model validation, with a focus placed on five species of interest (CO, CO2, H2, CH4, and C6H6). The syngas composition predictions from the model compared well with experimental results from the literature. A sensitivity analysis on the most important operating parameters of a gasifier (bed temperature and equivalence ratio) was performed as well, with the results of the analysis offering insight into the operations of a biosolids gasifier.

  3. Simulation and validation of the ruminal digestion of carbohydrates in cattle from kinetic parameters obtained by in vitro gas production technique

    Directory of Open Access Journals (Sweden)

    Luciano da Silva Cabral

    2011-09-01

    Full Text Available This study aimed to validate the estimates of the ruminal degradation of total carbohydrates (TC, ruminal and total digestion of fibrous carbohydrates (FC and microbial nitrogen flow in the abomasum evaluated by in vitro gas production technique (IVGP. Six ruminally and abomasally cannulated steers arranged in a double 3 × 3 latin square were used to measure described parameters with indigestible neutral detergent fiber (INDF utilization as marker. Total and fibrous carbohydrates degraded in the rumen were estimated through digestion rates obtained for fibrous (FC and non fibrous carbohydrates (NFC using in vitro gas production technique, corrected for its respective ruminal and postruminal passage rates. The estimation of the total digestion of FC was done by the sum of ruminal and post-ruminal digestion of these compounds. The microbial nitrogen flow in the abomasum was estimated by the calculating the microbial efficiency of bacteria that ferment FC and NFC, utilizing the microbial growth rate obtained by the ruminal digestion rate for carbohydrate fractions in IVGP. The utilization of the in vitro gas production technique allows obtaining accurate estimates of the ruminal digestion of total carbohydrates, total and ruminal digestion of fiber carbohydrates and microbial protein flow in the abomasum.

  4. Stochastic Kinetics of Nascent RNA

    Science.gov (United States)

    Xu, Heng; Skinner, Samuel O.; Sokac, Anna Marie; Golding, Ido

    2016-09-01

    The stochastic kinetics of transcription is typically inferred from the distribution of RNA numbers in individual cells. However, cellular RNA reflects additional processes downstream of transcription, hampering this analysis. In contrast, nascent (actively transcribed) RNA closely reflects the kinetics of transcription. We present a theoretical model for the stochastic kinetics of nascent RNA, which we solve to obtain the probability distribution of nascent RNA per gene. The model allows us to evaluate the kinetic parameters of transcription from single-cell measurements of nascent RNA. The model also predicts surprising discontinuities in the distribution of nascent RNA, a feature which we verify experimentally.

  5. Kinetic parameters of the phenomenon of light emission thermally stimulated in CaF{sub 2} doped with Tm{sup 3+} ions; Parametros cineticos del fenomeno de emision de luz termicamente estimulada en CaF{sub 2} dopado con iones de Tm{sup 3+}

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez M, P. R. [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Cruz Z, E.; Furetta, C., E-mail: pedro.gonzalez@inin.gob.mx [UNAM, Instituto de Ciencias Nucleares, Apdo. Postal 70-543, 04510 Mexico D. F. (Mexico)

    2015-10-15

    Full text: The characterization of new thermoluminescent materials used in radiation dosimetry, require the determination of kinetic parameters, which are associated with the number and shape of the peaks representing brightness curves. The most important parameters are: energy or depth of the traps (E), the frequency factor (s) and order kinetics (b). These are necessary to predict the stability of the thermoluminescent information saved after the effect of irradiation on the material. In this paper, the results of the determination of kinetic parameters of CaF{sub 2} doped with Tm{sup 3+} ions are presented, after being irradiated with gamma rays of {sup 60}Co. The methods used for the determination of kinetic parameters were: initial growth of thermoluminescent signal, Chen method of type general order and by deconvolution of the brightness curve. The results showed that the brightness curve of CaF{sub 2} has three peaks, the main peak at 491 K and two smaller peaks, one at 431 and another at 573 K. The dosimetric peak (491 K) has general order kinetics. (Author)

  6. Kinetic distance and kinetic maps from molecular dynamics simulation

    CERN Document Server

    Noe, Frank

    2015-01-01

    Characterizing macromolecular kinetics from molecular dynamics (MD) simulations requires a distance metric that can distinguish slowly-interconverting states. Here we build upon diffusion map theory and define a kinetic distance for irreducible Markov processes that quantifies how slowly molecular conformations interconvert. The kinetic distance can be computed given a model that approximates the eigenvalues and eigenvectors (reaction coordinates) of the MD Markov operator. Here we employ the time-lagged independent component analysis (TICA). The TICA components can be scaled to provide a kinetic map in which the Euclidean distance corresponds to the kinetic distance. As a result, the question of how many TICA dimensions should be kept in a dimensionality reduction approach becomes obsolete, and one parameter less needs to be specified in the kinetic model construction. We demonstrate the approach using TICA and Markov state model (MSM) analyses for illustrative models, protein conformation dynamics in bovine...

  7. 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

  8. Kinetic Interface

    DEFF Research Database (Denmark)

    2009-01-01

    A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises.......A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises....

  9. Kinetic properties of fractal media

    CERN Document Server

    Chumak, Oleg V

    2016-01-01

    Kinetic processes in fractal stellar media are analyzed in terms of the approach developed in our earlier paper (Chumak, Rastorguev, 2016) involving a generalization of the nearest neighbor and random force distributions to fractal media. Diffusion is investigated in the approximation of scale-dependent conditional density based on an analysis of the solutions of the corresponding Langevin equations. It is shown that kinetic parameters (time scales, coefficients of dynamic friction, diffusion, etc.) for fractal stellar media can differ significantly both qualitatively and quantitatively from the corresponding parameters for a quasi-uniform random media with limited fluctuations. The most important difference is that in the fractal case kinetic parameters depend on spatial scale length and fractal dimension of the medium studied. A generalized kinetic equation for stellar media (fundamental equation of stellar dynamics) is derived in the Fokker-Planck approximation with the allowance for the fractal properties...

  10. Erbium hydride decomposition kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  11. Adsorption studies of molasse's wastewaters on activated carbon: modelling with a new fractal kinetic equation and evaluation of kinetic models.

    Science.gov (United States)

    Figaro, S; Avril, J P; Brouers, F; Ouensanga, A; Gaspard, S

    2009-01-30

    Adsorption kinetic of molasses wastewaters after anaerobic digestion (MSWD) and melanoidin respectively on activated carbon was studied at different pH. The kinetic parameters could be determined using classical kinetic equations and a recently published fractal kinetic equation. A linear form of this equation can also be used to fit adsorption data. Even with lower correlation coefficients the fractal kinetic equation gives lower normalized standard deviation values than the pseudo-second order model generally used to fit adsorption kinetic data, indicating that the fractal kinetic model is much more accurate for describing the kinetic adsorption data than the pseudo-second order kinetic model.

  12. Kinetic Parameters of Interaction Between Cell Membrane and Drug by ppKCE%药物与细胞膜相互作用的ppKCE动力学参数

    Institute of Scientific and Technical Information of China (English)

    夏之宁; 李丽仙; 陈华; 熊彩侨; 杨丰庆

    2011-01-01

    在区段-区段动力学毛细管电泳(ppKCE)的理论基础上,以兔红细胞膜和人红细胞膜为受体,研究了药物跨膜转运的动力学过程,同时测得了表征药物与细胞膜间结合快慢的正向结合速率常数kon、反向解离速率常数koff及配体与受体间相互作用的结合常数Kb.考察了迁移时间及峰高的稳定性、pH值和温度对药物与细胞膜相互作用动力学参数的影响.结果表明,与人体生理pH值一致时,细胞膜具有最大的生物活性,细胞膜与药物的Kb及kon均达到最大值.测定了细胞膜与西酞普兰、依匹斯汀、加替沙星及罗沙替丁相互作用的kon,koff和Kb.采用"时间比法"和紫外-可见吸收光谱法对该方法的准确性进行了验证.本研究为评价药物疗效、研究毒性及药物动力学提供了一种新方法.%Based on the theory of plug-plug kinetic capillary electrophoresis (ppKCE), the rabbit red blood cell membrane and human red blood cell membrane were used to study the kinetic parameters of the interaction between the cell membrane and drug. The rate constants of complex formation kon, the dissociation koff and the binding constant Kb between cell membrane and drugs were directly determined simultaneously. The stability of peak height and migration time was studied. The influence of pH and temperature on the kinetic parameters of the interaction between the cell membrane and drugs were examined and analyzed. The results indicate that at physiological pH value, the cell membrane showed biggest biology activeness, the kon and Kb between cell membrane and drugs reached maximum value. The values of koff, kon and Kb between cell membrane and CIT,Epinastine, Gatifloxacin and Roxatidine were gained. The accuracy of ppKCE was confirmed by the time ratio method and UV-Vis absorption spectra. It could provide a new approach for the evaluation of drug efficiency,toxicity and pharmacokinetics in vivo.

  13. 不同条件下小麦根系吸收菲的动力学参数变化%Changes in kinetic parameters of phenanthrene uptake by wheat roots under different conditions

    Institute of Scientific and Technical Information of China (English)

    陆守昆; 杨青青; 王红菊; 李金凤; 沈羽; 占新华

    2016-01-01

    Polycyclic aromatic hydrocarbons(PAHs)are ubiquitous contaminants in the environment. Dietary intake of plant-based foods has become a major contribution to the total exposure of PAHs for the human beings. Because of well-documented carcinogenicity, muta-genicity and toxicity of PAHs to humans, it is of great importance to establish a model of PAH uptake by crop roots for health risk assess-ments of human exposure to PAHs. However, little information is available regarding such models of PAH uptake by crop roots including ac-tive transport. Here hydroponic experiments were employed to investigate the kinetic parameters of phenanthrene uptake by wheat roots un-der different temperatures, pHs, and wheat seedling ages. In a temperature range of 15~30 ℃, Km and V max increased with an increase in temperature. The relationship between Km or V max and temperature was well fitted with an exponential function. When the temperature was higher than 35 ℃, Km and V max decreased. At pH of 3.00~8.00, the affinity of phenanthrene to wheat root carrier proteins decreased with in-creasing pH. The V max was greatest at pH 5.50. However, the affinity of phenanthrene to wheat root carriers increased with seedling growth, but V max was just reverse. There was no significant difference in uptake kinetics between in vivo and in vitro wheat roots. Therefore, it was concluded that temperature, pH and seedling age have remarkable effects on kinetic parameters of phenanthrene uptake by wheat roots. Our results provide insights into both biochemical mechanisms underlying PAH uptake by plant roots and data for establishing model for PAH uptake by crop roots.%为揭示植物根系吸收多环芳烃(PAHs)的生物化学机制,建立疏水性有机污染物的植物根系吸收数学模型,并为科学预测农作物的污染风险提供依据,采用水培方法研究了不同温度、pH、培养时间以及地上部分去除与否条件下小麦根系吸收菲的动力学参数

  14. Optimization of parameters for cerium(III) biosorption onto biowaste materials of animal and plant origin using 5-level Box-Behnken design:Equilibrium, kinetic, thermodynamic and regeneration studies

    Institute of Scientific and Technical Information of China (English)

    Jaya Sre Varsihini C; Devlina Das; Nilanjana Das

    2014-01-01

    Response surface methodology (RSM) employing 5-level Box-Behnken design was used to optimize the biosorption of ce-rium(III) onto biowaste materials of animal and plant origin viz. prawn carapace (PC) and corn style (CS). Various process parame-ters viz. pH (A:3.0-9.0), biomass dosage (B:0.05-0.35 g/L), initial metal concentration (C:50-350 mg/L), contact time (D:2-6 h) and temperature (E:20-60 °C) were chosen for optimization. A log transformation was suggested by the Box-Cox plot in the present case. A low p-value of<0.0001 validated the significance of the model. Maximum Ce(III) uptake of 218.3 mg/g for PC and 180.2 mg/g for CS was noted under optimum conditions. Among the equilibrium isotherms, Freundlich model was found to be the best fit-ted one suggesting a heterogeneous mode of biosorption on PC whereas Langmuir model showed the best fit suggesting homogene-ous mode of cerium biosorption on CS. This was further confirmed by scanning electron microscopy (SEM). Kinetic studies showed better applicability of pseudo-first order model suggesting physisorption as phenomena underlying the process. Film-diffusion was suggested by the non-linearity of the Boyd plot. Thermodynamic studies showed that the process was endothermic and spontaneous. FTIR analysis confirmed a major involvement of the participation of amide, amines, ketones and primary alcohol groups during Ce(III) biosorption. EDAX analysis confirmed the major participation of carbon group during Ce(III) biosorption. This was the first report on parameter optimization of Ce(III) biosorption onto biowaste materials using 5-level Box-Behnken experimental design which might be helpful for the recovery of Ce(III) from aqueous environment.

  15. KINETICS STUDY ON NITRATION OF METHYL RICINOLEATE

    OpenAIRE

    Abdullah, Abdullah; Triyono, Triyono; Trisunaryanti, Wega; Haryadi, Winarto

    2012-01-01

    Kinetics parameter values of methyl ricinoleate nitration (rate constant, reaction order and the rate of reaction) have been determined. Nitration was carried out with both concentrations of HNO3 and acetic anhydride in excess to the concentration of methyl ricinoleate. Thus, the kinetics parameter value was only affected by the concentration of methyl ricinoleate. Based on kinetic study conducted, it could be concluded that the nitration follows pseudo first-order, and the reaction rate for ...

  16. Glucose-6-phosphate dehydrogenase from brewers' yeast. The effects of pH and temperature on the steady-state kinetic parameters of the two-chain protein species.

    Science.gov (United States)

    Kuby, S A; Roy, R N

    1976-05-04

    A systematic study has been made of the pH- and temperature-dependency of the steady-state kinetic parameters of the stabilized two-subunit enzyme species of glucose-6-phosphate dehydrogenase, in the absence of superimposed association-dissociation reactions. The Vmax(app) data obtained in several buffers between pH 5 and 10 and at 18-32 degrees C lead to the postulate that at least two sets of protonic equilibria may govern the catalysis (one near pH 5.7 AT 25 DEGREES C and another near pH 9.2); furthermore, two pathways for product formation (i.e., two Vmax's) appear to be required to explain the biphasic nature of the log Vmax(app) vs. pH curves, with Vmax(basic) greater than Vmax(acidic + neutral). Of the several buffers explored, either a uniform degree of interaction or a minimal degree of buffer species interaction could be assessed from the enthalpy changes associated with the derived values for ionization constants attributed to the protonic equilibria in the enzyme-substrates ternary complexes for the case of Tris-acetate-EDTA buffers, at constant ionic strength. With the selection of this buffer at 0.1 (T/2) and at 25 and 32 degrees C, a self-consistent kinetic mechanism has emerged which allows for the random binding of the two fully ionized substrates to the enzyme via two major pathways, and product formation by both E-A--B- and HE-A--B-. As before (Kuby et al. Arch. Biochem, Biophys. 165, 153-178, 1974), a quasi-equilibrium is presumed, with rate-limiting steps (k + 5 and k + 5') at the interconversion of the ternary complexes. Values for the two sets of protonic equilibria defined by this mechanism (viz., pKk, pKH2 for the first ionizations, and pKk', pKH' for the second) could then be estimated. From their numerical values (e.g., at 25 degrees C: pKK = 5.7 PKH2 = 5.2; and pKK' = 9.1, PKH' = 8.2) and from the values for delta H degrees ioniz (e.g., delta H degrees pKK APPROXIMATELY 5.1 KCAL/MOL; DELTA H degrees pKK' APPROXIMATELY 11 KCAL/MOL), A

  17. Kinetic model of fishing in highly-deviated well and parameter optimization of fishing tool%大斜度井投捞操作动力学模型及投捞器参数优化设计

    Institute of Scientific and Technical Information of China (English)

    宋显民; 黄重光; 刘士英; 范晓东

    2016-01-01

    Fishing in highly-deviated well is critical for valve inspection in gas lift oil production and for separated injection and allocation in water injection wells. The current researches in this aspect only focus on design of processes and tools, but there is no appropriate theoretical model available as a guide. In this paper, an energy-based kinetic model of fishing was established for highly-deviated wells which are developed by gas lift, using the kinetic principle and the formula of tool undershoot velocity with and without consideration to wireline towing. The relationships between the residual undershoot energy and the well deviation in fishing section and diameter/length of the fishing tool were analyzed. Moreover, a parameter optimization model of fishing tool was built on the basis of the maximum well deviation that the fishing technique can adapt to, and relevant calculations were made for the design. The results provide theoretical basis for current researches on fishing in highly-deviated wells and relevant tools, and also contribute to the future improvement of fishing technologies.%大斜度井投捞是气举采油检阀和水井分注调配的关键技术。目前大斜度井投捞研究仅限于工艺和工具设计,缺乏相关的理论模型指导工作。因此,以大斜度井气举投捞操作为研究对象,利用动力学原理及不考虑钢丝拖曳和考虑钢丝拖曳两种情况下投送器下冲速度公式,建立了能量形式的大斜度井投捞操作动力学模型,分析了下冲剩余能与投捞段井斜、投送器直径、投送器长度的关系;并以投捞技术适应的最大井斜为目标建立了投送器参数优化设计模型,进行了相关设计计算,为目前大斜度井投捞工艺和相关工具研究提供了理论基础,对今后投捞技术的改进与提高提供参考。

  18. 克百威光催化降解动力学的研究%Parameters effect on photocatalytic degradation kinetics of carbofuran in TiO2 aqueous solution

    Institute of Scientific and Technical Information of China (English)

    阳海; 周硕林; 尹明亮; 皮露露; 曾健; 易兵

    2013-01-01

    采用TiO2光催化技术对克百威的降解进行了研究,并系统地考察了催化剂用量,溶液初始pH值,底物浓度,活性氧物种和各种阴阳离子对其降解动力学的影响.用Langmuir-Hinshelwood动力学模型对克百威的光催化降解进行了研究,结果表明,克百威在弱碱性条件下降解速率最快,OH对克百威降解贡献比约为93.4%,h+和其他ROSs的贡献则相对较小.而水溶液中的阴离子BrO3-和S2O82对克百威的光催化降解有促进作用,I则有明显的抑制作用,并且水溶液中的K+,Ca2+,Na+,Mg2+和Cu2+等金属阳离子对克百威的降解也均体现了一定程度的抑制作用.%Photocatalytic degradation of carbofuran has been investigated in TiO2 aqueous solution under UV irradiation. The effects of various parameters such as catalyst amount, pH value, concentration of carbofuran, reactive oxidative species (ROSs), different anions and metal cations on photocatalytic degradation kinetics were studied. The degradation of carbofuran follows pseudo first-order kinetics by using Langmuir-Hinshelwood model. The results indicated that the weak alkaline solution was favor for the degradation of carbofuran. The ·OH radical is responsible for the major degradation of carbofuran, and its contribution is about 93.4%, while the other ROSs play a minor contribution to the degradation. Additionally, the anions of BrO3- and S2O82- accelerate the degradation rate of carbofuran, while I- anion inhibits degradation reaction obviously. The photocatalytic degradation reactions were also inhibited to some extent when K+, Ca2+, Na+, Mg2+ and Cu2+ cations were added to aqueous solution.

  19. Kinetic and Thermodynamic Parameters about Adsorption of XAD-4 Resin for O-aminophenol%XAD-4树脂吸附邻氨基苯酚的动力学及热力学研究

    Institute of Scientific and Technical Information of China (English)

    张启伟; 王桂仙

    2011-01-01

    研究XAD-4树脂对水相中邻氨基苯酚(OPA)吸附的动力学和热力学参数.动力学实验表明:树脂对邻氨基苯酚的吸附拟用准一级动力学处理.并测定不同温度下树脂对邻氨基苯酚吸附的表观速率常数及活化能.热力学研究表明:树脂对邻氨基苯酚的吸附符合Langmuir等温吸附方程.测得吸附热ΔH为-22.0 kJ/mol,说明树脂对邻氨基苯酚的吸附过程为放热过程,且ΔH〈40kJ/mol,表明吸附过程主要为物理吸附.同时测得吉布斯自由能ΔG〈0,表明吸附质从溶液到吸附剂表面的吸附过程是自发过程.%The kinetic and the thermodynamic parameters about adsorption of the XAD-4 Resin for o-aminophenol in aqueous solution were studied.Researches of kinetics showed that adsorption of the XAD-4 Resin for o-aminophenol could deal with pseudo first-order reaction.The apparent adsorption rate constants and activated energy were determined at different temperature.Researches of thermodynamics showed that the adsorption behavior of the XAD-4 Resin for o-aminophenol obeyed the Langmuir isotherm model.The heat of adsorption are ΔH=-22.0 kJ/mol,which means that the sorption process is an exothermic process,and ΔH40 kJ/mol,which means that the sorption process is mostly physical adsorption and ΔG0,which means that the sorption process is a spontaneous process.

  20. Oxidative desulfurization: kinetic modelling.

    Science.gov (United States)

    Dhir, S; Uppaluri, R; Purkait, M K

    2009-01-30

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel.

  1. Physisorption kinetics

    CERN Document Server

    Kreuzer, Hans Jürgen

    1986-01-01

    This monograph deals with the kinetics of adsorption and desorption of molecules physisorbed on solid surfaces. Although frequent and detailed reference is made to experiment, it is mainly concerned with the theory of the subject. In this, we have attempted to present a unified picture based on the master equation approach. Physisorption kinetics is by no means a closed and mature subject; rather, in writing this monograph we intended to survey a field very much in flux, to assess its achievements so far, and to give a reasonable basis from which further developments can take off. For this reason we have included many papers in the bibliography that are not referred to in the text but are of relevance to physisorption. To keep this monograph to a reasonable size, and also to allow for some unity in the presentation of the material, we had to omit a number of topics related to physisorption kinetics. We have not covered to any extent the equilibrium properties of physisorbed layers such as structures, phase tr...

  2. Kinetic Biochemistry

    Directory of Open Access Journals (Sweden)

    Lorentz JÄNTSCHI

    2003-03-01

    Full Text Available Mathematics and computer programming have a major contribution to chemistry. Two directions can be identified: one that searches and tries (rich to explain the structural binding and shape of the chemical compounds [1] with major applications in QSPR/QSAR studies [2], and applied sciences such as engineering of materials or agriculture [3]; the second direction is to models the kinetic processes that are involved in chemical reactions [4]. Many such models are available here. The present paper describes three variants of well the known kinetic models and presents the mathematical equations associated with them. The differential equations are numerically solved and fitted with MathCad program. [1] Diudea M., Gutman I., Jäntschi L., Molecular Topology, Nova Science, Huntington, New York, 332 p., 2001, 2002. [2] Diudea M. V., Ed., QSPR / QSAR Studies by Molecular Descriptors, Nova Science, Huntington, New York, 438 p., 2001. [3] Jäntschi L., Microbiology and Toxicology. Phytochemistry Studies (in Romanian, Amici, Cluj-Napoca, 184 p., 2003. [4] Jäntschi L., Unguresan M., Physical Chemistry. Molecular Kinetic and Dynamic (in Romanian, Mediamira, Cluj-Napoca, 159 p., 2001.

  3. Study on Kinetic Parameters of Crude Oil Cracking Gas and Its Application%原油裂解成气动力学参数及其应用研究

    Institute of Scientific and Technical Information of China (English)

    李贤庆; 仰云峰; 田辉; 肖贤明; 黄孝波; 王萌; 杨朝世

    2012-01-01

    The thermal simulation experiment of Yaha and Hade crude oil samples in Tarim Basin was carried out, by using the gold tube confined system. The yield characteristics and kinetic parameters of cracking gases from Yaha and Hade oil samples were studied. The results demonstrate that the Yaha and Hade oil samples have high total gas yields (738.87 ml/g, 598.98 ml/g) and C2_5 yields (256.85 ml/g, 188.63 ml/g). Differences are existed in the kinetic parameters of cracking gases in the Yaha and Hade oils. The activation energy distributions of methane, ethane and propane generated from the Yaha oil sample are in the range of (66 -83 ) × 4. 186kJ/mol, (59 -72) × 4. 186kJ/ mol, and (59 -65)×4. 186kJ/mol. Their frequency factors from the Yaha oil sample are 2.07 ×10^16s^-1, 1.0 ×10^14s^-1 , and 1.0 ×10^14s^-1 , respectively. The activation energy distributions of methane, ethane and propane from the Hade oil sample are in the range of (63 -84)×4. 186 kJ/mol, (57 ~63) ×4. 186 kJ/mol, and (58 ~70) ×4. 186 kJ/mol. Their frequency factors from the Hade oil sample are 1.42 ×10^16s^-1, 1 .0 ×10^14s^-1, and 1.0 ×10^14s^-1 , re- spectively. The Mandong 1 gas pool in the eastern Tarim Basin was taken as an example and its kinetic modeling of gas generation was studied. It is suggested that gas source of the Mandong 1 gas pool was resulted from a large number of crude oil cracking.%采用黄金管限定体系,对塔里木盆地牙哈、哈得原油样品进行了热模拟实验,研究了原油样品热裂解生成气态烃的产率特征及其动力学参数。结果表明,牙哈、哈得原油样品裂解具有高的C1-5产率(738.87ml/g、598.98ml/g)和C2-5产率(256.85ml/g、188.63ml/g)。牙哈、哈得原油样品裂解成气动力学参数存在差异:牙哈原油样品裂解气甲烷、乙烷、丙烷生成的活化能范围分别为(66—83)×4.186kJ/mol、(59~72)×4.186kJ/mol、(59—65)×4.186k

  4. Kinetic and Thermodynamic Studies of Charge-Transfer Complex ...

    African Journals Online (AJOL)

    Kinetic and Thermodynamic Studies of Charge-Transfer Complex Formation ... The activation parameters, i.e. activation energy, enthalpy, and entropy of ... KEYWORDS Charge-transfer complex, imipramine, DDQ, ionization potential, kinetic, ...

  5. Kinetic distance and kinetic maps from molecular dynamics simulation.

    Science.gov (United States)

    Noé, Frank; Clementi, Cecilia

    2015-10-13

    Characterizing macromolecular kinetics from molecular dynamics (MD) simulations requires a distance metric that can distinguish slowly interconverting states. Here, we build upon diffusion map theory and define a kinetic distance metric for irreducible Markov processes that quantifies how slowly molecular conformations interconvert. The kinetic distance can be computed given a model that approximates the eigenvalues and eigenvectors (reaction coordinates) of the MD Markov operator. Here, we employ the time-lagged independent component analysis (TICA). The TICA components can be scaled to provide a kinetic map in which the Euclidean distance corresponds to the kinetic distance. As a result, the question of how many TICA dimensions should be kept in a dimensionality reduction approach becomes obsolete, and one parameter less needs to be specified in the kinetic model construction. We demonstrate the approach using TICA and Markov state model (MSM) analyses for illustrative models, protein conformation dynamics in bovine pancreatic trypsin inhibitor and protein-inhibitor association in trypsin and benzamidine. We find that the total kinetic variance (TKV) is an excellent indicator of model quality and can be used to rank different input feature sets.

  6. Modelling of the Kinetics of Sulfure Compounds in Desulfurisation Processes Based on Industry Data of Plant

    Directory of Open Access Journals (Sweden)

    Krivtcova Nadezhda

    2016-01-01

    Full Text Available Modelling of sulfur compounds kinetics was performed, including kinetics of benzothiophene and dibenzothiophene homologues. Modelling is based on experimental data obtained from monitoring of industrial hydrotreating set. Obtained results include kinetic parameters of reactions.

  7. Estimation of the Kinetic Parameters and the Critical Rate of Temperature Rise in the Thermal Explosion from the Exothermic Autocatalytic Decomposition of 3,4-Bis(4′-nitrofurazan-3′-yl)-2-oxofurazan (BNFOF) Using Non-isothermal Differential Scanning Calorimetry

    Institute of Scientific and Technical Information of China (English)

    ZHAO Feng-Qi; ZHOU Yan-Shui; ZHAO Hong-An; GAO Sheng-Li; SHI Qi-Zhen; LU Gui-E; JIANG Jin-Yong; GUO Peng-Jiang; HU Rong-Zu; ZHANG Hai; XIA Zhi-Ming; GAO Hong-Xu; CHEN Pei; LUO Yang; ZHANG Zhi-Zhong

    2006-01-01

    A method of estimating the kinetic parameters and the critical rate of temperature rise in the thermal explosion for the autocatalytic decomposition of 3,4-bis(4′-nitrofurazan-3′-yl)-2-oxofurazan (BNFOF) with non-isothermal differential scanning calorimetry (DSC) was presented. The rate equation for the decomposition of BNFOF was established, and information was obtained on the rate of temperature increase in BNFOF when the empiric-order autocatalytic decomposition was converted into thermal explosion.

  8. Buprenorphine kinetics.

    Science.gov (United States)

    Bullingham, R E; McQuay, H J; Moore, A; Bennett, M R

    1980-11-01

    Buprenorphine kinetics was determined in surgical patients using radioimmunoassay. Buprenorphine was measured in the plasma of 24 patients who had received 0.3 mg buprenorphine intraoperatively. After 3 hr 10 of these patients then received a further 0.3 mg buprenorphine intravenously for postoperative pain relief, and 11 patients were given 0.3 mg intramuscularly; again, plasma levels were measured for 3 hr. The data fitted closely to a triexponential decay curve. There was a very fast initial phase, with a half-life (t1/2) of 2 min. The terminal t1/2 was slow, approximately 3 hr. Comparison of the kinetics of the same patient, awake and anesthetized, showed that the clearance was significantly lower in the anesthetized state. A notable feature of the drug given intramuscularly is rapid systemic availability, so that peaks are obtained in 2 to 5 min, and in 10 min the resulting levels are the same as for the intravenous and intramuscular routes.

  9. Effect of operational and water quality parameters on conventional ozonation and the advanced oxidation process O3/H2O2: Kinetics of micropollutant abatement, transformation product and bromate formation in a surface water.

    Science.gov (United States)

    Bourgin, Marc; Borowska, Ewa; Helbing, Jakob; Hollender, Juliane; Kaiser, Hans-Peter; Kienle, Cornelia; McArdell, Christa S; Simon, Eszter; von Gunten, Urs

    2017-10-01

    The efficiency of ozone-based processes under various conditions was studied for the treatment of a surface water (Lake Zürich water, Switzerland) spiked with 19 micropollutants (pharmaceuticals, pesticides, industrial chemical, X-ray contrast medium, sweetener) each at 1 μg L(-1). Two pilot-scale ozonation reactors (4-5 m(3) h(-1)), a 4-chamber reactor and a tubular reactor, were investigated by either conventional ozonation and/or the advanced oxidation process (AOP) O3/H2O2. The effects of selected operational parameters, such as ozone dose (0.5-3 mg L(-1)) and H2O2 dose (O3:H2O2 = 1:3-3:1 (mass ratio)), and selected water quality parameters, such as pH (6.5-8.5) and initial bromide concentration (15-200 μg L(-1)), on micropollutant abatement and bromate formation were investigated. Under the studied conditions, compounds with high second-order rate constants kO3>10(4) M(-1) s(-1) for their reaction with ozone were well abated (>90%) even for the lowest ozone dose of 0.5 mg L(-1). Conversely, the abatement efficiency of sucralose, which only reacts with hydroxyl radicals (OH), varied between 19 and 90%. Generally, the abatement efficiency increased with higher ozone doses and higher pH and lower bromide concentrations. H2O2 addition accelerated the ozone conversion to OH, which enables a faster abatement of ozone-resistant micropollutants. Interestingly, the abatement of micropollutants decreased with higher bromide concentrations during conventional ozonation due to competitive ozone-consuming reactions, except for lamotrigine, due to the suspected reaction of HOBr/OBr(-) with the primary amine moieties. In addition to the abatement of micropollutants, the evolution of the two main transformation products (TPs) of hydrochlorothiazide (HCTZ) and tramadol (TRA), chlorothiazide (CTZ) and tramadol N-oxide (TRA-NOX), respectively, was assessed by chemical analysis and kinetic modeling. Both selected TPs were quickly formed initially to reach a

  10. Chemical kinetics modeling

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C.K.; Pitz, W.J. [Lawrence Livermore National Laboratory, CA (United States)

    1993-12-01

    This project emphasizes numerical modeling of chemical kinetics of combustion, including applications in both practical combustion systems and in controlled laboratory experiments. Elementary reaction rate parameters are combined into mechanisms which then describe the overall reaction of the fuels being studied. Detailed sensitivity analyses are used to identify those reaction rates and product species distributions to which the results are most sensitive and therefore warrant the greatest attention from other experimental and theoretical research programs. Experimental data from a variety of environments are combined together to validate the reaction mechanisms, including results from laminar flames, shock tubes, flow systems, detonations, and even internal combustion engines.

  11. A Comprehensive Enzyme Kinetic Exercise for Biochemistry

    Science.gov (United States)

    Barton, Janice S.

    2011-01-01

    This article describes a comprehensive treatment of experimental enzyme kinetics strongly coupled to electronic data acquisition and use of spreadsheets to organize data and perform linear and nonlinear least-squares analyses, all in a manner that promotes development of important reasoning skills. Kinetic parameters are obtained for the stable…

  12. Kinetic buffers.

    Science.gov (United States)

    Alibrandi, Giuseppe; Fabbrizzi, Luigi; Licchelli, Maurizio; Puglisi, Antonio

    2015-01-12

    This paper proposes a new type of molecular device that is able to act as an inverse proton sponge to slowly decrease the pH inside a reaction vessel. This makes the automatic monitoring of the concentration of pH-sensitive systems possible. The device is a composite formed of an alkyl chloride, which kinetically produces acidity, and a buffer that thermodynamically modulates the variation in pH value. Profiles of pH versus time (pH-t plots) have been generated under various experimental conditions by computer simulation, and the device has been tested by carrying out automatic spectrophotometric titrations, without using an autoburette. To underline the wide variety of possible applications, this new system has been used to realize and monitor HCl uptake by a di-copper(II) bistren complex in a single run, in a completely automatic experiment. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Kinetics of microwave drying of apples

    Directory of Open Access Journals (Sweden)

    G. V. Kalashnikov

    2012-01-01

    Full Text Available The influence of main technological parameters was studied as a result of research of microwave drying of apples and the analysis of kinetic regularity of the process was performed.

  14. The kinetics of the hydrogen chloride oxidation

    Directory of Open Access Journals (Sweden)

    Gonzalez Martinez Isai

    2013-01-01

    Full Text Available Hydrogen chloride (HCl oxidation has been investigated on technical membrane electrode assemblies in a cyclone flow cell. Influence of Nafion loading, temperature and hydrogen chloride mole fraction in the gas phase has been studied. The apparent kinetic parameters like reaction order with respect to HCl, Tafel slope and activation energy have been determined from polarization data. The apparent kinetic parameters suggest that the recombination of adsorbed Cl intermediate is the rate determining step.

  15. Probability representation of kinetic equation for open quantum system

    CERN Document Server

    Man'ko, V I; Shchukin, E V

    2003-01-01

    The tomographic probability distribution is used to decribe the kinetic equations for open quantum systems. Damped oscillator is studied. Purity parameter evolution for different damping regime is considered.

  16. Crystallization Kinetics within a Generic Modeling Framework

    DEFF Research Database (Denmark)

    Meisler, Kresten Troelstrup; von Solms, Nicolas; Gernaey, Krist V.

    2014-01-01

    to the modeling of various kinetic phenomena like nucleation, growth, agglomeration, and breakage are discussed in terms of model forms, model parameters, their availability and/or estimation, and their selection and application for specific crystallization operational scenarios under study. The advantages......A new and extended version of a generic modeling framework for analysis and design of crystallization operations is presented. The new features of this framework are described, with focus on development, implementation, identification, and analysis of crystallization kinetic models. Issues related...... of employing a well-structured model library for storage, use/reuse, and analysis of the kinetic models are highlighted. Examples illustrating the application of the modeling framework for kinetic model discrimination related to simulation of specific crystallization scenarios and for kinetic model parameter...

  17. Correlação entre parâmetros da cinética de intumescimento com características estruturais e hidrofílicas de hidrogéis de poliacrilamida e metilcelulose Correlation between parameters of swelling kinetic with network and hydrophilic characteristics of polyacrylamide and methylcellulose hydrogels

    Directory of Open Access Journals (Sweden)

    Fauze A. Aouada

    2009-01-01

    Full Text Available In this paper, the effects of acrylamide (AAm, methylcellulose (MC contents, pH and ionic strength on kinetic, network and hydrophilic properties of polyacrylamide and methylcellulose hydrogels were investigated. The hydrogels were characterized by evaluating of network [average molecular weight between crosslinks (M C, crosslink density (q and the number of elastically effective chains (Ve], and kinetic parameters [diffusional exponent (n, diffusion constant (k and diffusion coefficient (D]. Such properties were controlled by adjusting of the AAm, MC contents, pH and ionic strength factors. Due to high hydrophilicity and fast water-uptake, the PAAm-MC hydrogels can be considered as materials for potential applications in agricultural fields, mainly in controlled release of water or pesticides.

  18. Inference from some pharmacokinetic and pharmacodynamic parameters of busulfan through the analysis of its induction kinetics of micronuclei polychromated erythrocytes; Inferencia de algunos parametros farmacocineticos y farmacodinamicos de busulfan, mediante el analisis de su cinetica de induccion de eritrocitos policromaticos micronucleados

    Energy Technology Data Exchange (ETDEWEB)

    Lopez I, M.R.; Vallarino K, T.; Morales R, P. [Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, 11801 Mexico D.F. (Mexico)

    2001-07-01

    The induction kinetics of micronuclei polychromated eritrocites (EPC-MN) which is produced by busulfan and compared with that produced by the ionizing radiation, allows to make inferences over the pharmacokinetics and pharmacodynamics of busulfan. Observing two induction mechanisms of MN, this one early at low doses and other later at high doses, this last is presented to a critical dose being very sheer and associated with an increase of the cytotoxicity. The data suggest the transformation or dependence between these two types of leisures, which to determine the narrow therapeutical margin of busulfan. The pharmacokinetic parameters determined in the early mechanisms kinetics indicate a latency period, a time of effective activity and of half life 5.7, 5.2 and 2.6 h respectively. (Author)

  19. KINETICS OF QUERCETIN NITRATIO N BY HORSERADISH PEROXIDASE

    Directory of Open Access Journals (Sweden)

    Andrija Šmelcerović

    2013-03-01

    Full Text Available In this study we investigated the kinetics of the nitration of quercetin by horseradish peroxidase. Quercetin nitration reaction was followed by recording the spectral changes over the time at 380 nm. The reaction rate increases with increasing of the quercetin concentration and follows the Michaelis-Menten type kinetics. Kinetic parameters of the studied enzymatic reaction were determined.

  20. KINETICS OF NEUTRAL HYDROLYSIS OF 1-BENZOYL-3-PHENYL-1,2,4-TRIAZOLE IN HIGHLY AQUEOUS-MEDIA - ANALYSIS OF EFFECTS OF ADDED ETHANOL AND PROPAN-1-OL IN TERMS OF PAIRWISE GROUP-INTERACTION PARAMETERS

    NARCIS (Netherlands)

    BENAK, H; ENGBERTS, JBFN; BLANDAMER, MJ

    1992-01-01

    Over the range 288.15 less-than-or-equal-to T/K less-than-or-equal-to 333.15, the first-order rate constant for the neutral hydrolysis of 1-benzoyl-3-phenyl-1,2,4-triazole in aqueous solutions (pH ca. 4) decreases when either ethanol or propan-1-ol is added. The kinetic data are analysed in terms of

  1. 基于免疫系统的自适应差分进化算法及在水银氧化动力学参数估计中的应用%An immune self-adaptive differential evolution algorithm with application to estimate kinetic parameters for homogeneous mercury oxidation

    Institute of Scientific and Technical Information of China (English)

    胡春平; 颜学峰

    2009-01-01

    A new version of differential evolution(DE)algorithm,in which immurle concepts and methods are applied to determine the parameter setting.named immune self-adaptive difierential evolution(ISDE),iS proposed to improve the performance of the DE algorithm.During the actual operation.ISDE seeks the optimal parameters arising from the evolutionary process.which enable ISDE to alter the algorithm for different optimization problems and improve the performance Of ISDE bv the control parameters'self-adaptation.The performance of the proposed method is studied with the use of nine benchmark problems and compared with original DE algorithm and other well-known self-adaptive DE algorithms.The experiments conducted show that the ISDE clearly outperforms the othcr DE algorithms in all benchmark functions.Furthermore.ISDE iS applied to develop the kinetic model for homogeneous mercury (Hg) oxidation in tlue gas,and satistactory results are obtained.

  2. Deconvolution of ultrafast kinetic data with inverse filtering

    Energy Technology Data Exchange (ETDEWEB)

    Banyasz, Akos [Department of Physical Chemistry, Eoetvoes University, P.O. Box 32, H-1518 Budapest 112 (Hungary); Research Institute for Solid State Physics and Optics, Hungarian Academy of Sciences, P.O. Box 49, H-1525 Budapest (Hungary); Matyus, Edit [Department of Physical Chemistry, Eoetvoes University, P.O. Box 32, H-1518 Budapest 112 (Hungary); Keszei, Erno [Department of Physical Chemistry, Eoetvoes University, P.O. Box 32, H-1518 Budapest 112 (Hungary)]. E-mail: keszei@chem.elte.hu

    2005-02-01

    Due to limitations of pulse widths in ultrafast laser or electron pulse kinetic measurements, in the case of subpicosecond characteristic times of the studied reactions, deconvolution with the pulses always distorts the kinetic signal. Here, we describe inverse filtering based on Fourier transformations to deconvolve measured ultrafast kinetic data without evoking a particular kinetic mechanism. Deconvolution methods using additional Wiener filtering or two-parameter regularization are found to give reliable results for simulated as well as experimental data.

  3. Kinetics of tetrataenite disordering

    Energy Technology Data Exchange (ETDEWEB)

    Dos Santos, E., E-mail: edisanfi@cbpf.br [Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro (Brazil); Gattacceca, J.; Rochette, P. [Centre Européen de Recherche et d’Enseignement des Géosciences de l’Environnement, UM34, CNRS/Aix-Marseille University, Aix-en-Provence (France); Fillion, G. [Laboratoire National des Champs Magnétiques Intenses (LNCMI), CNRS, UJF, 38042 Grenoble (France); Scorzelli, R.B. [Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro (Brazil)

    2015-02-01

    Tetrataenite is a chemically ordered L1{sub 0}-type Fe{sub 50}Ni{sub 50} alloy detected for the first time in 1977 by {sup 57}Fe Mössbauer spectroscopy studies in iron meteorites. The thermal history of meteorites, in particular short thermal events like those associated to hypervelocity impacts, can be constrained by tracing the presence of tetrataenite or its disordering into taenite. The knowledge of the disordering kinetics of tetrataenite, that is associated with changes in its magnetic properties, is still very fragmentary so that the time–temperature history of these meteorites cannot be constrained in details. Furthermore, knowledge of disordering kinetics is important due to potential technological application of tetrataenite as a rare-earth free strong magnet. Thus, this work provides the first time–temperature data for disordering reaction of tetrataenite. We have shown that disordering is not an instantaneous process but is a kinetic limited reaction. It was shown that disordering may take place at any temperature above the order–disorder transition for L{sub 10} superstructure phase (∼320 °C) when the appropriate time-scale is considered. This result means that the apparent Curie point for tetrataenite is not an absolute property in the sense that any estimate of this parameter should be referred to a given time-scale. - Highlights: • The first time–temperature data for tetrataenite disordering reaction is provided. • Previous works does not give a complete picture of tetrataenite disordering. • Apparent Curie temperature of tetrataenite should be referred to a time-scale. • Tetrataenite can be used as a probe to detect thermal/shock events recorded in meteorites.

  4. Evaluation of kinetic parameters of chitinases produced by Beauveria bassiana (Bals. Vuill. / Avaliação de parâmetros cinéticos de quitinases produzidas por Beauveria bassiana (Bals. Vuill.

    Directory of Open Access Journals (Sweden)

    Cristiane Mita

    2008-07-01

    Full Text Available Entomopathogenic fungus Beauveria bassiana is currently used as a biocontrol agent for agricultural pests. The infection process involves extracellular enzymes such as proteases and chitinases that degrade the cuticle of the insects. The objective of this work was to evaluate kinetic parameters of pH, temperature, ionic concentration and time of reaction on chitinases activity. The fungus B. bassiana CG432 was cultivated on coffee berry borer Hypothenemus hampei (Ferrari and the conidia grown on insect were used to prepare the inoculum containing 108conídia/mL. These conidia were inoculated at 1% (v/v in culture liquid medium containing D-glucose (10g, yeast extract (5g, NaNO3 (1,58g, Na2HPO4.7H2O (1,05g, KCl (1g, MgSO4.7H2O (0,6g and KH2PO4 (0,36g per liter. The cultivation was carried at 28°C and 180rpm during 5 days. Culture fluid was obtained by filtration and centrifugation at 8.000g, and the chitinases were isolated and concentrated by ultrafiltration using 10 and 100kDa cut off membranes under nitrogen pressure. Chitinase activity was detected and quantified using N-acetylglucosamine released by hydrolysis of colloidal chitin at 40 to 60ºC, at 50, 100 and 200 mM ionic concentrations of buffers sodium acetate (pH 4.0 to 6.0; sodium phosphate (pH 6.0 to 8.0; and Glycine-NaOH (pH 8.0 to 10.0 during 60 minutes. Maximum chitinase activity was at 45ºC and pH 5.5, and was also high at pH 6.0 and pH 8.5 using 50mM buffer. The chitinase activity increased and was stable during an hour at optimum conditions of the reaction, shown the stable nature of this enzyme.Beauveria bassiana é um fungo entomopatogênico utilizado no controle biológico de insetos-praga que infestam produtos agrícolas. O mecanismo de infecção envolve a produção de enzimas extracelulares, como proteases e quitinases que degradam a cutícula dos insetos. O objetivo deste trabalho foi avaliar parâmetros cinéticos de pH, temperatura, concentração iônica e tempo de

  5. Saffman-Taylor fingers with kinetic undercooling

    KAUST Repository

    Gardiner, Bennett P. J.

    2015-02-23

    © 2015 American Physical Society. The mathematical model of a steadily propagating Saffman-Taylor finger in a Hele-Shaw channel has applications to two-dimensional interacting streamer discharges which are aligned in a periodic array. In the streamer context, the relevant regularization on the interface is not provided by surface tension but instead has been postulated to involve a mechanism equivalent to kinetic undercooling, which acts to penalize high velocities and prevent blow-up of the unregularized solution. Previous asymptotic results for the Hele-Shaw finger problem with kinetic undercooling suggest that for a given value of the kinetic undercooling parameter, there is a discrete set of possible finger shapes, each analytic at the nose and occupying a different fraction of the channel width. In the limit in which the kinetic undercooling parameter vanishes, the fraction for each family approaches 1/2, suggesting that this "selection" of 1/2 by kinetic undercooling is qualitatively similar to the well-known analog with surface tension. We treat the numerical problem of computing these Saffman-Taylor fingers with kinetic undercooling, which turns out to be more subtle than the analog with surface tension, since kinetic undercooling permits finger shapes which are corner-free but not analytic. We provide numerical evidence for the selection mechanism by setting up a problem with both kinetic undercooling and surface tension and numerically taking the limit that the surface tension vanishes.

  6. Stochastic optimization-based study of dimerization kinetics

    Indian Academy of Sciences (India)

    Srijeeta Talukder; Shrabani Sen; Ralf Metzler; Suman K Banik; Pinaki Chaudhury

    2013-11-01

    We investigate the potential of numerical algorithms to decipher the kinetic parameters involved in multi-step chemical reactions. To this end, we study dimerization kinetics of protein as a model system. We follow the dimerization kinetics using a stochastic simulation algorithm and combine it with three different optimization techniques (genetic algorithm, simulated annealing and parallel tempering) to obtain the rate constants involved in each reaction step. We find good convergence of the numerical scheme to the rate constants of the process. We also perform a sensitivity test on the reaction kinetic parameters to see the relative effects of the parameters for the associated profile of the monomer/dimer distribution.

  7. [A study of the regulation of photosynthesis by the analysis of the effect of kinetic parameters on the characteristics of the oscillatory regime and the rate of CO2 assimilation].

    Science.gov (United States)

    Nguen, T T F; Karelina, T A; Kukushkina, A K

    2007-01-01

    Earlier at the biophysics department, the experimental data on the oscillations of delayed luminescence have been described with the help of a mathematical model. Here we studied the influence of the model parameters on the characteristics of the oscillatory regime. The frequencies and damping factors of the oscillations at different parameter values were calculated using the Lyapunov analysis. It was shown that, in addition to oscillations observed experimentally, other, rapidly damping oscillations may exist. The dependence of the CO2 assimilation rate on the model parameters was studied. It was shown that the intensity of the light absorbed by photosystems I and II may differently affect the assimilation of CO2.

  8. Drug-Target Kinetics in Drug Discovery.

    Science.gov (United States)

    Tonge, Peter J

    2017-07-14

    The development of therapies for the treatment of neurological cancer faces a number of major challenges including the synthesis of small molecule agents that can penetrate the blood-brain barrier (BBB). Given the likelihood that in many cases drug exposure will be lower in the CNS than in systemic circulation, it follows that strategies should be employed that can sustain target engagement at low drug concentration. Time dependent target occupancy is a function of both the drug and target concentration as well as the thermodynamic and kinetic parameters that describe the binding reaction coordinate, and sustained target occupancy can be achieved through structural modifications that increase target (re)binding and/or that decrease the rate of drug dissociation. The discovery and deployment of compounds with optimized kinetic effects requires information on the structure-kinetic relationships that modulate the kinetics of binding, and the molecular factors that control the translation of drug-target kinetics to time-dependent drug activity in the disease state. This Review first introduces the potential benefits of drug-target kinetics, such as the ability to delineate both thermodynamic and kinetic selectivity, and then describes factors, such as target vulnerability, that impact the utility of kinetic selectivity. The Review concludes with a description of a mechanistic PK/PD model that integrates drug-target kinetics into predictions of drug activity.

  9. Kinetic comparisons of mesophilic and thermophilic aerobic biomass

    NARCIS (Netherlands)

    Vogelaar, J.C.T.; Klapwijk, A.; Temmink, H.; Lier, van J.B.

    2003-01-01

    Kinetic parameters describing growth and decay of mesophilic (30degreesC) and thermophilic (55degreesC) aerobic biomass were determined in continuous and batch experiments by using oxygen uptake rate measurements
    Kinetic parameters describing growth and decay of mesophilic (30degreesC) and therm

  10. Kinetic comparisons of mesophilic and thermophilic aerobic biomass

    NARCIS (Netherlands)

    Vogelaar, J.C.T.; Klapwijk, A.; Temmink, H.; Lier, van J.B.

    2003-01-01

    Kinetic parameters describing growth and decay of mesophilic (30degreesC) and thermophilic (55degreesC) aerobic biomass were determined in continuous and batch experiments by using oxygen uptake rate measurements
    Kinetic parameters describing growth and decay of mesophilic (30degreesC) and

  11. Sulfide toxicity kinetics of a uasb reactor

    Directory of Open Access Journals (Sweden)

    D. R. Paula Jr.

    2009-12-01

    Full Text Available The effect of sulfide toxicity on kinetic parameters of anaerobic organic matter removal in a UASB (up-flow anaerobic sludge blanket reactor is presented. Two lab-scale UASB reactors (10.5 L were operated continuously during 12 months. The reactors were fed with synthetic wastes prepared daily using glucose, ammonium acetate, methanol and nutrient solution. One of the reactors also received increasing concentrations of sodium sulfide. For both reactors, the flow rate of 16 L.d-1 was held constant throughout the experiment, corresponding to a hydraulic retention time of 15.6 hours. The classic model for non-competitive sulfide inhibition was applied to the experimental data for determining the overall kinetic parameter of specific substrate utilization (q and the sulfide inhibition coefficient (Ki. The application of the kinetic parameters determined allows prediction of methanogenesis inhibition and thus the adoption of operating parameters to minimize sulfide toxicity in UASB reactors.

  12. Lumping procedure for a kinetic model of catalytic naphtha reforming

    Directory of Open Access Journals (Sweden)

    H. M. Arani

    2009-12-01

    Full Text Available A lumping procedure is developed for obtaining kinetic and thermodynamic parameters of catalytic naphtha reforming. All kinetic and deactivation parameters are estimated from industrial data and thermodynamic parameters are calculated from derived mathematical expressions. The proposed model contains 17 lumps that include the C6 to C8+ hydrocarbon range and 15 reaction pathways. Hougen-Watson Langmuir-Hinshelwood type reaction rate expressions are used for kinetic simulation of catalytic reactions. The kinetic parameters are benchmarked with several sets of plant data and estimated by the SQP optimization method. After calculation of deactivation and kinetic parameters, plant data are compared with model predictions and only minor deviations between experimental and calculated data are generally observed.

  13. Validation d'un formalisme cinétique par optimisation de paramètres : approche et méthode mathématiques Validation of a Kinetic Formalization by Means of Parameter Optimization: Approach and Mathematical Method

    Directory of Open Access Journals (Sweden)

    Alario F.

    2006-12-01

    Full Text Available Cet article est une synthèse du travail fait en commun entre la Division Informatique et Mathématiques Appliquées DIMAet la division Cinétique et Catalyse de l'Institut Français du Pétrole. On y expose une nouvelle approche mathématique pour la validation d'un formalisme cinétique : la déshydrocyclisation du n-heptane. This article is an overview of the work carried out together by the DIMAand the Cinétique et Catalysedivision of the Institut Français du Pétrole. It is a new mathematical approach to validate a kinetic formalization : the n-heptane dehydrocyclization.

  14. Kinetic investigation of wood pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Thurner, F.; Mann, U.; Beck, S. R.

    1980-06-01

    The objective of this investigation was to determine the kinetics of the primary reactions of wood pyrolysis. A new experimental method was developed which enabled us to measure the rate of gas, tar, and char production while taking into account the temperature variations during the wood heating up. The experimental method developed did not require any sophisticated instruments. It facilitated the collection of gas, tar and residue (unreacted wood and char) as well as accurate measurement of the temperature inside the wood sample. Expressions relating the kinetic parameters to the measured variables were derived. The pyrolysis kinetics was investigated in the range of 300 to 400/sup 0/C at atmospheric pressure and under nitrogen atmosphere. Reaction temperature and mass fractions of gas, tar, and residue were measured as a function of time. Assuming first-order reactions, the kinetic parameters were determined using differential method. The measured activation energies of wood pyrolysis to gas, tar, and char were 88.6, 112.7, and 106.5 kJ/mole, respectively. These kinetic data were then used to predict the yield of the various pyrolysis products. It was found that the best prediction was obtained when an integral-mean temperature obtained from the temperature-time curve was used as reaction temperature. The pyrolysis products were analyzed to investigate the influence of the pyrolysis conditions on the composition. The gas consisted mainly of carbon dioxide, carbon monoxide, oxygen, and C/sub 3//sup +/-compounds. The gas composition depended on reaction time as well as reactor temperature. The tar analysis indicated that the tar consisted of about seven compounds. Its major compound was believed to be levoglucosan. Elemental analysis for the char showed that the carbon content increased with increasing temperature.

  15. Complex kinetics of fluctuating enzymes: phase diagram characterization of a minimal kinetic scheme.

    Science.gov (United States)

    Min, Wei; Jiang, Liang; Xie, X Sunney

    2010-05-03

    Enzyme molecules are dynamic entities with stochastic fluctuation in both protein conformation and enzymatic activity. However, such a notion of fluctuating enzymes, best characterized by recent single-molecule experiments, was not considered in the classic Michaelis-Menten (MM) kinetic scheme. Here we incorporate the fluctuation concept into the reversible MM scheme, and solve analytically all the possible kinetics (i.e., substrate concentration dependent enzymatic velocity) for a minimal model of fluctuating enzymes. Such a minimal model is found to display a variety of distinct kinetic behaviors (phases) in addition to the classic MM kinetics; excess substrate inhibition, sigmoidal kinetics, and concave biphasic kinetics. We find that all these kinetic phases are interrelated and unified under the framework of fluctuating enzymes and can be adequately described by a phase diagram that consists of two master parameters. Functionally, substrate inhibition, sigmoidal kinetics, and convex biphasic phases exhibit positive cooperativity, whereas concave biphasic phases display negative cooperativity. Remarkably, all these complex kinetics are produced by fluctuating enzymes with single substrate binding site, but the two conformations are, therefore, fundamentally different from the classic MWC and KNF models that require multiple subunit or binding sites. This model also suggests that, for a given enzyme/substrate pair, the non-MM behaviors could undergo transitions among different kinetic phases induced by varying product concentrations, owing to the fundamental Haldane symmetry in the reversible MM scheme.

  16. Ozone mass transfer and kinetics experiments

    Energy Technology Data Exchange (ETDEWEB)

    Bollyky, L.J.; Beary, M.M.

    1981-12-01

    Experiments were conducted at the Hanford Site to determine the most efficient pH and temperature levels for the destruction of complexants in Hanford high-level defense waste. These complexants enhance migration of radionuclides in the soil and inhibit the growth of crystals in the evaporator-crystallizer. Ozone mass transfer and kinetics tests have been outlined for the determination of critical mass transfer and kinetics parameters of the ozone-complexant reaction.

  17. Methods of nonlinear kinetics

    OpenAIRE

    Gorban, A. N.; Karlin, I.V.

    2003-01-01

    Nonlinear kinetic equations are reviewed for a wide audience of specialists and postgraduate students in physics, mathematical physics, material science, chemical engineering and interdisciplinary research. Contents: The Boltzmann equation, Phenomenology and Quasi-chemical representation of the Boltzmann equation, Kinetic models, Discrete velocity models, Direct simulation, Lattice Gas and Lattice Boltzmann models, Minimal Boltzmann models for flows at low Knudsen number, Other kinetic equati...

  18. Kinetic characterization of the photosynthetic reaction centres in microalgae by means of fluorescence methodology

    NARCIS (Netherlands)

    Gargano, Immacolata; Olivieri, Giuseppe; Spasiano, Danilo; Andreozzi, Roberto; Pollio, Antonino; Marotta, Raffaele; Ambrosio, D' Nicola; Marzocchella, Antonio

    2015-01-01

    The kinetic characterization of the photosynthetic activity in autotrophic microalgae plays a key role in the design of optimized photobioreactors. This paper presents a procedure to assess kinetic parameters of a three-state photosynthetic reaction centres model. Four kinetic parameters of the

  19. Enhancement of the adsorption capacity of the light-weight expanded clay aggregate surface for the metronidazole antibiotic by coating with MgO nanoparticles: Studies on the kinetic, isotherm, and effects of environmental parameters.

    Science.gov (United States)

    Kalhori, Ebrahim Mohammadi; Al-Musawi, Tariq J; Ghahramani, Esmaeil; Kazemian, Hossein; Zarrabi, Mansur

    2017-02-09

    The synthesized MgO nanoparticles were used to coat the light-weight expanded clay aggregates (LECA) and as a metronidazole (MNZ) adsorbent. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier-transformed infrared (FTIR) techniques were employed to study the surface morphology and characteristics of the adsorbents. MgO/LECA clearly revealed the advantages of the nanocomposite particles, showing high specific surface area (76.12 m(2)/g), significant adsorption sites and functional groups. Between pH 5 and 9, the MNZ sorption was not significantly affected. Kinetic studies revealed that the MNZ adsorption closely followed the Avrami model, with no dominant process controlling the sorption rate. The study of the effects of foreign ions revealed that the addition of carbonate raised the MNZ removal efficiency of LECA by 8% and the total removal of MNZ by MgO/LECA. Furthermore, nitrate and hardness only marginally influenced the MNZ removal efficiency and their effects can be ranked in the order of carbonate>nitrate>hardness. The isotherm adsorption of MNZ was best fitted with the Langmuir model enlighten the monolayer MNZ adsorption on the homogeneous LECA and MgO/LECA surfaces. The maximum adsorption capacity under optimum conditions was enhanced from 56.31 to 84.55 mg/g for LECA and MgO/LECA, respectively. These findings demonstrated that the MgO/LECA nanocomposite showed potential as an efficient adsorbent for MNZ removal.

  20. Removal of tylosine from aqueous solution by UV/nano Ag/S{sub 2}O{sub 8}{sup 2-}process : Influence of operational parameters and kinetic study

    Energy Technology Data Exchange (ETDEWEB)

    Moghaddam, Saeideh Kamali; Rasoulifard, Mohammadhossein; Vahedpour, Morteza; Eskandarian, Mohammadreza [University of Zanjan, Zanjan (Iran, Islamic Republic of)

    2014-09-15

    The present work deals with the photooxidative degradation of tylosin antibiotic (TYL) in the presence of potassium peroxydisulfate (K{sub 2}S{sub 2}O{sub 8}) irradiated by UV-C in the presence of immobilized nano silver. Effects of pH, temperature, peroxydisulfate concentration and immobilized nano silver dosage on the degradation efficiency of TYL were examined. Degradation efficiency was small when the oxidation was carried out in the absence of UV irradiation. Results showed that degradation of TYL increases with temperature, nano Ag and peroxydisulfate initial concentration and decreases with pH. Due to UV/nano Ag/S{sub 2}O{sub 8}{sup 2-}processes, more than 90% of TYL can be degraded at room temperature in 35min at an initial concentration of 50mgl{sup -1}. Degradation reaction order of TYL by UV/nano Ag/S{sub 2}O{sub 8}{sup 2-}process is 1.89. Meanwhile, the initial rates of degradation in UV/nano Ag/S{sub 2}O{sub 8}{sup 2-}processes can be described well by the Langmuir-Hinshelwood kinetic model.

  1. Method of Tallying Adjoint Fluence and Calculating Kinetics Parameters in Monte Carlo Codes%在蒙特卡罗程序中统计共轭通量并计算中子动力学参数的方法

    Institute of Scientific and Technical Information of China (English)

    汪量子; 姚栋; 王侃

    2012-01-01

    A method of using iterated fission probability to estimate the adjoint fluence during particles simulation, and using it as the weighting function to calculate kinetics parameters βell and A in Monte Carlo codes, was introduced in this paper. Implements of this method in continuous energy Monte Carlo code MCNP and multi-group Monte Carlo code MCMG are both elaborated. Verification results show that, with regardless additional computing cost, using this method, the adjoint fluence accounted by MCMG matches well with the result computed by ANISN, and the kinetics parameters calculated by MCNP agree very well with benchmarks. This method is proved to be reliable, and the function of calculating kinetics parameters in Monte Carlo codes is carried out effectively, which could be the basement for Monte Carlo codes' utility in the analysis of nuclear reactors' transient behavior.%文章介绍了在蒙特卡罗程序中,使用反复裂变几率的统计结果作为共轭通量的估计,并作为权重函数计算动力学参数βeff和Λ的方法,阐释了在连续能量蒙特卡罗程序MCNP和多群蒙特卡罗程序MCMG中实现这种方法的过程.数值校验结果表明:在几乎不带来附加计算量的同时,在MCMG中使用该方法统计得到的共轭通量与ANISN的共轭通量计算结果符合较好,在MCNP中使用该方法计算得到的中子动力学参数与基准测量结果符合较好.在蒙特卡罗程序中实现了高效率计算中子动力学参数的功能,为蒙特卡罗程序进一步用于反应堆动态行为的分析奠定了基础.

  2. Parâmetros cinéticos da degradação in vitro de alimentos incubados com inóculo microbiano de diferentes espécies de ruminantes Kinetic parameters of the ruminal in vitro degradation of feedstuffs given to different ruminant species

    Directory of Open Access Journals (Sweden)

    A.R.G.F. Bezerra

    2005-08-01

    Full Text Available Parâmetros cinéticos da degradação ruminal de alguns alimentos utilizados para ruminantes de zoológicos foram estimados mediante incubação in vitro com líquido ruminal de audade (Ammotragus lervia, cervo sambar (Cervus unicolor, elande (Taurotragus oryx, bovino (Bos taurus, bubalino (Bubalus bubalis, caprino (Capra hircus e ovino (Ovis aries. Os parâmetros cinéticos foram estimados pela técnica da produção de gás, cujos dados foram ajustados pelos modelos de um e de duplo compartimento. Não foram detectadas diferenças nos parâmetros cinéticos que permitissem agrupar os alimentos (fibrosos × não fibrosos e os animais (domésticos × silvestres. O modelo de duplo compartimento foi o mais adequado para a estimação dos parâmetros cinéticos da degradação ruminal. Inóculo microbiano oriundo de ruminantes domésticos não é recomendado para estimar parâmetros cinéticos da degradação ruminal de alimentos utilizados para ruminantes silvestres de zoológicos.The estimation of the ruminal kinetic parameters of pumpkin, potato-sweet, beet, broccoli, carrot, alfalfa hay, alfalfa pellet and bean, currently used for feeding wild and domestic ruminants raised in the Rio de Janeiro Zoo, was made through in vitro incubation of the feedstuffs together with ruminal fluid obtained from aoudad (Ammotragus lervia, sambar deer (Cervus unicolor, eland (Taurotragus oryx, cattle (Bos taurus, buffalo (Bubalus bubalis, goat (Capra hircus and sheep (Ovis aries. The gas production technique was used to obtain gas profiles, and the data were fitted by the mono or double compartmental model. The kinetic parameters were discrepant among both, animals and feedstuffs, and the double compartmental model gave the best estimation. Ruminal inocula from domestic ruminants can not be used to estimate the kinetic parameters of ruminal degradation of feedstuffs for wild ruminants.

  3. The Kinetics of Sorption of Lead Ions on Clinoptilolite in the H-Form

    Science.gov (United States)

    Akimbaeva, A. M.; Ergozhin, E. E.

    2008-03-01

    The kinetics of ion exchange of lead ions on clinoptilolite in the H-form was studied experimentally. The kinetic parameters of sorption of lead ions by the natural zeolite were calculated as depending on zeolite dispersity and solution concentration.

  4. A numerical study of natural hydrate formation kinetics in petroleum pipelines by the phase field method: influence of the model parameters; Estudo da cinetica de formacao de hidratos em dutos de petroleo pelo metodo do campo de fase: influencia dos parametros do modelo

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Mabelle Biancardi; Castro, Jose Adilson de; Silva, Alexandre Jose da; Ferreira, Alexandre Furtado [Universidade Federal Fluminense (UFF), Volta Redonda, RJ (Brazil). Pos-Graduacao em Engenharia Metalurgica], e-mail: mabelle@metal.eeimvr.uff.br, e-mail: adilson@metal.eeimvr.uff.br, e-mail: ajs@metal.eeimvr.uff.br, e-mail: furtado@metal.eeimvr.uff.br

    2006-07-01

    The objective of this work is to study the influence of the parameters of the phase field model field on the formation of natural hydrates. It was investigated parameters such as superficial tension, effect of the super-cooling, homogeneous and heterogeneous nucleation. The influence of these parameters was analyzed according to morphology of the interface and the rate of formation. The mathematical model to describe the evolution of the natural hydrates formation is based on the simultaneous solution of the phase and energy equations. The finite volume numerical method was used to discretize the governing differential equations. Results of the simulation indicated that the reduction of the superficial tension leads to the increase of the surface rugosity, interface thickness and instability of the interface resulting in a decrease of the rate growth. In order to investigate the nucleation effect of the natural hydrates, two conditions had been simulated a) the random distribution of nuclei: where the evolution of formed hydrates suffered coalescence and the kinetic decreased due to impingement of hydrates regions and b) Nucleation in the pipeline wall, where rough interfaces were observed. (author)

  5. Kinetics of yttrium oxide carbochlorination

    Energy Technology Data Exchange (ETDEWEB)

    Gaviria, J.P., E-mail: gaviriaj@cab.cnea.gov.ar [Division Cinetica Quimica - Complejo Tecnologico Pilcaniyeu - Centro Atomico Bariloche - Comision Nacional de Energia Atomica, Av. Bustillo km 9500 (8400), S.C. de Bariloche, Rio Negro (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (Argentina); Fouga, G.G. [Division Cinetica Quimica - Complejo Tecnologico Pilcaniyeu - Centro Atomico Bariloche - Comision Nacional de Energia Atomica, Av. Bustillo km 9500 (8400), S.C. de Bariloche, Rio Negro (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (Argentina); Bohe, A.E. [Division Cinetica Quimica - Complejo Tecnologico Pilcaniyeu - Centro Atomico Bariloche - Comision Nacional de Energia Atomica, Av. Bustillo km 9500 (8400), S.C. de Bariloche, Rio Negro (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (Argentina); Centro Regional Universitario Bariloche - Universidad Nacional del Comahue (Argentina)

    2011-04-20

    Research highlights: {yields} Chlorination kinetics of Y{sub 2}O{sub 3}-C system was studied by thermogravimetry. {yields} The influence of carbon content, flow rate, sample mass and pCl{sub 2} were evaluated. {yields} Reaction proceeds through three successive stages until the formation of YCl{sub 3}(l). {yields}STAGE I is the formation of YOCl(s) and is under chemical control for T < 700 {sup o}C. {yields}STAGE I follows a nucleation and growth model. Kinetics parameters were obtained. - Abstract: The chlorination kinetics of the Y{sub 2}O{sub 3}-sucrose carbon system was studied by thermogravimetry. This work is a continuation of a previous one in which the reaction stages and the stoichiometry of each reaction have been determined. The influence of carbon content, total flow rate, sample initial mass and chlorine partial pressure was evaluated. The effect of carbon content on the reactive mixture was studied between 6.7 and 70% (carbon mass/total mass). The results showed that the reaction rate of each stage is strongly increased as the carbon content increases and the range of occurrence of the stages depends on the amount of carbon in the solid reactive mixture. The formation reaction of YOCl (STAGE I) is chemically controlled for temperatures lower than 700 {sup o}C with average effective activation energies of 165 {+-} 6 and 152 {+-} 7 kJ/mol for 8.7 and 16.7%C, respectively. The formation of the YOCl follows a nucleation and growth mechanism, with a combination of continuous nucleation and site saturation, and anisotropic growth controlled by diffusion. The kinetics of STAGE I can be expressed by the following global rate equation that includes the variables analyzed: (d{alpha})/(dt) =k{sub 0}Bexp(-(Ea)/(R{sub g}T) )pCl{sub 2}{l_brace}n(1-{alpha})[-ln(1-{alpha})]{r_brace}{sup (n-1)/n} where k{sub 0}B = 1.9 x 10{sup 4}, n = 1.20 for 8.7%C, and k{sub 0}B = 8.4 x 10{sup 3}, n = 1.14 for 16.7%C. STAGES II and III correspond to the YOCl carbochlorination to

  6. Inference of some pharmacokinetic parameters of the C mitomycin, through the analysis of its micro nucleate polychromatic erythrocytes induction kinetics; Inferencia de algunos parametros farmacocineticos de la mitomicina C, mediante el analisis de su cinetica de induccion de eritrocitos policromaticos micronucleados

    Energy Technology Data Exchange (ETDEWEB)

    Morales R, P.; Vallarino K, T.; Cruz V, V.; Delgadillo H, A. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)

    2003-07-01

    The objective of the present work was to establish pharmacokinetic parameters of the C Mitomycin (MMC) in vivo, comparing its kinetics of induction of polychromatic micro nucleate erythrocytes (EPGMN) with that of the gamma radiation. The used doses were of 0.75; 1.5 and 3. 0 {mu}moles/kg of MMC. It was observed that the MMC produces MN in the first cycle of cellular division and it is independent of the cytotoxic effect. This agent requires of a relatively long period of latency that is not compatible with her great reactivity, for what the pharmacokinetic values obtained in fact reflect the time that takes the processing of leisure in the DNA and the subsequent induction of ruptures that produce MN. (Author)

  7. Experimental study on kinetic parameters of thermal cracking of biomass tar%生物质焦油热裂解动力学参数实验研究

    Institute of Scientific and Technical Information of China (English)

    黎柴佐; 冉景煜

    2012-01-01

    For the reason of the unstable evaporation in the tar sampling process and the difficulty of measuring and controlling reaction temperature,a moving bed as the tar sample introduction system was designed. A sample tray carrying tar was moved into the furnace with linear temperature distribution of the entrance zone. The movement of the tray instead of that of the tar,makes the tar sample introduction process more stable and the temperature easer to control. On this basis,tar cracking process and kinetic characteristics with the different sample introduction rate were studied. The results indicate the tar cracking rate is accelerated with increasing temperature at 573 ~ 1 123 K. The tar cracking rate reaches 58% at 1 123 K. The tar thermal cracking reaction is a first order reaction. On average,the activation energy is 39. 5 kJ/mol and the pre-exponential factor is 1. 58 min-1.%基于进样过程中焦油蒸发的不稳定性以及反应温度的测定和控制难度,设计了移动床焦油进样系统,使用样品槽携带焦油进入具有线性温度分布的炉膛空间,以样品槽的运动进样代替焦油流动进样,以获得稳定的焦油蒸发进样和更容易控制的反应温度.在此基础上,研究了不同进样速率下的焦油热裂解及其动力学特性.结果表明,在573 ~1 123 K,焦油的裂解率随温度的升高而加速升高,并在1 123 K时达到58%的裂解率;焦油热裂解遵循一级动力学反应,其平均活化能为39.5 kJ/mol,指前因子为1.58 min-1.

  8. Kinetic study of biological hydrogen production by anaerobic fermentation

    Energy Technology Data Exchange (ETDEWEB)

    Sangeetha, R. [Annamalai Univ., Chidambaram (India). Dept. of Chemical Engineering; Karunanithi, T. [Annamalai Univ., Tamilnadu (India). Dept. of Chemical Engineering

    2009-07-01

    This study examined the kinetics of batch biohydrogen production from glucose. Clostridium pasteurianum was used to produce biohydrogen by dark anaerobic fermentation. The initial substrate concentration, initial pH and temperature were optimized for biohydrogen production. The maximum production of hydrogen under optimum conditions was found to be 5.376 l/l. The kinetic parameters were determined for the optimized medium and conditions in the batch reactor. The by product was expressed as total acidic equivalent. This presentation discussed the logistic equation that was used to model the growth of the organism and described how the kinetic parameters were calculated. The Leudeking piret kinetic model was used to express the hydrogen production and substrate use because it combines both growth associated and non associated contributions. It was concluded the production of biohydrogen can be predicted well using the logistic model for cell growth kinetics and the logistic incorporated Leudeking Piret model for product and substrate utilization kinetics.

  9. Articulatory Parameters.

    Science.gov (United States)

    Ladefoged, Peter

    1980-01-01

    Summarizes the 16 parameters hypothesized to be necessary and sufficient for linguistic phonetic specifications. Suggests seven parameters affecting tongue shapes, three determining the positions of the lips, one controlling the position of the velum, four varying laryngeal actions, and one controlling respiratory activity. (RL)

  10. Parameter Estimation

    DEFF Research Database (Denmark)

    Sales-Cruz, Mauricio; Heitzig, Martina; Cameron, Ian;

    2011-01-01

    of optimisation techniques coupled with dynamic solution of the underlying model. Linear and nonlinear approaches to parameter estimation are investigated. There is also the application of maximum likelihood principles in the estimation of parameters, as well as the use of orthogonal collocation to generate a set...

  11. Simulation of the kinetics of oxygen complexes in crystalline silicon

    Science.gov (United States)

    Joo Lee, Young; von Boehm, J.; Nieminen, R. M.

    2002-10-01

    The formation kinetics of thermal double donors (TDD's) is studied by a general kinetic model with parameters based on accurate ab initio total-energy calculations. The kinetic model includes all relevant association, dissociation, and restructuring processes. The simulated kinetics agrees qualitatively and in most cases quantitatively with the experimentally found consecutive kinetics of TDD's. It also supports our earlier assignments of the ring-type oxygen chains to TDD's [Pesola et al., Phys. Rev. Lett. 84, 5343 (2000)]. We demonstrate with the kinetic model that the most common assumption that only the O2 dimer acts as a fast diffusing species would lead to an unrealistic steady increase of the concentration of O3. The neglect of restructuring processes leads to an anomalous increase of oxygen dimers and negligible concentrations of TDD's. The capture of interstitial oxygens by diffusing oxygen chains and the escaping of interstitial oxygens from the chains fully dominate the formation kinetics.

  12. Kinetics of methane fermentation

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Y. R.; Hashimoto, A. G.

    1978-01-01

    The kinetics on methane fermentation are described using published data for livestock residue, sewage sludge, and municipal refuse. Methods are presented to determine the kinetic constants and the finally attainable methane production using steady-state methane production data. The effects of temperature, loading rate, and influent substrate concentration on methane fermentation kinetics are discussed. These relationships were used to predict the rate of methane production of a pilot-scale fermentor with excellent results.

  13. Relationship between lumbar instability and radiographic parameters:a kinetic MRI report%动态磁共振成像参数与腰椎不稳的关系

    Institute of Scientific and Technical Information of China (English)

    沈忆新; 李生文; 汪益; 金志高; 王义刚

    2011-01-01

    目的:探讨腰椎不稳与脊柱功能单元中的动态磁共振成像参数(椎间盘退变、小关节骨关节炎及黄韧带肥厚)之间关系.方法:按Kong的标准诊断为腰椎不稳患者79例(237个脊柱功能单元),采用动态MRI在患者中立及过屈、过伸3个体位成像.测定L3/L4、L4/L5及L5/S1椎间盘退变(Ⅰ~Ⅴ级)、小关节骨关节炎(1~4级)、黄韧带肥厚(>3mm为黄韧带肥厚阳性)参数,评估其与腰椎不稳的相关性.结果:L4/L5节段不稳(36个)的发生较L3/L4(18个)及L5/S1节段多(25个).椎间]盘退变、小关节骨关节炎以及黄韧带肥厚(+)均与L3/L4 、L4/L5、L5/S1 3个节段腰椎不稳相关(P<0.05).结论:Ⅳ级椎间盘退变、3级小关节骨关节炎及黄韧带肥厚(+)分别与腰椎不稳的形成有关,在诊断腰椎不稳时,动态MRI及其3个参数具有辅助诊断的作用.%Objective:To evaluate the relationship between lumbar instability and parameters in the functional spinal unit including disc degeneration,facet joint osteoarthritis and ligamentum flavum hypertrophy.Method: According to the Kong's criteria,79 cases (a total of 237 functional spinal units)with lumbar instability were subjected to MRI under neutral,flexion and extension position.Segmental range of motion was measured at three levels (L3/L4, L4/L5, L5/S1).Then three radiographic parameters including disc degeneration (grade I-V ), facet joint osteoarthritis (grade 1-4) and ligamentum flavum hypertrophy (>3mm indicating the presence of ligamentum flavum hypertrophy) were used to evaluate the relationship between them and lumbar instability .Result :L4/5 instability(36 cases) was more prevalent than L3/4(18 cases) and L5/S1 (25 cases).Disc degeneration, facet joint osteoarthritis and ligamentum flavum hypertrophy all showed relationship with L3/L4.L4/L5 and L5/S1 instability (P<0.05).Conclusion:Radiographic parameters including grade Ivdisc degeneration,grade 3 facet joint osteoarthritis and

  14. Introduction to chemical kinetics

    CERN Document Server

    Soustelle, Michel

    2013-01-01

    This book is a progressive presentation of kinetics of the chemical reactions. It provides complete coverage of the domain of chemical kinetics, which is necessary for the various future users in the fields of Chemistry, Physical Chemistry, Materials Science, Chemical Engineering, Macromolecular Chemistry and Combustion. It will help them to understand the most sophisticated knowledge of their future job area. Over 15 chapters, this book present the fundamentals of chemical kinetics, its relations with reaction mechanisms and kinetic properties. Two chapters are then devoted to experimental re

  15. Principles of chemical kinetics

    CERN Document Server

    House, James E

    2007-01-01

    James House's revised Principles of Chemical Kinetics provides a clear and logical description of chemical kinetics in a manner unlike any other book of its kind. Clearly written with detailed derivations, the text allows students to move rapidly from theoretical concepts of rates of reaction to concrete applications. Unlike other texts, House presents a balanced treatment of kinetic reactions in gas, solution, and solid states. The entire text has been revised and includes many new sections and an additional chapter on applications of kinetics. The topics covered include quantitative rela

  16. Thermodynamic basis for cluster kinetics

    DEFF Research Database (Denmark)

    Hu, Lina; Bian, Xiufang; Qin, Xubo

    2006-01-01

    Due to the inaccessibility of the supercooled region of marginal metallic glasses (MMGs) within the experimental time window, we study the cluster kinetics above the liquidus temperature, Tl, to acquire information on the fragility of the MMG systems. Thermodynamic basis for the stability...... of locally ordered structure in the MMG liquids is discussed in terms of the two-order-parameter model. It is found that the Arrhenius activation energy of clusters, h, is proportional to the chemical mixing enthalpy of alloys, Hchem. Fragility of the MMG forming liquids can be described by the ratio...

  17. Inventory parameters

    CERN Document Server

    Sharma, Sanjay

    2017-01-01

    This book provides a detailed overview of various parameters/factors involved in inventory analysis. It especially focuses on the assessment and modeling of basic inventory parameters, namely demand, procurement cost, cycle time, ordering cost, inventory carrying cost, inventory stock, stock out level, and stock out cost. In the context of economic lot size, it provides equations related to the optimum values. It also discusses why the optimum lot size and optimum total relevant cost are considered to be key decision variables, and uses numerous examples to explain each of these inventory parameters separately. Lastly, it provides detailed information on parameter estimation for different sectors/products. Written in a simple and lucid style, it offers a valuable resource for a broad readership, especially Master of Business Administration (MBA) students.

  18. Inflationary dynamics of kinetically-coupled gauge fields

    DEFF Research Database (Denmark)

    Ferreira, Ricardo J. Z.; Ganc, Jonathan

    2015-01-01

    We investigate the inflationary dynamics of two kinetically-coupled massless U(1) gauge fields with time-varying kinetic-term coefficients. Ensuring that the system does not have strongly coupled regimes shrinks the parameter space. Also, we further restrict ourselves to systems that can be quant...

  19. A STUDY ON THE CRYSTALLIZATION KINETICS OF NYLON 1010

    Institute of Scientific and Technical Information of China (English)

    CHEN Shouxi

    1997-01-01

    The kinetic behavior of isothermal and nonisothermal crystallization of nylon-1010has been studied by means of dilatometry and differential scanning calorimetry, respectively. The isothermal and nonisothermal process can be described by Avrami equation and Ozawa equation, respectively. From the experimental results the kinetic parameters of crystallization and crystalline mechanism for isothermal and nonisothermal measurements are discussed.

  20. Kinetics of the Exothermic Decomposition Reaction of s-Tripicryaminotrinitrobenzene

    Institute of Scientific and Technical Information of China (English)

    ZHAO Feng-qi; HU Rong-zu; GAO Hong-xu; LUO Yang; GAO Sheng-li; SONG Ji-rong; SHI Qi-zhen

    2007-01-01

    The kinetic parameters of the exothermic decomposition reaction of s-Tripicryaminotrinitrobenzene under linear temperature rise condition are studied by means of DSC. The results show that the empirical kinetic model function in difs-1, respectively. The critical temperature of thermal explosion of the compound is 267.36 ℃.

  1. Hydration kinetics of transgenic soybeans

    Directory of Open Access Journals (Sweden)

    Aline Francielle Fracasso

    2015-01-01

    Full Text Available The kinetic and experimental analyses of the hydration process of transgenic soybeans (BRS 225 RR are provided. The importance of the hydration process consists of the grain texture modifications which favor grinding and extraction of soybeans. The soaking isotherms were obtained for four different temperatures. Results showed that temperature affected transgenic soybeans´ hydration rate and time. Moisture content d.b. of the soybeans increased from 0.12 ± 0.01 kg kg-1 to 1.45 ± 0.19 kg kg-1 during 270 min. of process. Two models were used to fit the kinetic curves: an empirical model developed by Peleg (1988 and a phenomenological one, proposed by Omoto et al. (2009. The two models adequately represented the hydration kinetics. Peleg model was applied to the experimental data and the corresponding parameters were obtained and correlated to temperature. The model by Omoto et al. (2009 showed a better statistical fitting. Although Ks was affected by temperature (Ks = 0.38079 exp (-2289.3 T-1, the equilibrium concentration remained practically unchanged.

  2. Fribrinolysis Kinetics and Its Application

    Institute of Scientific and Technical Information of China (English)

    WEI Wenning; YANG Rui; GUO Tao; YANG Yan; HU Yu

    2007-01-01

    A new, convenient, and rapid method for kinetic measurement of human fibrinolysis was established. The alteration of absorbance (A) in the process of blood coagulation and lyses was automatically scanned and recorded using a UV2000 spectrophotometer connected to a computer. The parameters of human fibrinolysis kinetics were established. Urokinase at 20 U/mL was the optimal concentration used. There was significant difference in fibrinolysis kinetics and plasma plasminogen concentration between 22 normal subjects and 27 patients with acute myeloblastic leukemia (P<0.05 and <0.01 respectively). The coefficience of variation was (5.24±1.51)%. This method could also be used to measure the plasma fibrinogen concentration at the same time. It was concluded that this method was stable and was capable of providing dynamic, direct experimental data and multiparemeters for clinicians. It was also valuable in evaluating the anti- and pro-fibrinolytic capcity of patients' plasmas, allowing for monitoring of therapy, choice of drugs and adjustment of drug concentrations.

  3. Electrode kinetics and double layer structure

    NARCIS (Netherlands)

    Timmer, B.; Sluyters-Rehbach, M.; Sluyters, J.H.

    1969-01-01

    Several electrochemical methods have been developed in recent years for the study of the kinetic parameters of electrode reactions. These methods have been used for obtaining an abundance of experimental data for the standard heterogeneous rate constant, ksh, of electrode reactions, mostly limited t

  4. Kinetic Analysis of Char Thermal Deactivation

    DEFF Research Database (Denmark)

    Zolin, Alfredo; Jensen, Anker; Dam-Johansen, Kim

    2001-01-01

    data for all chars obtained from the TGA, kinetic parameters in an annealing model reported in the literature were determined. A shifted Gamma distribution taking into account a positive activation energy at the beginning of deactivation, as well as a lower bound of char reactivity corresponding...

  5. Kinetics of Hydrolyzing Isolated Soy Protein by an Endopeptidase and its Conceptual Application in Process Engineering

    Directory of Open Access Journals (Sweden)

    Zebin Wang

    2012-04-01

    Full Text Available A response study and the effects of different parameters (pH, temperature and enzyme dose on kinetics of isolated soy protein hydrolysis by a trypsin-like endopeptidase (TL1 were conducted. Degree of hydrolysis (%DH data varied at different times under different hydrolysis conditions. Fitting the kinetics data to Michaelis-Menten kinetics model did not result in reasonable kinetic parameters, which implied that Michaelis-Menten kinetics was invalid for such a hydrolysis process. A kinetics model proposed by (Gonzalez-Tello, Camacho, Jurado, Paez, & Guadix, 1994 was found to fit the kinetics curve well and resulted in acceptable model parameters. A simple simulation example was performed to demonstrate the concept of how the kinetics equation could be applied in process engineering.

  6. 非等温TG-DTG法确定2,2'-联吡啶-对甲氧基苯甲酸铕(Ⅲ)热分解反应的机理函数和动力学参数%Determination of Mechanism Function and Kinetic Parameters of Thermal Decomposition of the 2,2'-Dipyridine-tris(p-methoxybenzoate) Europium(Ⅲ) with Non-isothermal TG and DTG Curves

    Institute of Scientific and Technical Information of China (English)

    张建军; 王瑞芬; 翟学良; 赵建路; 杨惠芳; 默丽萍

    2000-01-01

    The thermal decomposition of the 2,2'-dipyridine-tris(p-methoxybenzoats) europium (Ⅲ) and its kinetics were studied under the non-isothermal condition in air by TG-DTG and DTA methods. The intermediate and residue for each decomposition were identified from TG curve. The non-isothermal kinetic data were analyzed by means of integral and differential methods. The possible reaction mechanisms were investigated by comparing the kinetic parameters. The kinetic equation for the first stage can be expressed as dα/dt =Aexp(-E/RT)2(1-α)1/2.%采用TG-DTG和DTA技术研究了2,2'-联吡啶-对甲氧基苯甲酸铕(Ⅲ)在静态空气中的非等温热分解过程及动力学,根据TG曲线确定了热分解过程中的中间产物及最终产物,运用微分法与积分法对非等温动力学数据进行分析,推断出第一步的动力学方程为dα/dt=Aexp(-E/RT)2(1-α)1/2.

  7. Oxidation kinetics of aluminum diboride

    Energy Technology Data Exchange (ETDEWEB)

    Whittaker, Michael L., E-mail: michaelwhittaker2016@u.northwestern.edu [Department of Materials Science and Engineering, University of Utah, 122S. Central Campus Drive, Salt Lake City, UT 84112 (United States); Sohn, H.Y. [Department of Metallurgical Engineering, University of Utah, 135S 1460 E, Rm 00412, Salt Lake City, UT 84112 (United States); Cutler, Raymond A. [Ceramatec, Inc., 2425S. 900W., Salt Lake City, UT 84119 (United States)

    2013-11-15

    The oxidation characteristics of aluminum diboride (AlB{sub 2}) and a physical mixture of its constituent elements (Al+2B) were studied in dry air and pure oxygen using thermal gravimetric analysis to obtain non-mechanistic kinetic parameters. Heating in air at a constant linear heating rate of 10 °C/min showed a marked difference between Al+2B and AlB{sub 2} in the onset of oxidation and final conversion fraction, with AlB{sub 2} beginning to oxidize at higher temperatures but reaching nearly complete conversion by 1500 °C. Kinetic parameters were obtained in both air and oxygen using a model-free isothermal method at temperatures between 500 and 1000 °C. Activation energies were found to decrease, in general, with increasing conversion for AlB{sub 2} and Al+2B in both air and oxygen. AlB{sub 2} exhibited O{sub 2}-pressure-independent oxidation behavior at low conversions, while the activation energies of Al+2B were higher in O{sub 2} than in air. Differences in the composition and morphology between oxidized Al+2B and AlB{sub 2} suggested that Al{sub 2}O{sub 3}–B{sub 2}O{sub 3} interactions slowed Al+2B oxidation by converting Al{sub 2}O{sub 3} on aluminum particles into a Al{sub 4}B{sub 2}O{sub 9} shell, while the same Al{sub 4}B{sub 2}O{sub 9} developed a needle-like morphology in AlB{sub 2} that reduced oxygen diffusion distances and increased conversion. The model-free kinetic analysis was critical for interpreting the complex, multistep oxidation behavior for which a single mechanism could not be assigned. At low temperatures, moisture increased the oxidation rate of Al+2B and AlB{sub 2}, but both appear to be resistant to oxidation in cool, dry environments. - Graphical abstract: Isothermal kinetic data for AlB{sub 2} in air, showing a constantly decreasing activation energy with increasing conversion. Model-free analysis allowed for the calculation of global kinetic parameters despite many simultaneous mechanisms occurring concurrently. (a) Time

  8. SF Blue染料在UV、UV/TiO2、UV/H2 O2体系中的降解动力学参数%Kinetics Parameters of Degradation of Dye SF Blue in UV、UV/TiO2 and UV/H2 O2 Systems

    Institute of Scientific and Technical Information of China (English)

    蔡邦宏

    2014-01-01

    对SF Blue制衣染料在UV、UV/TiO2、UV/H2 O2三种不同体系中的降解动力学参数进行研究,得到不同体系中染料各级光降解反应的表观速率常数和活化能。结果表明,SF Blue染料在UV/TiO2和UV/H2 O2体系中都具有良好的降解效果,但两者动力学可能有所不同,前者对二级反应符合度最高,后者则对一级反应符合度最高。染料在UV体系中也有一定程度降解,且对零级、一级反应都有很好的符合度。%The kinetics parameters of degradation of dye SF Blue in UV、UV/TiO2 and UV/H2 O2 systems is investigated, and the apparent rate constants and activation energies of different reaction orders are obtained. The results show that both UV/TiO2 and UV/H2 O2 has a high activity on degradation of the dye,but the kinetics is not alike probably. The results also show that the dye in UV system is degraded to a certain degree.

  9. Part I. Evaluation of thermodynamic and kinetic parameters for electron transfer and following chemical reaction from a global analysis of current-potential-time data. Part II. Electro-catalytic detection in high-performance liquid chromatography of vitamin B[sub 12] and other molecules of biological and environmental interest

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, V.T.

    1992-01-01

    Simultaneous evaluation of electron transfer rate constant, k[sup 0], following chemical reaction rate constant, k[sub f], electron transfer coefficient, [alpha] and standard potential, E[sup 0][prime] for an electrochemical reaction following the EC mechanism is described. A mathematical model for the current response to a potential step is developed, starting with the Butler-Volmer equation for electrode kinetics and concentration expressions for the redox couple. The resulting integral equations are solved numerically via the Step Function method. Current-potential and current-time curves are simulated and tested under limiting conditions. The four parameters of the system are evaluated by fitting simulated current-voltage-time (i-E-t) surface to the theoretical equation. The method is applied to study an important biological molecule, viz., methyl cobalamin, in DMSO. Included in the discussion part is the use of kinetic zone diagrams to depict chronoamperometric current response as a function of dimensionless rate constants for the EC reaction scheme. This compact display of the influence of the two rate constants on current in all time windows can be used to select the best data for analysis. Theoretical limits of measurable rate constants can be estimated from the zone diagram. The development of a dropping mercury electrode detector for High Performance Liquid Chromatography (HPLC) and its application to analysis of B[sub 12] and other vitamins is described. This EC detector is able to achieve high levels of sensitivity by exploiting the catalytic hydrogen evolution undergone by many nitrogenous organic molecules. Vitamin B[sub 12], thiamine, riboflavin and niacinamide were analyzed individually and in mixtures on reverse phase C18 column. Preliminary results from the analysis of commercial multivitamin preparations are also discussed.

  10. A kinetic model for predicting biodegradation.

    Science.gov (United States)

    Dimitrov, S; Pavlov, T; Nedelcheva, D; Reuschenbach, P; Silvani, M; Bias, R; Comber, M; Low, L; Lee, C; Parkerton, T; Mekenyan, O

    2007-01-01

    Biodegradation plays a key role in the environmental risk assessment of organic chemicals. The need to assess biodegradability of a chemical for regulatory purposes supports the development of a model for predicting the extent of biodegradation at different time frames, in particular the extent of ultimate biodegradation within a '10 day window' criterion as well as estimating biodegradation half-lives. Conceptually this implies expressing the rate of catabolic transformations as a function of time. An attempt to correlate the kinetics of biodegradation with molecular structure of chemicals is presented. A simplified biodegradation kinetic model was formulated by combining the probabilistic approach of the original formulation of the CATABOL model with the assumption of first order kinetics of catabolic transformations. Nonlinear regression analysis was used to fit the model parameters to OECD 301F biodegradation kinetic data for a set of 208 chemicals. The new model allows the prediction of biodegradation multi-pathways, primary and ultimate half-lives and simulation of related kinetic biodegradation parameters such as biological oxygen demand (BOD), carbon dioxide production, and the nature and amount of metabolites as a function of time. The model may also be used for evaluating the OECD ready biodegradability potential of a chemical within the '10-day window' criterion.

  11. MODELLING OF BACTERIAL SULPHATE REDUCTION IN ANAEROBIC PONDS : KINETIC INVESTIGATIONS

    OpenAIRE

    Harerimana, Casimir; Vasel, Jean-Luc; Jupsin, Hugues; Ouali, Amira

    2011-01-01

    The aim of the study was first to develop a simple and practical model of anaerobic digestion including sulphate-reduction in anaerobic ponds. The basic microbiology of our model consists of three steps, namely, acidogenesis, methanogenesis, and sulphate reduction. This model includes multiple reaction stoichiometry and substrate utilization kinetics. The second aim was to determine some kinetic parameters associated with this model. The values of these parameters for sulfidogenic bacteria ar...

  12. Kinetic simulating experiment on the secondary hydrocarbon generation of kerogen

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The kinetic parameters of generation have been obtained for different hydrocarbon classes, including methane, C2-C5 gas hydrocarbons, C6-C13 light hydrocarbons and C13+ heavy hydrocarbons, and vitrinite reflectance (Ro) by the kinetic simulating experiment of kerogen cracking. Then, combined with the detailed geology of Sichuan Basin, the effective gas-generating intensity of the Lower Cambrian source rock is approximately estimated by applying these parameters.

  13. Modelling heart rate kinetics.

    Science.gov (United States)

    Zakynthinaki, Maria S

    2015-01-01

    The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual's cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women).

  14. Modelling heart rate kinetics.

    Directory of Open Access Journals (Sweden)

    Maria S Zakynthinaki

    Full Text Available The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise. Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual's cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women.

  15. Modelling Heart Rate Kinetics

    Science.gov (United States)

    Zakynthinaki, Maria S.

    2015-01-01

    The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual’s cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women). PMID:25876164

  16. Levantamento de parâmetros cinéticos medidos em reator anaeróbio de manta de lodo (UASB em escala-piloto tratando efluentes de laticínio = Survey of kinetic parameters measured in upflow anaerobic sludge blanket (UASB in pilot-scale treatment of dairy wastewater

    Directory of Open Access Journals (Sweden)

    Bruno Botelho Saléh

    2009-01-01

    Full Text Available O objeto desta pesquisa foi à obtenção e avaliação dos parâmetros cinéticos do reator anaeróbio de manta de lodo (UASB-Upflow Anaerobic Sludge Blanket na remoção da carga orgânica poluidora dos despejos da atividade laticinista. O sistema com suas principais unidades foi composto de tratamento preliminar (caixa de areia e flotadores,tanque de contato (TC, reator UASB, filtro anaeróbio (FAB e lodo ativo em batelada (LAB. Os TDH’s (tempos de detenção hidráulicos e a temperatura adotados para o reator UASB foram de 44, 35, 30, 26 e 20h após a fase de estabilização do sistema, com temperatura média de 24,8ºC ± 1,8ºC. O volume do reator era de 394 L. A partir dos dadosDQOT (mg L-1, Sólidos Totais Fixos e Voláteis (mg L-1, Temperatura (°C, Vazão (L dia-1 e Perfil de Lodo no reator (Sólidos Voláteis Totais em mg L-1, monitorados durante todo o período de pesquisa na estação-piloto, em cada um dos tempos de detenção hidráulicos(TDH’s no reator UASB, foi conduzido o estudo para obtenção dos parâmetros cinéticos: coeficiente de crescimento ‘Y’ (mg DQO mg SVT-1 d-1, coeficiente de decaimento ‘Kd’ (d-1, taxa máxima de crescimento ‘μmáx’ (d-1 e concentração de substrato limitante ‘Ks’ (mg DQO L-1. Os parâmetros cinéticos determinados se basearam em estudos de regressão linear para determinação de Y, Kd, μmáx e Ks, respectivamente, dando, assim, respaldo técnico-científicoaos dados físico-químicos levantados durante a operacionalização do sistema.The goal of this research was to obtain and withdraw the kinetic parameters from an Upflow Anaerobic Sludge Blanket – UASB in removing the organic load from the waste by-product of a dairy activity. The treatment system was composed of a Sand Interceptor (Grit Chamber, Grease Intercept Chambers, Stirred Contact Tank (CT, a UASB reactor, Anaerobic Filter (AF, and Batch Activated Sludge System (BASS. The HRT (Hydraulic Retention Time and

  17. Adsorption kinetics of methyl violet onto perlite.

    Science.gov (United States)

    Doğan, Mehmet; Alkan, Mahir

    2003-01-01

    This study examines adsorption kinetics and activation parameters of methyl violet on perlite. The effect of process parameters like contact time, concentration of dye, temperature and pH on the extent of methyl violet adsorption from solution has been investigated. Results of the kinetic studies show that the adsorption reaction is first order with respect to dye solution concentration with activation energy of 13.2 kJ mol(-1). This low activation energy value indicates that the adsorption reaction is diffusion controlled. The activation parameters using Arrhenius and Eyring equations have been calculated. Adsorption increases with increase of variables such as contact time, initial dye concentration, temperature and pH.

  18. Kinetic properties of fractal stellar media

    Science.gov (United States)

    Chumak, O. V.; Rastorguev, A. S.

    2017-01-01

    Kinetic processes in fractal stellar media are analysed in terms of the approach developed in our earlier paper involving a generalization of the nearest neighbour and random force distributions to fractal media. Diffusion is investigated in the approximation of scale-dependent conditional density based on an analysis of the solutions of the corresponding Langevin equations. It is shown that kinetic parameters (time-scales, coefficients of dynamic friction, diffusion, etc.) for fractal stellar media can differ significantly both qualitatively and quantitatively from the corresponding parameters for a quasi-uniform random media with limited fluctuations. The most important difference is that in the fractal case, kinetic parameters depend on spatial scalelength and fractal dimension of the medium studied. A generalized kinetic equation for stellar media (fundamental equation of stellar dynamics) is derived in the Fokker-Planck approximation with the allowance for the fractal properties of the spatial stellar density distribution. Also derived are its limit forms that can be used to describe small departures of fractal gravitating medium from equilibrium.

  19. Enzyme kinetics informatics: from instrument to browser.

    Science.gov (United States)

    Swainston, Neil; Golebiewski, Martin; Messiha, Hanan L; Malys, Naglis; Kania, Renate; Kengne, Sylvestre; Krebs, Olga; Mir, Saqib; Sauer-Danzwith, Heidrun; Smallbone, Kieran; Weidemann, Andreas; Wittig, Ulrike; Kell, Douglas B; Mendes, Pedro; Müller, Wolfgang; Paton, Norman W; Rojas, Isabel

    2010-09-01

    A limited number of publicly available resources provide access to enzyme kinetic parameters. These have been compiled through manual data mining of published papers, not from the original, raw experimental data from which the parameters were calculated. This is largely due to the lack of software or standards to support the capture, analysis, storage and dissemination of such experimental data. Introduced here is an integrative system to manage experimental enzyme kinetics data from instrument to browser. The approach is based on two interrelated databases: the existing SABIO-RK database, containing kinetic data and corresponding metadata, and the newly introduced experimental raw data repository, MeMo-RK. Both systems are publicly available by web browser and web service interfaces and are configurable to ensure privacy of unpublished data. Users of this system are provided with the ability to view both kinetic parameters and the experimental raw data from which they are calculated, providing increased confidence in the data. A data analysis and submission tool, the kineticswizard, has been developed to allow the experimentalist to perform data collection, analysis and submission to both data resources. The system is designed to be extensible, allowing integration with other manufacturer instruments covering a range of analytical techniques.

  20. Irreversible processes kinetic theory

    CERN Document Server

    Brush, Stephen G

    2013-01-01

    Kinetic Theory, Volume 2: Irreversible Processes deals with the kinetic theory of gases and the irreversible processes they undergo. It includes the two papers by James Clerk Maxwell and Ludwig Boltzmann in which the basic equations for transport processes in gases are formulated, together with the first derivation of Boltzmann's ""H-theorem"" and a discussion of this theorem, along with the problem of irreversibility.Comprised of 10 chapters, this volume begins with an introduction to the fundamental nature of heat and of gases, along with Boltzmann's work on the kinetic theory of gases and s

  1. Atypical cytochrome p450 kinetics: implications for drug discovery.

    Science.gov (United States)

    Tracy, Timothy S

    2006-01-01

    The Michaelis-Menten model is commonly used to estimate a drug's potential in vivo hepatic clearance based on in vitro data obtained during drug discovery and development. This paradigm assumes that the drug obeys 'typical' enzyme kinetics and thus can be described by this model. However, it is increasingly being recognised that a number of drugs metabolised not only by the cytochrome P450 enzymes but also by other enzymes and transporters can exhibit atypical kinetic profiles, and thus are not accurately modeled with the Michaelis-Menten model. Application of an incorrect model can then lead to mis-estimation of in vitro intrinsic clearance and thus affect the prediction of in vivo clearance. This review discusses several types of atypical kinetic profiles that may be observed, including examples of homotropic cooperativity (i.e. sigmoidal kinetics, biphasic kinetics and substrate inhibition kinetics) as well as heterotropic cooperativity (i.e. activation). Application of the incorrect kinetic model may profoundly affect estimations of intrinsic clearance. For example, incorrectly applying the Michaelis-Menten model to a kinetic profile exhibiting substrate inhibition kinetics will result in an underestimation of Km (Michaelis-Menten constant) and V(max) (maximal velocity), whereas application of the Michaelis-Menten model to sigmoidal kinetic data typically results in an overestimation of Km and V(max) at the lower substrate concentrations that are typically therapeutically relevant. One must also be careful of potential artefactual causes of atypical kinetic profiles, such as enzyme activation by solvents, buffer dependent kinetic profiles, or altered kinetic parameter estimates due to nonspecific binding of the substrate to proteins. Despite a plethora of data on the effects of atypical kinetic profiles in vitro, only modest effects have been noted in vivo (with the exception of substrate dependent inhibition). Thus, the clinical relevance of these phenomena

  2. Kinetic modeling in pre-clinical positron emission tomography

    Energy Technology Data Exchange (ETDEWEB)

    Kuntner, Claudia [AIT Austrian Institute of Technology GmbH, Seibersdorf (Austria). Biomedical Systems, Health and Environment Dept.

    2014-07-01

    Pre-clinical positron emission tomography (PET) has evolved in the last few years from pure visualization of radiotracer uptake and distribution towards quantification of the physiological parameters. For reliable and reproducible quantification the kinetic modeling methods used to obtain relevant parameters of radiotracer tissue interaction are important. Here we present different kinetic modeling techniques with a focus on compartmental models including plasma input models and reference tissue input models. The experimental challenges of deriving the plasma input function in rodents and the effect of anesthesia are discussed. Finally, in vivo application of kinetic modeling in various areas of pre-clinical research is presented and compared to human data.

  3. Computer prediction system on solid/solid reaction kinetics

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A computer software system of kinetic predication of solid/solid reaction, KinPreSSR, was developed using Visual C++ and FoxPro. It includes two main modules, REACTION and DIFFUSION. KinPreSSR deals with the kinetics on the diffusion in solids as well as solid/solid reactions. The REACTION module in KinPreSSR was mainly described, which has organized the commonly recognized kinetic models, parameters, and employed both numerical and graphical methods for data analyses. The proper combination between the kinetic contents and the analytical methods enables users to use KinPreSSR for the evaluation and prediction of solid/solid reactions interested. As an example to show some of functions of KinPreSSR, the kinetics analysis for the reaction between SrCO3 and TiO2 powders to form SrTiO3 with a series of kinetic data from isothermal measurements was demonstrated.

  4. Experimental Studies on Turbulence Kinetic Energy in Confined Vortex Flows

    Institute of Scientific and Technical Information of China (English)

    L.Yan; G.H.Vatistas; 等

    2000-01-01

    Turbulence kinetic energies in confined vortex flows have been studied.The studies were based on the experiments performed in a vortex chamber,In the experiments,a Laser Doppler Anemometry(LDA) was used to perform flow measurements inside the vortex chamber,which provided the data for the kinetic energy analysis.The studies concentrated on the influences of the contraction ratio and the inlet air flow rate on the kinetic energy,and analyzed the characteristics of the kinetic energy in the confined vortex flows,including the distributions of the tangential component,radial component and total turbulence kinetic energy,In the paper,both the experimental techniques and the experimental results were presented.Based on a similarity analyis and the experimental data,an empirical scaling formula was proposed so that the tangential component of the turbulence kinetic energy was dependent only on the parameter of the contraction ratio.

  5. MODELLING AND PARAMETER ESTIMATION IN REACTIVE CONTINUOUS MIXTURES: THE CATALYTIC CRACKING OF ALKANES. PART I

    Directory of Open Access Journals (Sweden)

    PEIXOTO F. C.

    1999-01-01

    Full Text Available Fragmentation kinetics is employed to model a continuous reactive mixture. An explicit solution is found and experimental data on the catalytic cracking of a mixture of alkanes are used for deactivation and kinetic parameter estimation.

  6. Kinetic equations: computation

    CERN Document Server

    Pareschi, Lorenzo

    2013-01-01

    Kinetic equations bridge the gap between a microscopic description and a macroscopic description of the physical reality. Due to the high dimensionality the construction of numerical methods represents a challenge and requires a careful balance between accuracy and computational complexity.

  7. Thermal kinetic inductance detector

    Energy Technology Data Exchange (ETDEWEB)

    Cecil, Thomas; Gades, Lisa; Miceli, Antonio; Quaranta, Orlando

    2016-12-20

    A microcalorimeter for radiation detection that uses superconducting kinetic inductance resonators as the thermometers. The detector is frequency-multiplexed which enables detector systems with a large number of pixels.

  8. Chemical Kinetics Database

    Science.gov (United States)

    SRD 17 NIST Chemical Kinetics Database (Web, free access)   The NIST Chemical Kinetics Database includes essentially all reported kinetics results for thermal gas-phase chemical reactions. The database is designed to be searched for kinetics data based on the specific reactants involved, for reactions resulting in specified products, for all the reactions of a particular species, or for various combinations of these. In addition, the bibliography can be searched by author name or combination of names. The database contains in excess of 38,000 separate reaction records for over 11,700 distinct reactant pairs. These data have been abstracted from over 12,000 papers with literature coverage through early 2000.

  9. Electrochemical kinetics theoretical aspects

    CERN Document Server

    Vetter, Klaus J

    1967-01-01

    Electrochemical Kinetics: Theoretical Aspects focuses on the processes, methodologies, reactions, and transformations in electrochemical kinetics. The book first offers information on electrochemical thermodynamics and the theory of overvoltage. Topics include equilibrium potentials, concepts and definitions, electrical double layer and electrocapillarity, and charge-transfer, diffusion, and reaction overvoltage. Crystallization overvoltage, total overvoltage, and resistance polarization are also discussed. The text then examines the methods of determining electrochemical reaction mechanisms

  10. Cure Reaction Kinetics of Low Pressure Sheet Molding Compound System Thickened by Crystalline Polymer

    Institute of Scientific and Technical Information of China (English)

    QIN Yan; LIU Haihua; HUANG Zhixiong; MEI Qilin

    2007-01-01

    Several kinetic models for unsaturated polyester cure reaction and some existing parameter estimation techniques of these models were introduced. Correlated kinetic parameters and kinetic equations of the autocatalytic empirical kinetic model of LPSMC system were determined by using isothermal DSC to scan the system which was thickened by crystalline polymer (PEG-MAH). Through using a serial curing degree of the system to validate the model, the experimental results were basically identical with the predictions of the autocatalytic empirical kinetic model. This model could provide a theoretical reference to the determination of molding techniques of low pressure SMC.

  11. Determination of kinetic parameters of an upflow anaerobic sludge blanket reactor (uasb, treating swine wastewater Determinação dos parâmetros cinéticos de um reator anaeróbio de manta de lodo (UASB, tratando efluente líquido de suinocultura

    Directory of Open Access Journals (Sweden)

    Mario Tauzene Afonso Matangue

    2011-12-01

    Full Text Available This research aimed to estimate the kinetic parameters of a UASB reactor treating swine wastewater from farming. The system consisted of: a degritter with a triangular-notch weir in order to measure the flow; a static sieve; an acidification/equalization tank (AET; ABR and UASB reactors; a settling tank; two infiltration ponds and a greenhouse for fertirrigation. The hydraulic retention times (HRT adopted for the UASB reactor, were: 8.0; 9.6; 8.4; 6.0 and 4.8 hours. The operational temperature was 23.4º C±1.5º C. The analyzed physical-chemical parameters were temperature COD (total and filtered, BOD (total and filtered, total volatile solids (affluent, effluent and of the reactor's profile sludge, flow rate and nutrients (N and P. The kinetic coefficients estimated were: growth coefficient Y=0.091 mg tCOD mg TVS-1.d-1, decay coefficient Kd=0.01 d-1; concentration of limiting substrate Ks=282.5 tCOD mg L-1 and maximum growth rate µmax= 0.051 d-1. For data validation, simple linear regression models were applied and their interaction verified with a "t" test. The results matched with the those found in other references for the same type of kinetic studies.Foram estimados e analisados os parâmetros cinéticos em um reator UASB construído com a finalidade de reduzir a carga orgânica de efluentes líquidos originados de uma granja suinícola. O sistema foi composto de caixa de areia equipada com vertedor Thompson para a medição da vazão, uma peneira estática para a separação de sólidos, tanque de acidificação e equalização (TAE, um RAC e um UASB, tanque de decantação, duas lagoas de infiltração e uma casa de vegetação destinada a fertirrigação. Os tempos de detenção hidráulica (TDH adotados no reator UASB foram de 8.0; 9.6; 8.4; 6.0 e 4.8 horas. A temperatura média operacional foi de 23,4º C±1,5º C. Foram analisados os seguintes parâmetros físico-químicos: temperatura, vazão, sólidos totais (SFT e SVT afluente

  12. Parameter estimation in food science.

    Science.gov (United States)

    Dolan, Kirk D; Mishra, Dharmendra K

    2013-01-01

    Modeling includes two distinct parts, the forward problem and the inverse problem. The forward problem-computing y(t) given known parameters-has received much attention, especially with the explosion of commercial simulation software. What is rarely made clear is that the forward results can be no better than the accuracy of the parameters. Therefore, the inverse problem-estimation of parameters given measured y(t)-is at least as important as the forward problem. However, in the food science literature there has been little attention paid to the accuracy of parameters. The purpose of this article is to summarize the state of the art of parameter estimation in food science, to review some of the common food science models used for parameter estimation (for microbial inactivation and growth, thermal properties, and kinetics), and to suggest a generic method to standardize parameter estimation, thereby making research results more useful. Scaled sensitivity coefficients are introduced and shown to be important in parameter identifiability. Sequential estimation and optimal experimental design are also reviewed as powerful parameter estimation methods that are beginning to be used in the food science literature.

  13. Downstream plasma parameters in laminar shocks from ion kinetics

    Science.gov (United States)

    Gedalin, M.

    2016-10-01

    Ion dynamics in oblique shocks is governed by the macroscopic electric and magnetic fields of the shock front. In laminar shocks, these fields are time-independent and depend only on the coordinate along the shock normal. The shock ramp is narrow and the ion motion across the shock is manifestly non-adiabatic. The ion distribution just behind the ramp is significantly non-gyrotropic. Gyrotropy is achieved well behind the ramp mainly due to the gyrophase mixing. The asymptotic values of the ion density and temperature are determined by the eventual collisionless relaxation of the gyrating ion distribution. Given a distribution at the downstream edge of the ramp, the moments of the distribution after gyrophase mixing are derived using proper spatial averaging. The obtained expressions can be used for independent determination of the downstream plasma state and implementation in Rankine-Hugoniot relations.

  14. KINETICS OF HYDROLYSIS OF TRIBUTYRIN BY LIPASE

    Directory of Open Access Journals (Sweden)

    SULAIMAN AL-ZUHAIR

    2006-06-01

    Full Text Available Kinetics of the enzymatic hydrolysis of tributyrin using lipase has been investigated. The initial rate of reaction was determined experimentally at different substrate concentration by measuring the rate of butyric acid produced. Michaels-Menten kinetic model has been proposed to predict the initial rate of hydrolysis of tributyrin in micro-emulsion system. The kinetic parameters were estimated by fitting the data to the model using three methods, namely, the Lineweaver-Burk, Edie-Hofstee and Hanes methods. The Michaels-Menten model with the constant predicted by Edie-Hofstee and Hanes methods predicted the initial rate of reaction at various substrate concentrations better than the model with the constant predicted Lineweaver-Burk method, especially at high substrate concentrations.

  15. Surface-active ionic liquids in micellar catalysis: impact of anion selection on reaction rates in nucleophilic substitutions† †Electronic supplementary information (ESI) available: Formulae for calculating aggregation parameters and fitting of kinetic constants and copies of NMR spectra. See DOI: 10.1039/c6cp00493h Click here for additional data file.

    Science.gov (United States)

    Cognigni, Alice; Gaertner, Peter; Zirbs, Ronald; Peterlik, Herwig; Prochazka, Katharina; Schröder, Christian

    2016-01-01

    A series of surface-active ionic liquids based on the 1-dodecyl-3-methylimidazolium cation and different anions such as halides and alkylsulfates was synthesized. The aggregation behavior of these ionic liquids in water was characterized by surface tension, conductivity measurements and UV-Vis spectroscopy in order to determine the critical micelle concentration (CMC) and to provide aggregation parameters. The determination of surface activity and aggregation properties of amphiphilic ionic liquids was accompanied by SAXS studies on selected surface-active ionic liquids. The application of these surface-active ionic liquids with different anions was tested in nucleophilic substitution reactions for the degradation of organophosphorus compounds. Kinetic studies via UV-Vis spectrophotometry showed a strong acceleration of the reaction in the micellar system compared to pure water. In addition, an influence of the anion was observed, resulting in a correlation between the anion binding to the micelle and the reaction rate constants, indicating that the careful choice of the surface-active ionic liquid can considerably affect the outcome of reactions. PMID:27121134

  16. Kinetics of solid state phase transformations: Measurement and modelling of some basic issues

    Indian Academy of Sciences (India)

    S Raju; E Mohandas

    2010-01-01

    A brief review of the issues involved in modelling of the solid state transformation kinetics is presented. The fact that apart from the standard thermodynamic parameters, certain path variables like heating or cooling rate can also exert a crucial influence on the kinetic outcome is stressed. The kinetic specialties that are intrinsic to phase changes proceeding under varying thermal history are enumerated. A simple and general modelling methodology for understanding the kinetics of non-isothermal transformations is outlined.

  17. Non-isothermal decomposition kinetics of magnesite Decomposição não isotérmica de magnesita

    OpenAIRE

    Maitra, S; Mukherjee, S.; Saha, N; Pramanik, J

    2007-01-01

    Kinetics of thermal decomposition of Indian magnesite was studied by thermo-gravimetric analysis under non-isothermal condition. Coats and Redfern Integral approximation method was used to determine the kinetic parameters. Using the kinetic parameters different kinetic functions were analyzed with the experimental data to ascertain the decomposition mechanism of magnesium carbonate and it was observed that the decomposition reaction followed a contracting sphere kinetic mechanism.A cinética d...

  18. The models of cosmological inflation in the context of kinetic approximation

    Science.gov (United States)

    Fomin, I.

    2016-07-01

    In this work the building of models of cosmological inflation with approximate linear dependence of the scalar field kinetic energy on the state parameter is considered. The key parameters of cosmological perturbations are also calculated.

  19. 利用叶绿素含量及荧光动力学参数评价青贮玉米耐旱关键指标研究%Evaluation of drought tolerance in silage maize based on chlorophyll content and fluorescence kinetics parameters

    Institute of Scientific and Technical Information of China (English)

    何文铸; 张彪; 王培; 杨俊品; 冷益丰; 康继伟; 唐海涛; 陈洁; 谭君

    2013-01-01

    In attempt to provide a reliable theoretical basis for breeding of drought tolerance in silage maize in the arid hilly areas,the drought tolerance in silage maize were determined.The chlorophyll content and chlorophyll fluorescence kinetics parameters of 26 silage maize inbred lines and 105 crosses were measured using chlorophyll fluorometer.The principal component and correlation analysis were conducted against their key indices of drought tolerance,combining ability and genetic parameters.The order of influencing factors of Fv/Fm was:leaf Fv > leaf Fm > leaf Fo > leaf Area > leaf SPAD > bracteal leaf Fv/Fm > bracteal leaf SPAD.9 inbred lines which had higher general combining ability (GCA) and 19 crosses which had higher specific combining ability (SCA) were screened from the present study for 5 traits including leaf Fm,leaf Fv,leaf Area,leaf Fv/Fm and leaf SPAD.At silking stage in F1,the additive variation was principal in leaf Fo and leaf Area; leaf Fm and leaf Fv were commonly controlled by additive and no-additive effects; non-additive variation was principal in leaf Fv/Fm and leaf SPAD.The order of narrow heritability (h2N) was:leaf SPAD > leaf Area > leaf Fo > leaf Fv > leaf Fm> leaf Fv/Fm.It could increase biological yield of silage maize in the arid areas through early generation positive direct selection for leaf Fv,early generation negative direct selection for leaf Fo,and utilization of heterosis for leaf Fv/Fm.Chlorophyll content and chlorophyll fluorescence kinetics parameters could be employed for screening of drought tolerance in silage maize.%利用叶绿素荧光仪测定了26份青贮玉米自交系和105个组合的叶绿素含量及荧光动力学参数,对其生理性状关键耐旱指标进行主成分及相关分析,并进行配合力及遗传参数分析.青贮玉米Fv/Fm的影响因素大小依次为:叶片Fv>叶片Fm>叶片Fo>叶片Area>叶片SPAD>苞叶Fv/Fm>苞叶SPAD.筛选出了5个关键指标(叶

  20. Kinetic Study and Thermal Decomposition Behavior of Lignite Coal

    Directory of Open Access Journals (Sweden)

    Mehran Heydari

    2015-01-01

    Full Text Available A thermogravimetric analyzer was employed to investigate the thermal behavior and extract the kinetic parameters of Canadian lignite coal. The pyrolysis experiments were conducted in temperatures ranging from 298 K to 1173 K under inert atmosphere utilizing six different heating rates of 1, 6, 9, 12, 15, and 18 K min−1, respectively. There are different techniques for analyzing the kinetics of solid-state reactions that can generally be classified into two categories: model-fitting and model-free methods. Historically, model-fitting methods are broadly used in solid-state kinetics and show an excellent fit to the experimental data but produce uncertain kinetic parameters especially for nonisothermal conditions. In this work, different model-free techniques such as the Kissinger method and the isoconversional methods of Ozawa, Kissinger-Akahira-Sunose, and Friedman are employed and compared in order to analyze nonisothermal kinetic data and investigate thermal behavior of a lignite coal. Experimental results showed that the activation energy values obtained by the isoconversional methods were in good agreement, but Friedman method was considered to be the best among the model-free methods to evaluate kinetic parameters for solid-state reactions. These results can provide useful information to predict kinetic model of coal pyrolysis and optimization of the process conditions.

  1. Supergranular Parameters

    Science.gov (United States)

    Udayashankar, Paniveni

    2016-07-01

    I study the complexity of supergranular cells using intensity patterns from Kodaikanal solar observatory. The chaotic and turbulent aspect of the solar supergranulation can be studied by examining the interrelationships amongst the parameters characterizing supergranular cells namely size, horizontal flow field, lifetime and physical dimensions of the cells and the fractal dimension deduced from the size data. The findings are supportive of Kolmogorov's theory of turbulence. The Data consists of visually identified supergranular cells, from which a fractal dimension 'D' for supergranulation is obtained according to the relation P α AD/2 where 'A' is the area and 'P' is the perimeter of the supergranular cells. I find a fractal dimension close to about 1.3 which is consistent with that for isobars and suggests a possible turbulent origin. The cell circularity shows a dependence on the perimeter with a peak around (1.1-1.2) x 105 m. The findings are supportive of Kolmogorov's theory of turbulence.

  2. 发酵产菊糖果糖转移酶的培养基设计及菌体生长动力学研究%Optimization of Inulin Fructotransferase-producing Medium and Determination of Cell Growth Kinetic Parameter for Arthrobacter ureafaciens SK-8.001

    Institute of Scientific and Technical Information of China (English)

    卢峥嵘; 赵萌; 沐万孟; 张涛; 江波

    2009-01-01

    In this paper,the optimal inulin fructotransferase-producing medium and fermentation kinetic parameters of Arthrobacter ureafaciens SK -8.001 were studied. The recipes of optimal media included 2. 5% inulin,0. 3% NaN0_3,0. 1% yeast extract,0. 01% MgSO_4,0. 04% KH_2P0_4,0. 001% FeSO_4·7H_2O. The maximum enzyme activity reached 19. 85 U/mL,which was 2. 04 fold higher than in initial media. The study on the fermentation process in the optimal media suggested the right time to add inducers into the media was 12 h or 66th hours during the fermentation. The cell growth kinetic model for SK-8.001 in batch fermentation was X (t) = 9. 356 05/ [1 + exp~((4.4222-0.1102l)) ].%对1株产菊糖果糖转移酶(inulin fructotransferase)的金黄色节杆菌(Arthrobacter ureafaciens)SK-8.001的产酶培养基进行了优化,同时对其在分批发酵过程中培养基组分变化和菌体生长动力学进行了研究.所得到的改进型产酶培养基配方为25 g/L菊糖,3 g/L NaNO_3,1g/L酵母膏,0.1 g/L MgSO_4,0.4g/L KH_2PO_4,0.01g/LFeSO_4·7H_2O.在此培养基中的最高酶活达到19.85 U/mL,较初始培养基提高了2.04倍.对在此培养基中Sk-8.001的发酵过程研究发现发酵12 h和66 h是较为理想的诱导物添加时刻.得到SK-8.001在优化培养基中分批培养的菌体生长动力学模型为:X(t)=9.356 05/[1+exp~((4.4222-0.1102:))].

  3. Multiple alternative substrate kinetics.

    Science.gov (United States)

    Anderson, Vernon E

    2015-11-01

    The specificity of enzymes for their respective substrates has been a focal point of enzyme kinetics since the initial characterization of metabolic chemistry. Various processes to quantify an enzyme's specificity using kinetics have been utilized over the decades. Fersht's definition of the ratio kcat/Km for two different substrates as the "specificity constant" (ref [7]), based on the premise that the important specificity existed when the substrates were competing in the same reaction, has become a consensus standard for enzymes obeying Michaelis-Menten kinetics. The expansion of the theory for the determination of the relative specificity constants for a very large number of competing substrates, e.g. those present in a combinatorial library, in a single reaction mixture has been developed in this contribution. The ratio of kcat/Km for isotopologs has also become a standard in mechanistic enzymology where kinetic isotope effects have been measured by the development of internal competition experiments with extreme precision. This contribution extends the theory of kinetic isotope effects to internal competition between three isotopologs present at non-tracer concentrations in the same reaction mix. This article is part of a special issue titled: Enzyme Transition States from Theory and Experiment.

  4. Onsager reciprocity principle for kinetic models and kinetic schemes

    CERN Document Server

    Mahendra, Ajit Kumar

    2013-01-01

    Boltzmann equation requires some alternative simpler kinetic model like BGK to replace the collision term. Such a kinetic model which replaces the Boltzmann collision integral should preserve the basic properties and characteristics of the Boltzmann equation and comply with the requirements of non equilibrium thermodynamics. Most of the research in development of kinetic theory based methods have focused more on entropy conditions, stability and ignored the crucial aspect of non equilibrium thermodynamics. The paper presents a new kinetic model formulated based on the principles of non equilibrium thermodynamics. The new kinetic model yields correct transport coefficients and satisfies Onsager's reciprocity relationship. The present work also describes a novel kinetic particle method and gas kinetic scheme based on this linkage of non-equilibrium thermodynamics and kinetic theory. The work also presents derivation of kinetic theory based wall boundary condition which complies with the principles of non-equili...

  5. Kinetic features of breunnerite decarbonization

    Science.gov (United States)

    Vusikhis, A. S.; Gulyaeva, R. I.; Leont'ev, L. I.; Ovchinnikova, L. A.; Selivanov, E. N.

    2016-09-01

    The decarbonization of breunnerite from talc waste is analyzed by thermogravimetry. The temperatures of thermal effects are determined, and kinetic models for the process are proposed to describe the mechanism of breunnerite decomposition. The unit cell parameters of breunnerite (Mg x Fe1- x )CO3 and the product of its decomposition, iron-magnesium oxide (Mg,Fe)O, are calculated. The apparent activation energies E a of the decomposition are calculated using the Ozawa-Flynn-Wall and Kissenger model-free methods and the Avrami-Erofeev one-step model. Depending on the chosen model, the values of E a range within 180-185 kJ/mol. The conditions of breunnerite roasting for the subsequent use of the obtained material in metallurgical processes are substantiated.

  6. 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.

  7. Substrate specificity and stereoselectivity of horse liver alcohol dehydrogenase. Kinetic evaluation of binding and activation parameters controlling the catalytic cycles of unbranched, acyclic secondary alcohols and ketones as substrates of the native and active-site-specific Co(II)-substituted enzyme.

    Science.gov (United States)

    Adolph, H W; Maurer, P; Schneider-Bernlöhr, H; Sartorius, C; Zeppezauer, M

    1991-11-01

    1. The steady-state parameters kcat and Km and the rate constants of hydride transfer for the substrates isopropanol/acetone; (S)-2-butanol, (R)-2-butanol/2-butanone; (S)-2-pentanol, (R)-2-pentanol/2-pentanone; 3-pentanol/3-pentanone; (S)-2-octanol and (R)-2-octanol have been determined for the native Zn(II)-containing horse-liver alcohol dehydrogenase (LADH) and the specific active-site-substituted Co(II)LADH. 2. A combined evaluation of steady-state kinetic data and rate constants obtained from stopped-flow measurements, allowed the determination of all rate constants of the following ordered bi-bi mechanism: E in equilibrium E.NAD in equilibrium E.NAD.R1R2 CHOH in equilibrium E.NADH.R1R2CO in equilibrium E.NADH in equilibrium E. 3. On the basis of the different substrate specificities of LADH and yeast alcohol dehydrogenase (YADH), a procedure has been developed to evaluate the enantiomeric product composition of ketone reductions. 2-Butanone and 2-pentanone reductions revealed (S)-2-butanol (86%) and (S)-2-pentanol (95%) as the major products. 4. The observed enantioselectivity implies the existence of two productive ternary complexes; E.NADH.(pro-S) 2-butanone and E.NADH.(pro-R) 2-butanone. All rate constants describing the kinetic pathways of the system (S)-2-butanol, (R)-2-butanol/2-butanone have been determined. These data have been used to estimate the expected enantiomer product composition of 2-butanone reductions using apparent kcat/Km values for the two different ternary-complex configurations of 2-butanone. Additionally, these data have been used for computer simulations of the corresponding reaction cycles. Calculated, simulated and experimental data were found to be in good agreement. Thus, the system (S)-2-butanol, (R)-2-butanol/2-butanone is the first example of a LADH-catalyzed reaction for which the stereochemical course could be described in terms of rate constants of the underlying mechanism. 5. The effects of Co(II) substitution on the

  8. Kinetics of Dyes Adsorbed by Chitosan

    Institute of Scientific and Technical Information of China (English)

    CHEN Liang; CHEN Dong-hui; GAO Liang

    2002-01-01

    A study on adsorption of Acidic Blue RAWL and Cationic Blue X-GRRL dyes by chitosan have been conducted.The adsorption kinetic parameters including adsorption rate K and effective diffusing coefficient D'i under the optimal pH ranges have been determined. Analysis through the enthalpy calculation reveals a substantial thermodynamic difference between the adsorption processes of the two dyes, which helps to understand the adsorption mechanism by chitosan.

  9. Quantum kinetic theory

    CERN Document Server

    Bonitz, Michael

    2016-01-01

    This book presents quantum kinetic theory in a comprehensive way. The focus is on density operator methods and on non-equilibrium Green functions. The theory allows to rigorously treat nonequilibrium dynamics in quantum many-body systems. Of particular interest are ultrafast processes in plasmas, condensed matter and trapped atoms that are stimulated by rapidly developing experiments with short pulse lasers and free electron lasers. To describe these experiments theoretically, the most powerful approach is given by non-Markovian quantum kinetic equations that are discussed in detail, including computational aspects.

  10. Cinética da degradação ruminal dos carboidratos de quatro gramíneas tropicais em diferentes idades de corte e doses de adubação nitrogenada: técnica de produção de gases Kinetic parameters of carbohydrates ruminal degradation of four tropical grasses in different cutting ages and nitrogen fertilizer levels

    Directory of Open Access Journals (Sweden)

    Edenio Detmann

    2009-01-01

    Full Text Available Objetivou-se neste experimento avaliar a cinética de degradação ruminal dos capins setária (Setaria anceps Stapf, hemarthria (Hemarthria altissima [Poir] Stapf. & Hubbard, angola (Brachiaria purpurascens [Raddi] Henr. e acroceres (Acroceras macrum Stapf. adubados com 0, 100, 200, 300 ou 400 kg de N/ha e colhidos aos 28, 42, 56 ou 70 dias de idade. Os resultados foram avaliados por intermédio de análise de fatores. Após redução e avaliação da variação conjunta total das variáveis, optou-se pela adoção de três fatores, que englobaram 86,4% da variação total: o primeiro fator (Fator 1 associou-se ao volume de gás oriundo das frações de lenta e de rápida degradação e à taxa de degradação da fração rapidamente degradável (Vf1, Vf2 e k2; o segundo fator (Fator 2 associou-se à taxa de degradação de lenta digestão e à latência (k1 e L; e o terceiro fator (Fator 3, por sua vez, associou-se à digestibilidade in vitro da matéria seca (DIVMS. Os parâmetros da cinética de degradação foram influenciados pelas idades de corte. A digestibilidade in vitro da matéria seca reduziu com o avançar da idade das plantas. A adubação nitrogenada não promoveu respostas evidentes nos parâmetros avaliados. O capim-hemarthria se destacou dos demais em virtude de maior digestibilidade.The objective of this experiment was to evaluate the effects of levels 0, 100, 200, 300 and 400 kg of nitrogen/ha and cutting ages of 28, 42, 56 and 70 days on the kinetic parameters of ruminal degradation of carbohydrate of the following tropical forages: Setaria grass (Setaria anceps Stapf, Limpo grass (Hemarthria altissima [Poir] Stapf. & Hubbard, California grass (Brachiaria purpurascens [Raddi] Henr. and Nilo grass (Acroceras macrum Stpaf. The results were submitted to a factor analysis. After reduction and evaluation of the combined variation from the total variables, three factors comprising 86.44% of the total variation were considered

  11. A comparative study of kinetics of nuclear reactors

    Directory of Open Access Journals (Sweden)

    Obaidurrahman Khalilurrahman

    2009-01-01

    Full Text Available The paper deals with the study of reactivity initiated transients to investigate major differences in the kinetics behavior of various reactor systems under different operating conditions. The article also states guidelines to determine the safety limits on reactivity insertion rates. Three systems, light water reactors (pressurized water reactors, heavy water reactors (pressurized heavy water reactors, and fast breeder reactors are considered for the sake of analysis. The upper safe limits for reactivity insertion rate in these reactor systems are determined. The analyses of transients are performed by a point kinetics computer code, PKOK. A simple but accurate method for accounting total reactivity feedback in kinetics calculations is suggested and used. Parameters governing the kinetics behavior of the core are studied under different core states. A few guidelines are discussed to project the possible kinetics trends in the next generation reactors.

  12. Thermal Decomposition Kinetics of Ni(Ⅱ) Complex with Norfloxacin

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    The thermal decomposition of the [Ni(NFA)2(NO3)2]*2H2O (NFA=C16H18FN3O3, norfloxacin) and its kinetics were studied under the non-isothermal condition in nitrogen by TG-DTG and DTA methods. The intermediate and residue for each decomposition were identified from TG curve. The Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method were used to analyze the non-isothermal kinetic data. The possible reaction mechanisms were investigated by comparing the kinetic parameters. The kinetic equation for the third stage and the mathematical expressions for the kinetic compensation effects of the third stage were obtained.

  13. Kinetics and Catalysis Demonstrations.

    Science.gov (United States)

    Falconer, John L.; Britten, Jerald A.

    1984-01-01

    Eleven videotaped kinetics and catalysis demonstrations are described. Demonstrations include the clock reaction, oscillating reaction, hydrogen oxidation in air, hydrogen-oxygen explosion, acid-base properties of solids, high- and low-temperature zeolite reactivity, copper catalysis of ammonia oxidation and sodium peroxide decomposition, ammonia…

  14. Kinetic Gravity Separation

    NARCIS (Netherlands)

    Van Kooy, L.; Mooij, M.; Rem, P.

    2004-01-01

    Separations by density, such as the separation of non-ferrous scrap into light and heavy alloys, are often realized by means of heavy media. In principle, kinetic gravity separations in water can be faster and cheaper, because they do not rely on suspensions or salt solutions of which the density

  15. Kinetics and Mechanism of Ruthenium(III) Catalyzed Oxidation of Butanone and Uncatalyzed Oxidation of Cychlohexanone by Cerium(IV) in Acid Sulphate Medium

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Priyamvada; Hemkar, Shalini; Khandelwal, C. L.; Sharma, P. D. [Univ. of Rajasthan, Jaipur (India)

    2012-02-15

    The kinetics of ruthenium(III) chloride catalyzed oxidation of butanone and uncatalyzed oxidation of cyclohexanone by cerium(IV) in sulphuric acid medium have been studied. The kinetic rate law(I) in case of butanone conforms to the proposed mechanism. Kinetics and activation parameters have been evaluated conventionally. Kinetically preferred mode of reaction is via ketonic and not the enolic forms.

  16. Kinetic energy transfer during the tennis serve

    Directory of Open Access Journals (Sweden)

    C.L. de Subijana

    2010-12-01

    Full Text Available Several studies have established the pattern used in the over arm hitting and throwing movements, however to date there has not been one which statistically expresses the Kinetic Link Principle of the tennis serve. The main goals of this study were: first to investigate the kinetic energy transmission pattern using a complete mechanical body model and second, to create a tool which could help evaluating the individual technique of a tennis player. This tool was a statistical procedure which expressed the individual technique of a player as a mathematical function. Fourteen and twelve flat tennis serves of two top tennis players landing in an aiming area were recorded with two synchronized video cameras at 125 Hz. The experimental technique was 3D photogrammetry. A 28 points body model with five solid-rigid (the pelvis, the thorax, the upper arms and the racquet was built. The kinetic energies from the body segments were considered the biomechanical parameters. The mean speeds of the balls were 41.9 m/s (150.9 km/hr and 38.1 m/s (137.2 km/hr. A Kinetic Sequential Action Muscle principle based on the kinetic energy transfer was probed statistically by mean a correlation analysis [3]. This pattern showed the existence of a proximal to distal sequence of kinetic energy maximums. A significant (p<0.05 discriminant function for each player could predict the category of the serve (“good” or “bad” in the 78.6% and 100% of the cases. This function facilitated the understanding of the individual technique of a tennis player showing that this could be a tool for the tennis training complementary to the qualitative (observational analysis.

  17. The hydrothermal reaction kinetics of aspartic acid

    Science.gov (United States)

    Cox, Jenny S.; Seward, Terry M.

    2007-02-01

    kinetics of aspartic acid are very sensitive to parameters such as temperature, reactor materials (i.e., reactive surfaces), and additives, and that previous observations on aspartic acid were specific to the choice of experimental conditions.

  18. Parameter identification of thermophilic anaerobic degradation of valerate

    DEFF Research Database (Denmark)

    Flotats, X.; Ahring, Birgitte Kiær; Angelidaki, Irini

    2003-01-01

    The considered mathematical model of the decomposition of valerate presents three unknown kinetic parameters, two unknown stoichiometric coefficients, and three unknown initial concentrations for biomass. Applying a structural identifiability study, we concluded that it is necessary to perform si...

  19. A Pseudo-Kinetic Approach for Helmholtz Equation

    Institute of Scientific and Technical Information of China (English)

    Radjesvarane ALEXANDRE; Jie LIAO

    2013-01-01

    A lattice Boltzmann type pseudo-kinetic model for a non-homogeneous Helmholtz equation is derived in this paper.Numerical results for some model problems show the robustness and efficiency of this lattice Boltzmann type pseudo-kinetic scheme.The computation at each site is determined only by local parameters,and can be easily adapted to solve multiple scattering problems with many scatterers or wave propagation in nonhomogeneous medium without increasing the computational cost.

  20. IMPORTANCE OF KINETIC MEASURES IN TRAJECTORY PREDICTION WITH OPTIMAL CONTROL

    Directory of Open Access Journals (Sweden)

    Ömer GÜNDOĞDU

    2001-02-01

    Full Text Available A two-dimensional sagittally symmetric human-body model was established to simulate an optimal trajectory for manual material handling tasks. Nonlinear control techniques and genetic algorithms were utilized in the optimizations to explore optimal lifting patterns. The simulation results were then compared with the experimental data. Since the kinetic measures such as joint reactions and moments are vital parameters in injury determination, the importance of comparing kinetic measures rather than kinematical ones was emphasized.

  1. Kinetics and mechanism of synthetic CoS oxidation process

    Directory of Open Access Journals (Sweden)

    Štrbac N.

    2006-01-01

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

  2. Kinetic derivation of a Hamilton-Jacobi traffic flow model

    CERN Document Server

    Borsche, Raul; Kimathi, Mark

    2012-01-01

    Kinetic models for vehicular traffic are reviewed and considered from the point of view of deriving macroscopic equations. A derivation of the associated macroscopic traffic flow equations leads to different types of equations: in certain situations modified Aw-Rascle equations are obtained. On the other hand, for several choices of kinetic parameters new Hamilton-Jacobi type traffic equations are found. Associated microscopic models are discussed and numerical experiments are presented discussing several situations for highway traffic and comparing the different models.

  3. Evaluation of reliability of Coats-Redfern method for kinetic analysis of non-isothermal TGA

    Institute of Scientific and Technical Information of China (English)

    R. Ebrahimi-Kahrizsangi; M. H. Abbasi

    2008-01-01

    A critical examination was made on the reliability of kinetic parameters of nonisothermal thermoanalytical rate measurement by the widely applied Coats-Redfern(CR) equation. For this purpose, simulated TGA curves were made for reactions with different kinetic models, including chemical, diffusion (Janders) and mixed mechanism at different heating rates. The results show that, for reactions controlled kinetically by one mechanism, all solid state reaction models show linear trends by use of CR method and this method can not distinct the correct reaction model. For reactions with mixed mechanism, the CR method shows nonlinear trends and the reaction models and kinetic parameters can not be extracted from CR curves. The overall conclusion from this comparative appraisal of the characteristics of the CR approach to kinetic analysis of TGA data is that the CR approach is generally unsuitable for determination of kinetic parameters.

  4. A novel fractional technique for the modified point kinetics equations

    Directory of Open Access Journals (Sweden)

    Ahmed E. Aboanber

    2016-10-01

    Full Text Available A fractional model for the modified point kinetics equations is derived and analyzed. An analytical method is used to solve the fractional model for the modified point kinetics equations. This methodical technique is based on the representation of the neutron density as a power series of the relaxation time as a small parameter. The validity of the fractional model is tested for different cases of step, ramp and sinusoidal reactivity. The results show that the fractional model for the modified point kinetics equations is the best representation of neutron density for subcritical and supercritical reactors.

  5. The bainite reaction kinetics in austempered ductile iron

    Energy Technology Data Exchange (ETDEWEB)

    Taran, Yu.N.; Uzlov, K.I.; Kutsov, A.Yu. [State Metall. Acad., Dnepropetrovsk (Ukraine). Phys. Metall. Dept.

    1997-11-01

    Bainitic reaction kinetics in ductile iron contained according to Ukrainian standard (weight%) 3.60-3.80 carbon, 2.60-2.80 Si, {proportional_to}0.12 Mn, {proportional_to}0.60 Cu and additionally alloyed by Mo (0.15-0.20) has been studied. It was found that the overall transformation kinetics becomes slower as transformation temperature increase. This is because more intensive redistribution of carbon into austenite at higher temperatures. Two austenites with different carbon content have been fixed and kinetics of their lattices parameters has been studied. (orig.). 6 refs.

  6. Adsorption kinetics of propane on energetically heterogeneous activated carbon

    KAUST Repository

    Ismail, Azhar Bin

    2014-11-01

    The modeling of the adsorption isotherms and kinetics of the adsorbent+adsorbate pair is essential in simulating the performance of a pressurized adsorption chiller. In this work, the adsorption kinetics is analyzed from data measured using a magnetic suspension balance. The Statistical Rate Theory describes the Dubinin-Astakhov (DA) equation and extended to obtain an expression for transient analysis. Hence both the experimental excess equilibria data and the adsorption kinetics data may then be fitted to obtain the necessary parameters to fit the curves. The results fit the data very well within 6% of the error of regression. © 2014 Elsevier Ltd.

  7. ASSESSMENT OF KINETIC PROCESSES OF HARDENING OF BUILDING MATERIALS

    Directory of Open Access Journals (Sweden)

    P. V. Voronov

    2010-12-01

    Full Text Available Problem statement. Kinetic processes are of huge importance when producing building units and operating them as well. However, both technological and operation parameters are determined by the structure of a material under study.Results and conclusions. Kinetics with asymptotic approximation at hardening of building materials is analyzed. The validity of use of new kinetic equation is proved, characterizing harden composite systems and taking into consideration structural and topological peculiarities of new solid-like phase formation directly effecting the evolution of the processes. Results of research of change of strength at solidification a cement-sandy solution with various additives are submitted.

  8. CADLIVE optimizer: web-based parameter estimation for dynamic models

    Directory of Open Access Journals (Sweden)

    Inoue Kentaro

    2012-08-01

    Full Text Available Abstract Computer simulation has been an important technique to capture the dynamics of biochemical networks. In most networks, however, few kinetic parameters have been measured in vivo because of experimental complexity. We develop a kinetic parameter estimation system, named the CADLIVE Optimizer, which comprises genetic algorithms-based solvers with a graphical user interface. This optimizer is integrated into the CADLIVE Dynamic Simulator to attain efficient simulation for dynamic models.

  9. A Review of Kinetic Modeling Methodologies for Complex Processes

    Directory of Open Access Journals (Sweden)

    de Oliveira Luís P.

    2016-05-01

    Full Text Available In this paper, kinetic modeling techniques for complex chemical processes are reviewed. After a brief historical overview of chemical kinetics, an overview is given of the theoretical background of kinetic modeling of elementary steps and of multistep reactions. Classic lumping techniques are introduced and analyzed. Two examples of lumped kinetic models (atmospheric gasoil hydrotreating and residue hydroprocessing developed at IFP Energies nouvelles (IFPEN are presented. The largest part of this review describes advanced kinetic modeling strategies, in which the molecular detail is retained, i.e. the reactions are represented between molecules or even subdivided into elementary steps. To be able to retain this molecular level throughout the kinetic model and the reactor simulations, several hurdles have to be cleared first: (i the feedstock needs to be described in terms of molecules, (ii large reaction networks need to be automatically generated, and (iii a large number of rate equations with their rate parameters need to be derived. For these three obstacles, molecular reconstruction techniques, deterministic or stochastic network generation programs, and single-event micro-kinetics and/or linear free energy relationships have been applied at IFPEN, as illustrated by several examples of kinetic models for industrial refining processes.

  10. A steady-state kinetic analysis of the prolyl-4-hydroxylase mechanism.

    Science.gov (United States)

    Soskel, N T; Kuby, S A

    1981-01-01

    Published kinetic data by Kivirikko, et al. on the prolyl-4-hydroxylase reaction have been re-evaluated using the overall steady-state velocity equation in the forward and reverse directions for an ordered ter ter kinetic mechanism. Qualitatively, the published data for prolyl-4-hydroxylase appear to fit the predicted patterns for this kinetic mechanism. More kinetic data are needed to confirm these results and to quantitate the kinetic parameters but, tentatively, the order of substrate addition would appear to be alpha-ketoglutarate, oxygen, and peptide; and the order of product release would be hydroxylated peptide (or collagen), carbon dioxide, and succinate.

  11. Kinetics model for lutate dosimetry

    Energy Technology Data Exchange (ETDEWEB)

    Lima, M.F.; Mesquita, C.H., E-mail: mflima@ipen.br, E-mail: chmesqui@ipen.br [Instituto de Pesquisas Energeticas (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2013-11-01

    The use of compartmental analysis to predict the behavior of drugs in the organism is considered the better option among numerous methods employed in pharmacodynamics. A six compartments model was developed to determinate the kinetic constants of 177Lu-DOTATATO biodistribution using data from one published study with 67 patients treated by PRRT (Peptide receptor radionuclide therapy) and followed by CT during 68,25 hours. The compartmental analysis was made using the software AnaComp Registered-Sign . The influence of the time pos-injection over the dose assessment was studied taking into account the renal excretion management by aminoacid coinfusion, whose direct effects persist in the first day. The biodistribution curve was split in five sectors: 0-0.25h; 0-3.25h; 3.25-24.25h; 24.25-68.25h and 3.25-68.25h. After the examination of that influence, the study was concentrated in separate the biodistribution curve in two phases. Phase 1: governed by uptake from the blood, considering the time pos-injection until 3.25h and phase 2: governed by renal excretion, considering the time pos-injection from 3.25h to 68.25h. The model considered the organs and tissues superposition in the CT image acquisition by sampling parameters as the contribution of the the activity concentration in blood and relation between the sizes of the whole body and measured organs. The kinetic constants obtained from each phase (1 and 2) were used in dose assessment to patients in 26 organs and tissues described by MIRD. Dosimetry results were in agreement with the available results from literature, restrict to whole body, kidneys, bone marrow, spleen and liver. The advantage of the proposed model is the compartmental method quickness and power to estimate dose in organs and tissues, including tumor that, in the most part, were not discriminate by voxels of phantoms built using CT images. (author)

  12. Characterization of an inhibitor on glutathione-S-tranferase by analyzing the changes of kinetic parameters%测定谷胱甘肽-S-转硫酶动力学参数的变化表征其抑制剂

    Institute of Scientific and Technical Information of China (English)

    张灵; 杨晓兰; 白婧; 廖娟; 刘红博; 廖飞

    2011-01-01

    Objective:To establish a method based on analysis of the changes of kinetic parameters to characterize an inhibitor of glutathione-S-transferase (glutathione-S-transferases,GST). Methods:The acidic GST isozyme was purified from the porcine liver via anion-exchange chromatography and affinity chromatography. The reaction of glutathione (glutathione, GSH) and 1 -chloro-2,4-dini-trobenzene( 1, - chloro- 2,4- dinitrobenzene,CDNB) gave S-(2,4 -dinitrobenzyl) -glutathione (GS-DNB) as a candidate inhibitor. Michaelis-Menten constant(Km) and maximal reaction rate(Vm) were estimated to determine the inhibition constant (Ki) of GS-DNB. Results: Specific activity of GST was increased by more than 146 times with overall activity yield of about 30%. GST followed random bi-substrate kinetics and had Km of 42 |xmol/L for GSH,and Km of 0.86 mmol/L for CDNB. The competitive Ki of GS-DNB was (21 ± 1)μmol/L (n=2) against CDNB,and (17 ± 1) μmol/L (ra=2) against GSH. Conclusion:GS-DNB is an effective competitive inhibitor of GST;the estimation of Ki from responses of Km and Vm to inhibitor concentrations can be a conventional method to screen GST inhibitors.%目的:测定谷胱甘肽-S-转移酶(Glutathione-S-transferases,GST)动力学参数变化,建立表征其抑制剂的方法.方法:从猪肝经阴离子交换层析和亲和层析制备GST酸性同工酶,用还原型谷胱甘肽(Glutathione,GSH)和1-氯-2,4-二硝基苯(1,-chloro-2,4-dinitrobenzene,CDNB)合成S-(2,4-二硝基苯基)-谷胱甘肽(GS-DNB)为候选抑制剂,以GSH与CDNB为底物测定GST在GS-DNB作用下的米氏常数(Km)和最大反应速度(Vm),从而确定GS-DNB对GST的抑制常数(Ki).结果:此GST被纯化146倍以上,活性总收率近30%.该GST对GSH和CDNB的Km分别为42 μmol/L和0.86 mmol/L,属于随机双底物动力学模型.GS-DNB对CDNB竞争性Ki为(21±1)μmol/L (n=2);对GSH竞争性Ki为(17±1)μmol/L (n=2).结论:产物GS-DNB是GST的高亲和力竞争性抑制剂;测定GST动力学

  13. Kinetic Damage from Meteorites

    Science.gov (United States)

    Cooke, W.; Brown, P.; Matney, M.

    2017-01-01

    Comparing the natural meteorite flux at the Earth's surface to that of space debris, re-entering debris is 2 orders of magnitude less of a kinetic hazard at all but the very largest (and therefore rarest) sizes compared to natural impactors. Debris re-entries over several metric tonnes are roughly as frequent as natural impactors, but the survival fraction is expected to be much higher. Kinetic hazards from meteorites are very small, with only one recorded (indirect) injury reported. We expect fatalities to be even more rare, on the order of one person killed per several millennia. That several reports exist of small fragments/sand hitting people during meteorite falls is consistent with our prediction that this should occur every decade or so.

  14. Kinetic Actviation Relaxation Technique

    CERN Document Server

    Béland, Laurent Karim; El-Mellouhi, Fedwa; Joly, Jean-François; Mousseau, Normand

    2011-01-01

    We present a detailed description of the kinetic Activation-Relaxation Technique (k-ART), an off-lattice, self-learning kinetic Monte Carlo algorithm with on-the-fly event search. Combining a topological classification for local environments and event generation with ART nouveau, an efficient unbiased sampling method for finding transition states, k-ART can be applied to complex materials with atoms in off-lattice positions or with elastic deformations that cannot be handled with standard KMC approaches. In addition to presenting the various elements of the algorithm, we demonstrate the general character of k-ART by applying the algorithm to three challenging systems: self-defect annihilation in c-Si, self-interstitial diffusion in Fe and structural relaxation in amorphous silicon.

  15. Photon kinetics in plasmas

    Directory of Open Access Journals (Sweden)

    V.G. Morozov

    2009-01-01

    Full Text Available We present a kinetic theory of radiative processes in many-component plasmas with relativistic electrons and nonrelativistic heavy particles. Using the non-equilibrium Green's function technique in many-particle QED, we show that the transverse field correlation functions can be naturally decomposed into sharply peaked (non-Lorentzian parts that describe resonant (propagating photons and off-shell parts corresponding to virtual photons in the medium. Analogous decompositions are obtained for the longitudinal field correlation functions and the correlation functions of relativistic electrons. We derive a kinetic equation for the resonant photons with a finite spectral width and show that the off-shell parts of the particle and field correlation functions are essential to calculate the local radiating power in plasmas and recover the results of vacuum QED. The plasma effects on radiative processes are discussed.

  16. Kinetic Tetrazolium Microtiter Assay

    Science.gov (United States)

    Pierson, Duane L.; Stowe, Raymond; Koenig, David

    1993-01-01

    Kinetic tetrazolium microtiter assay (KTMA) involves use of tetrazolium salts and Triton X-100 (or equivalent), nontoxic, in vitro color developer solubilizing colored metabolite formazan without injuring or killing metabolizing cells. Provides for continuous measurement of metabolism and makes possible to determine rate of action of antimicrobial agent in real time as well as determines effective inhibitory concentrations. Used to monitor growth after addition of stimulatory compounds. Provides for kinetic determination of efficacy of biocide, greatly increasing reliability and precision of results. Also used to determine relative effectiveness of antimicrobial agent as function of time. Capability of generating results on day of test extremely important in treatment of water and waste, disinfection of hospital rooms, and in pharmaceutical, agricultural, and food-processing industries. Assay also used in many aspects of cell biology.

  17. Thermal Decomposition Kinetics of Lead 2,4,6-Trinitroresorcinate Monohydrate

    Institute of Scientific and Technical Information of China (English)

    HU Rong-zu; YAO Pu; LI Jing; CHEN San-ping; GAO Sheng-li; ZHAO Feng-qi; SONG Ji-rong; SHI Qi-zhen; CHEN Pei; LUO Yang; ZHAO Hong-an

    2004-01-01

    The non-isothermal decomposition of lead 2,4,6-trinitroresorcinate monohydrate, Pb (TNR) · H2O. was investigated by means of TG-DTA, DSC and IR. The thermal decomposition mechanism and the dissociated kinetics were also investigated. The kinetic parameters were obtained from the analysis of the DSC curves by integral and differential methods. The most probable kinetic model function of the dehydration reaction of Pb(TNR) · H2O was suggested by the comparison of the kinetic parameters.

  18. Recovering kinetics from a simplified protein folding model using replica exchange simulations: a kinetic network and effective stochastic dynamics.

    Science.gov (United States)

    Zheng, Weihua; Andrec, Michael; Gallicchio, Emilio; Levy, Ronald M

    2009-08-27

    We present an approach to recover kinetics from a simplified protein folding model at different temperatures using the combined power of replica exchange (RE), a kinetic network, and effective stochastic dynamics. While RE simulations generate a large set of discrete states with the correct thermodynamics, kinetic information is lost due to the random exchange of temperatures. We show how we can recover the kinetics of a 2D continuous potential with an entropic barrier by using RE-generated discrete states as nodes of a kinetic network. By choosing the neighbors and the microscopic rates between the neighbors appropriately, the correct kinetics of the system can be recovered by running a kinetic simulation on the network. We fine-tune the parameters of the network by comparison with the effective drift velocities and diffusion coefficients of the system determined from short-time stochastic trajectories. One of the advantages of the kinetic network model is that the network can be built on a high-dimensional discretized state space, which can consist of multiple paths not consistent with a single reaction coordinate.

  19. Flocculation Kinetics of Chitosan

    Institute of Scientific and Technical Information of China (English)

    陈亮; 林志艳; 陈东辉

    2003-01-01

    Under the various conditions, the experiments of flocculation of bentonite solution with chitosan were carried out. And the flocculation kinetics was studied by the changes of floc size along with time. The results show that hydraulic gradient G (s-1) plays a key role in growing up of floc size and both of molecular weight and initial turbidity of bentonite solution influence the floc size in steady state and the time needed for steady floc size.

  20. Non-isothermal Kinetics of the Dehydration Process of Na2MoO4·2H20

    Institute of Scientific and Technical Information of China (English)

    张建军; 张秀芳; 武克忠; 任宁; 周雪; 刘晓地

    2004-01-01

    The dehydration process of Na2MoO4·2H2O and its kinetics have been studied by TG-DTG. Using Malek method, SB(m,n) was defined as the kinetic model of the dehydration process. The corresponding kinetic and thermodynamic parameters were obtained.

  1. Good relationship between saliva cotinine kinetics and plasma cotinine kinetics after smoking one cigarette.

    Science.gov (United States)

    Yuki, Dai; Kikuchi, Akira; Miura, Naoki; Kakehi, Aoi; Onozawa, Masahiro

    2013-11-01

    This study investigated the relationship between plasma and saliva cotinine kinetics after smoking one cigarette and the relationship between cotinine kinetics and estimated nicotine intake, which was calculated as mouth level exposure (MLE) of nicotine, from smoking two test cigarettes with different nicotine yields. This study was conducted in 16 healthy adult Japanese smokers, who did not have null nor reduced-activity alleles of CYP2A6, with a quasi-randomized crossover design of smoking a low-tar cigarette or a high-tar cigarette. Saliva cotinine showed similar concentration profiles to plasma cotinine, and all of the calculated pharmacokinetic parameters of cotinine showed the same values in plasma and saliva. The Cmax and AUC of cotinine showed almost the same dose-responsiveness to the estimated MLE of nicotine between plasma and saliva, but the tmax and t1/2 of cotinine were not affected by the estimated MLE of nicotine in either plasma or saliva. The results show that saliva cotinine kinetics reflects plasma cotinine kinetics, and measurement of saliva cotinine concentration gives the same information as plasma cotinine on the nicotine intake. Thus, saliva cotinine would be a good and less-invasive exposure marker of cigarette smoke, reflecting the plasma cotinine concentration and kinetics.

  2. Drying kinetics of some building materials

    Directory of Open Access Journals (Sweden)

    A. Moropoulou

    2005-06-01

    Full Text Available Moisture is one of the most deteriorating factors of buildings. The deteriorating effect of moisture occurs mainly during the drying phase, and not in the wetting phase. Appropriate parameters of the drying kinetics are required for the building materials. Environmental factors, such as air temperature, air humidity, and air velocity affect drying. An experimental air dryer of controlled drying air conditions was used to investigate the drying performance of 4 stone materials, 2 bricks and 7 plasters. Drying kinetics was examined at 4 air temperatures, 6 air humidities, and 3 air velocities. A first-order kinetics model was obtained, in which the drying time constant was a function of the drying conditions, and the equilibrium material moisture content was described by the Oswin equation. The parameters of the proposed model were found to be affected strongly by the material and the drying air conditions. The results obtained are very useful in selecting the appropriate plaster to protect existing historic buildings.

  3. Thermodynamically consistent model calibration in chemical kinetics

    Directory of Open Access Journals (Sweden)

    Goutsias John

    2011-05-01

    Full Text Available Abstract Background The dynamics of biochemical reaction systems are constrained by the fundamental laws of thermodynamics, which impose well-defined relationships among the reaction rate constants characterizing these systems. Constructing biochemical reaction systems from experimental observations often leads to parameter values that do not satisfy the necessary thermodynamic constraints. This can result in models that are not physically realizable and may lead to inaccurate, or even erroneous, descriptions of cellular function. Results We introduce a thermodynamically consistent model calibration (TCMC method that can be effectively used to provide thermodynamically feasible values for the parameters of an open biochemical reaction system. The proposed method formulates the model calibration problem as a constrained optimization problem that takes thermodynamic constraints (and, if desired, additional non-thermodynamic constraints into account. By calculating thermodynamically feasible values for the kinetic parameters of a well-known model of the EGF/ERK signaling cascade, we demonstrate the qualitative and quantitative significance of imposing thermodynamic constraints on these parameters and the effectiveness of our method for accomplishing this important task. MATLAB software, using the Systems Biology Toolbox 2.1, can be accessed from http://www.cis.jhu.edu/~goutsias/CSS lab/software.html. An SBML file containing the thermodynamically feasible EGF/ERK signaling cascade model can be found in the BioModels database. Conclusions TCMC is a simple and flexible method for obtaining physically plausible values for the kinetic parameters of open biochemical reaction systems. It can be effectively used to recalculate a thermodynamically consistent set of parameter values for existing thermodynamically infeasible biochemical reaction models of cellular function as well as to estimate thermodynamically feasible values for the parameters of new

  4. Chemical, physical, and theoretical kinetics of an ultrafast folding protein.

    Science.gov (United States)

    Kubelka, Jan; Henry, Eric R; Cellmer, Troy; Hofrichter, James; Eaton, William A

    2008-12-01

    An extensive set of equilibrium and kinetic data is presented and analyzed for an ultrafast folding protein--the villin subdomain. The equilibrium data consist of the excess heat capacity, tryptophan fluorescence quantum yield, and natural circular-dichroism spectrum as a function of temperature, and the kinetic data consist of time courses of the quantum yield from nanosecond-laser temperature-jump experiments. The data are well fit with three kinds of models--a three-state chemical-kinetics model, a physical-kinetics model, and an Ising-like theoretical model that considers 10(5) possible conformations (microstates). In both the physical-kinetics and theoretical models, folding is described as diffusion on a one-dimensional free-energy surface. In the physical-kinetics model the reaction coordinate is unspecified, whereas in the theoretical model, order parameters, either the fraction of native contacts or the number of native residues, are used as reaction coordinates. The validity of these two reaction coordinates is demonstrated from calculation of the splitting probability from the rate matrix of the master equation for all 10(5) microstates. The analysis of the data on site-directed mutants using the chemical-kinetics model provides information on the structure of the transition-state ensemble; the physical-kinetics model allows an estimate of the height of the free-energy barrier separating the folded and unfolded states; and the theoretical model provides a detailed picture of the free-energy surface and a residue-by-residue description of the evolution of the folded structure, yet contains many fewer adjustable parameters than either the chemical- or physical-kinetics models.

  5. FY2014 Parameters for Helions and Gold Ions in Booster, AGS, and RHIC

    Energy Technology Data Exchange (ETDEWEB)

    Gardner, C. J. [Brookhaven National Lab. (BNL), Upton, NY (United States). Collider-Accelerator Dept.

    2014-08-15

    The nominal parameters for helions (helion is the bound state of two protons and one neutron, the nucleus of a helium-3 atom) and gold ions in Booster, AGS, and RHIC are given for the FY2014 running period. The parameters are found using various formulas to derive mass, helion anomalous g-factor, kinetic parameters, RF parameters, ring parameters, etc..

  6. Thermal Decomposition Kinetics of Triethylene Glycol Dinitrate

    Institute of Scientific and Technical Information of China (English)

    CHEN,Pei(陈沛); ZHAO,Feng-Qi(赵凤起); LUO,Yang(罗阳); HU,Rong-Zu(胡荣祖); LI,Shang-Wen(李上文); GAO,Yin(高茵)

    2004-01-01

    The thermal behavior and kinetic parameters of the decomposition reaction of triethylene glycol dinitrate (TEGDN) in a temperature-programmed mode at different pressures (0.1, 2, 4 and 6 MPa) have been investigated by means of DSC and TG-DTG. The results show that the properties of the thermal decomposition of TEGDN are affected by the change of pressure, and the kinetic model function, the apparent activation energy Ea and TEGDN obtained by the values Teo and Tpo of the onset temperature Te and the peak temperature TP when the heating rate tends to zero are 191.05,209.86 ℃ at 0.1 MPa, 207.59 and 221.65 ℃ at 2 MPa, respectively.

  7. 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.

  8. Energy transfer and kinetics in mechanochemistry.

    Science.gov (United States)

    Chen, Zhiliang; Lu, Shengyong; Mao, Qiongjing; Buekens, Alfons; Wang, Yuting; Yan, Jianhua

    2017-09-13

    Mechanochemistry (MC) exerts extraordinary degradation and decomposition effects on many chlorinated, brominated, and even fluorinated persistent organic pollutants (POPs). However, its application is still limited by inadequate study of its reaction kinetic aspects. In the present work, the ball motion and energy transfer in planetary ball mill are investigated in some detail. Almost all milling parameters are summarised in a single factor-total effective impact energy. Furthermore, the MC kinetic between calcium oxide/Al and hexachlorobenzene is well established and modelled. The results indicate that total effective impact energy and reagent ratio are the two factors sufficient for describing the MC degradation degree of POPs. The reaction rate constant only depends on the chemical properties of reactants, so it could be used as an important index to appraise the quality of MC additives. This model successfully predicts the reaction rate for different operating conditions, indicating that it could be suitably applied for conducting MC reactions in other reactors.

  9. Reaction Kinetics of Nanostructured Silicon Carbide

    Science.gov (United States)

    Wallis, Kendra; Zerda, T. W.

    2006-10-01

    Nanostructured silicon carbide (SiC) is of interest particularly for use in nanocomposites that demonstrate high hardness as well as for use in semiconductor applications. Reaction kinetics studies of solid-solid reactions are relatively recent and present a method of determining the reaction mechanism and activation energy by measuring reaction rates. We have used induction heating to heat quickly, thus reducing the error in reaction time measurements. Data will be presented for reactions using silicon nanopowder (melting point of silicon. Using the well-known Avrami-Erofeev model, a two-parameter chi- square fit of the data provided a rate constant (k) and parameter (n), related to the reaction mechanism, for each temperature. From these data, an activation energy of 138 kJ/mol was calculated. In addition, the parameter n suggests the reaction mechanism, which will also be discussed. Experiments are continuing at higher temperatures to consider the liquid- solid reaction as well.

  10. Size dependence of adsorption kinetics of nano-MgO: a theoretical and experimental study

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Shuting; Wen, Yanzhen; Cui, Zixiang; Xue, Yongqiang, E-mail: xyqlw@126.com [Taiyuan University of Technology (China)

    2016-01-15

    Nanoparticles present tremendous differences in adsorption kinetics compared with corresponding bulk particles which have great influences on the applications of nanoparticles. A size-dependent adsorption kinetic theory was proposed, the relations between adsorption kinetic parameters, respectively, and particle size of nano-adsorbent were derived theoretically, and the influence mechanism of particle size on the adsorption kinetic parameters was discussed. In experiment, nanoscale magnesium oxide (nano-MgO) with different diameters between 11.5 and 41.4 nm with narrow size distribution and low agglomeration were prepared, and the kinetic parameters of adsorption of benzene on nano-MgO in aqueous solution were obtained. Then the influence regularities of the particle size on the adsorption kinetic parameters were obtained. The experimental results are consistent with the nano-adsorption kinetic theory. With particle size decreasing, the adsorption rate constant increases; the adsorption activation energy and the adsorption pre-exponential factor decrease. Furthermore, the logarithm of adsorption rate constant, the adsorption activation energy, and the logarithm of adsorption pre-exponential factor are linearly related to the reciprocal of particle diameter, respectively. The mechanism of particle size influence on the kinetic parameters is that the activation energy is influenced by the molar surface enthalpy of nano-adsorbent, the pre-exponential factor by the molar surface entropy, and the rate constant by both the molar surface enthalpy and the molar surface entropy.

  11. Estimação de parâmetros da cinética de trânsito de partículas em bovinos sob pastejo por diferentes seqüências amostrais Estimation of solid transit kinetics parameters in cattle under grazing by different sample series

    Directory of Open Access Journals (Sweden)

    Edenio Detmann

    2001-02-01

    of a non-linear model in the process parameter estimation of the solid transit kinetics of bovine at pasture, using different sequences of fecal sampling. Five F1 Limousin X Nellore steers, fistulated in esophagus and rumen on Brachiaria decumbens grazing and concentrate supplemented during the rainy season period were used. The experiment was developed in three experimental periods; in a randomized completely blocks design. Chromium mordant, produced from extrusa samples, was used as marker. The double exponential time-dependent model was adjusted to the curves of fecal excretion of marker, and the following sample sequences were used: SEQ 1 - 22 samples (complete sample sequence; SEQ 2 and SEQ 3 - 17 samples (reduction of collection points in the ascendant and descendent phases of the curve, respectively; and SEQ 4 and SEQ 5 - 13 and 10 fecal samples (reduction of the number of samples in the whole profile of the curve. The reduced sequences were produced starting from the omission of specific points of the complete sample sequence (SEQ 1. The comparison among the estimates of the kinetic parameters and fecal excretion; the descriptive analysis of the necessary number of iterations to the convergence of the model and of the determination coefficient; and the evaluation of lack of fitness showed no differences among the sequences. However, the residual analysis pointed improvements in the graphic behavior and runs of signal profile of the residues with the reduction of the number of collections in SEQ 4 and SEQ 5. In function of small efficiency loss, evaluated from the residual variance, observed in SEQ 5, the employment of 13 fecal collections (SEQ 4 for evaluation of the fecal excretion curve of the marker in similar studies was recommended.

  12. Stochastic Electrochemical Kinetics

    CERN Document Server

    Beruski, O

    2016-01-01

    A model enabling the extension of the Stochastic Simulation Algorithm to electrochemical systems is proposed. The physical justifications and constraints for the derivation of a chemical master equation are provided and discussed. The electrochemical driving forces are included in the mathematical framework, and equations are provided for the associated electric responses. The implementation for potentiostatic and galvanostatic systems is presented, with results pointing out the stochastic nature of the algorithm. The electric responses presented are in line with the expected results from the theory, providing a new tool for the modeling of electrochemical kinetics.

  13. Recognizing and analyzing variability in amyloid formation kinetics: Simulation and statistical methods.

    Science.gov (United States)

    Hall, Damien; Zhao, Ran; So, Masatomo; Adachi, Masayuki; Rivas, Germán; Carver, John A; Goto, Yuji

    2016-10-01

    We examine the phenomenon of variability in the kinetics of amyloid formation and detail methods for its simulation, identification and analysis. Simulated data, reflecting intrinsic variability, were produced using rate constants, randomly sampled from a pre-defined distribution, as parameters in an irreversible nucleation-growth kinetic model. Simulated kinetic traces were reduced in complexity through description in terms of three characteristic parameters. Practical methods for assessing convergence of the reduced parameter distributions were introduced and a bootstrap procedure was applied to determine convergence for different levels of intrinsic variation. Statistical methods for assessing the significance of shifts in parameter distributions, relating to either change in parameter mean or distribution shape, were tested. Robust methods for analyzing and interpreting kinetic data possessing significant intrinsic variance will allow greater scrutiny of the effects of anti-amyloid compounds in drug trials.

  14. Extending ITC to Kinetics with kinITC.

    Science.gov (United States)

    Dumas, Philippe; Ennifar, Eric; Da Veiga, Cyrielle; Bec, Guillaume; Palau, William; Di Primo, Carmelo; Piñeiro, Angel; Sabin, Juan; Muñoz, Eva; Rial, Javier

    2016-01-01

    Isothermal titration calorimetry (ITC) has long been used for kinetic studies in chemistry, but this remained confined to enzymatic studies in the biological field. In fact, the biological community has long had the tendency of ignoring the kinetic possibilities of ITC considering it solely as a thermodynamic technique, whereas surface plasmon resonance is seen as the kinetic technique par excellence. However, the primary signal recorded by ITC is a heat power which is directly related to the kinetics of the reaction. Here, it is shown how this kinetic signal can be recovered by using kinITC, the kinetic extension of ITC. The theoretical basis of kinITC is detailed for the most common situation of a second-order reaction A+B Ω C characterized by kinetic parameters kon, koff. A simplified kinITC-ETC method based upon the determination of an "Equilibration Time Curve" (ETC) is presented. The ETC is obtained by automatic determination of the "effective end" of each injection. The method is illustrated with experimental results with a comparison to Surface Plasmon Resonance (SPR) data. kon values were obtained in a wide range, from 10(3) to 0.5×10(6) M(-1) s(-1). All procedures were implemented in the program AFFINImeter (https://www.affinimeter.com/).

  15. KINETICS OF NON-ISOTHERMAL CRYSTALLIZATION OF POLY (ETHYLENE TEREPHTHALATE) MODIFIED BY POLY (ETHYLENE GLYCOL)

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhiying; WU Shizhen; DU Yinghua; CAO Zhenlin

    1991-01-01

    The non-isothermal crystallization kinetics of poly(ethylene terephthalate) (PET) modified by poly (ethlene glycol) (PEG) were determined by DSC. The dual linear regression method was used to evaluate the relationship between the reciprocal of t1/2 ( the half life of crystallization ) and the appropriate temperature variable. The parameters such as the activation energy (Ed) for transport,the equilibrium melting temperature (T0m),the nucleation parameter (ψ),the maximum crystallization temperature (Tc, max ) , and the kinetic crystallizability (G) for the copolyesters were obtained. The influence of the PEG content in PET chains on the parameters characterizing crystallization kinetics and crystallization thermodynamics was discussed.

  16. Kinetic Modelling of Macroscopic Properties Changes during Crosslinked Polybutadiene Oxidation

    Science.gov (United States)

    Audouin, Ludmila; Coquillat, Marie; Colin, Xavier; Verdu, Jacques; Nevière, Robert

    2008-08-01

    The thermal oxidation of additive free hydroxyl-terminated polybutadiene (HTPB) isocyanate crosslinked rubber bulk samples has been studied at 80, 100 and 120 °C in air. The oxidation kinetics has been monitored by gravimetry and thickness distribution of oxidation products was determined by FTIR mapping. Changes of elastic shear modulus G' during oxidation were followed during oxidation at the same temperatures. The kinetic model established previously for HTPB has been adapted for bulk sample oxidation using previously determined set of kinetic parameters. Oxygen diffusion control of oxidation has been introduced into the model. The mass changes kinetic curves and oxidation products profiles were simulated and adequate fit was obtained. Using the rubber elasticity theory the elastic modulus changes were simulated taking into account the elastically active chains concentration changes due to chain scission and crosslinking reactions. The reasonable fit of G' as a function of oxidation time experimental curves was obtained.

  17. Kinetics of pressure induced structural phase transitions—A review

    Indian Academy of Sciences (India)

    N V Chandra Shekar; K Govinda Rajan

    2001-02-01

    The current status of experimental as well as theoretical advances in the understanding of kinetics of structural phase transitions is reviewed. A brief outline of the classification of phase transitions and classical ideas in the theory of kinetics of phase change is presented first. High pressure experimental techniques developed for studying the kinetics of structural transitions are reviewed and the salient features of each technique is brought out. The experimental technique using the diamond anvil cell (DAC) and image processing gets special mention as it promises to impart a new direction to this field. The usefulness of kinetic parameters in understanding the mechanism of a phase transition is examined. Typical examples from the literature are provided to give a flavour for these kind of studies. In conclusion, several open questions are raised which could pave way for future work in this area.

  18. Automated Transition State Theory Calculations for High-Throughput Kinetics.

    Science.gov (United States)

    Bhoorasingh, Pierre L; Slakman, Belinda L; Seyedzadeh Khanshan, Fariba; Cain, Jason Y; West, Richard Henry

    2017-08-18

    A scarcity of known chemical kinetic parameters leads to the use of many reaction rate estimates, which are not always sufficiently accurate, in the construction of detailed kinetic models. To reduce the reliance on these estimates and improve the accuracy of predictive kinetic models, we have developed a high-throughput, fully automated, reaction rate calculation method, AutoTST. The algorithm integrates automated saddle-point geometry search methods and a canonical transition state theory kinetics calculator. The automatically calculated reaction rates compare favorably to existing estimated rates. Comparison against high level theoretical calculations show the new automated method performs better than rate estimates when the estimate is made by a poor analogy. The method will improve by accounting for internal rotor contributions and by improving methods to determine molecular symmetry.

  19. Kinetics examination of pressurised steam gasification of beech wood

    Directory of Open Access Journals (Sweden)

    Grzywacz Przemysław

    2016-01-01

    Full Text Available In Poland, among all renewable energy sources, share of biomass in electricity production is the largest. Great potential in biomass utilization involves use of gasification technology. The course of biomass gasification process in steam atmosphere is the subject of numerous scientific studies. The aim of this study was kinetics examination of pressurized beech wood waste gasification, that can be successfully used in industrial gasification. Measurements were carried out on a unique laboratory installation, that allows kinetics examination of solid fuels gasification with steam at wide range of pressures, via using thermovolumetric method. Formation rates of main gaseous products were determined, moreover, composition of post-reaction gas, as well as biomass conversion degree depending on the temperature were specified. Kinetic parameters of gasification were calculated and series of kinetic models were used to their designation ie Isoconvesional method, Integrated Core Model (ICM, Grain Model (GM and Random Pore Model (RPM.

  20. [The kinetic theory of the aging of living systems].

    Science.gov (United States)

    Viktorov, A A; Kholodnov, V A

    2013-01-01

    Kinetic theory of aging of living systems is proposed. Theory is based on the concept of continuous adaptation of biological system (BS) from its birth to changing conditions of environment (ENV). Adaptation rate as rate of risk of destructions accumulation in BS is studied as competition between two simultaneous processes: BS destruction and recombination of damages defined by kinetics of autocatalytic chemical reactions. Kinetic theory assumes critical phenomenon: failure of adaptation when intensity of ENV impact becomes higher some critical level. Choice of parameters of kinetic mathematical model and accounting dependence of ENV impact intensity on time allows describing the following results observed in medical practice: child mortality, depletion of adaptive reserves, slowing the rate of aging of long-living persons, damped harmonic oscillations of biological response at pulse toxic intervention and to estimate risks of disease and death.

  1. Non-isothermal differential adsorption kinetics for binary gas mixture

    Energy Technology Data Exchange (ETDEWEB)

    Sircar, S. (Air Products and Chemicals, Inc., Allentown, PA (United States))

    1994-06-01

    Analytical solutions are developed for non-isothermal adsorption kinetics of a binary gas mixture in a differential adsorption test (DAT). Linear driving force models are used to describe the adsorption kinetics of individual components. It is demonstrated that a very small change in the adsorbent temperature can introduce a substantial difference between isothermal and non-isothermal kinetic behaviors of the components of the mixture. The fractional uptake of a component of the mixture can exceed unity and go through a maximum value during the DAT due to the non-isothermal effects. An isothermal kinetic model for binary mixture adsorption using both straight and cross transport coefficients can also describe such uptake behavior, but the model parameters will be artificial due to the ignorance of adsorbent non-isothermality.

  2. Kinetic modelling of the Fischer-Tropsch synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Gambaro, C.; Pollesel, P.; Zennaro, R. [Eni S.p.A., San Donato Milanese (Italy); Lietti, L.; Tronconi, E. [Politecnico di Milano (Italy)

    2006-07-01

    In this work the development of a CO conversion kinetic model of the Fischer-Tropsch process will be presented. Kinetic data were produced testing a Co-based catalyst on two lab units, equipped with a slurry autoclave and a fixed bed reactor respectively. Accordingly, information on the catalytic performances of the same catalyst in two reactor configurations were also obtained. The experimental results were then analyzed with different kinetic models, available in the literature: two mechanistic models, derived by Sarup-Wojciechowski and Yates-Satterfield, and a simple power law rate expression were compared. The parameters of the different rate expressions were estimated by non-linear regression of the kinetic data collected on the two lab units. (orig.)

  3. Non-Isothermal Desolvation Kinetics of Erythromycin A Acetone Solvate

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The desolvation of erythromycin acetone solvate was investigated under non-isothermal conditions by a thermogravimetric analyzer. This paper emphasized the kinetic analysis of non-isothermal TG-DTA data by Achar method and Coats-Redfern method to fit various solid-state reaction models, and to achieve kinetic parameters of desolvation. The mechanism of thermal desolvation was evaluated using the kinetic compensation effect. The results show that kinetics of desolvation of erythromycin acetone solvate was compatible with the mechanism of a two-dimensional diffusion controlled and was best expressed by Valensi equation. Corresponding to the integral method and the differential method, the activation energy of desolvation of erythromycin acetone solvate was estimated to be 51.26-57.11 kJ/mol, and the pre-exponential factor was 8.077 × 106 s-1-4.326 × 107 s-1,respectively.

  4. Thermal Characterization and Decomposition Kinetics of Free Anthraquinones from Rhubarb

    Institute of Scientific and Technical Information of China (English)

    Li Ming ZHANG; Xia LI; Yu Jie DAI

    2006-01-01

    The thermal behaviour of aloe-emodin, chrysophanol and physcion and their kinetics have been investigated under non-isothermal conditions by means of differential thermal analysis (DTA) and thermogravimetry (TG). The thermal characteristics have been determined using the DTA and TG-DTG curves. The non-isothermal kinetic data were analyzed by means of the Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method. The possible reaction mechanisms have been investigated by comparing the kinetic parameters. The kinetic equation for aloe-emodin, chrysophanol and physcion can be expressed as dα/dt=Aexp(-E/RT)1/3(1-α)[-In(1-α)]-2. The activation energy E (kJ mol-1) of the three free anthraquinones are 78.09, 89.54,and 107.5 and their lnA/s-1 are 22.98, 36.85 and 43.60, respectively.

  5. Moment equations for chromatography based on Langmuir type reaction kinetics.

    Science.gov (United States)

    Miyabe, Kanji

    2014-08-22

    Moment equations were derived for chromatography, in which the reaction kinetics between solute molecules and functional ligands on the stationary phase was represented by the Langmuir type rate equation. A set of basic equations of the general rate model of chromatography representing the mass balance, mass transfer rate, and reaction kinetics in the column were analytically solved in the Laplace domain. The moment equations for the first absolute moment and the second central moment in the real time domain were derived from the analytical solution in the Laplace domain. The moment equations were used for predicting the chromatographic behavior under hypothetical HPLC conditions. The influence of the parameters relating to the adsorption equilibrium and to the reaction kinetics on the chromatographic behavior was quantitatively evaluated. It is expected that the moment equations are effective for a detailed analysis of the influence of the mass transfer rates and of the Langmuir type reaction kinetics on the column efficiency.

  6. Biodegradation kinetics during different start up of the anaerobic tapered fluidized bed reactor

    Directory of Open Access Journals (Sweden)

    Rangasamy Parthiban

    2011-10-01

    Full Text Available Kinetic study for different start up conditions of the anaerobic digestion of wastewater derived from the sago processingfrom tubers of tapioca (Mannihot utillisema is discussed. The experiment is carried out with synthetic waste water usinga tapered fluidized bed reactor. Mesoporous granulated activated carbon is used as a bacterial support. The kinetic modelfollows half order kinetics for substrate utilization and for methane formation and it exhibits an order of 0.20 during thestart up of the reactor without acclimatization. For the remaining start up with acclimatized sludge, kinetic parameters areexpressed in terms of Langmuir-Hinshelwood kinetics for the substrate utilization. The methane formation kinetics followsan order of the reaction as 0.30. The values of the kinetic constants are in the range of 0.13–0.21.

  7. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II ? reactions of organic species

    OpenAIRE

    2005-01-01

    International audience; This article, the second in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of Organic species, which were last published in 1999, and were updated on the IUPAC website in late 2002. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and eight appendices con...

  8. Kinetics of coal pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Seery, D.J.; Freihaut, J.D.; Proscia, W.M. (United Technologies Research Center, East Hartford, CT (USA)); Howard, J.B.; Peters, W.; Hsu, J.; Hajaligol, M.; Sarofim, A. (Massachusetts Inst. of Tech., Cambridge, MA (USA)); Jenkins, R.; Mallin, J.; Espindola-Merin, B. (Pennsylvania State Univ., University Park, PA (USA)); Essenhigh, R.; Misra, M.K. (Ohio State Univ., Columbus, OH (USA))

    1989-07-01

    This report contains results of a coordinated, multi-laboratory investigation of coal devolatilization. Data is reported pertaining to the devolatilization for bituminous coals over three orders of magnitude in apparent heating rate (100 to 100,000 + {degree}C/sec), over two orders of magnitude in particle size (20 to 700 microns), final particle temperatures from 400 to 1600{degree}C, heat transfer modes ranging from convection to radiative, ambient pressure ranging from near vacuum to one atmosphere pressure. The heat transfer characteristics of the reactors are reported in detail. It is assumed the experimental results are to form the basis of a devolatilization data base. Empirical rate expressions are developed for each phase of devolatilization which, when coupled to an awareness of the heat transfer rate potential of a particular devolatilization reactor, indicate the kinetics emphasized by a particular system reactor plus coal sample. The analysis indicates the particular phase of devolatilization that will be emphasized by a particular reactor type and, thereby, the kinetic expressions appropriate to that devolatilization system. Engineering rate expressions are developed from the empirical rate expressions in the context of a fundamental understanding of coal devolatilization developed in the course of the investigation. 164 refs., 223 figs., 44 tabs.

  9. 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

  10. Adsorption analysis equilibria and kinetics

    CERN Document Server

    Do, Duong D

    1998-01-01

    This book covers topics of equilibria and kinetics of adsorption in porous media. Fundamental equilibria and kinetics are dealt with for homogeneous as well as heterogeneous particles. Five chapters of the book deal with equilibria and eight chapters deal with kinetics. Single component as well as multicomponent systems are discussed. In kinetics analysis, we deal with the various mass transport processes and their interactions inside a porous particle. Conventional approaches as well as the new approach using Maxwell-Stefan equations are presented. Various methods to measure diffusivity, such

  11. KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYNTHESIS

    Energy Technology Data Exchange (ETDEWEB)

    Dragomir B. Bukur; Gilbert F. Froment; Tomasz Olewski

    2006-09-29

    This report covers the fourth year of a research project conducted under the University Coal Research Program. The overall objective of this project is to develop a comprehensive kinetic model for slurry-phase Fischer-Tropsch synthesis (FTS) employing iron-based catalysts. This model will be validated with experimental data obtained in a stirred-tank slurry reactor (STSR) over a wide range of process conditions. The model will be able to predict molar flow rates and concentrations of all reactants and major product species (water, carbon dioxide, linear 1- and 2-olefins, and linear paraffins) as a function of reaction conditions in the STSR. During the fourth year of the project, an analysis of experimental data collected during the second year of this project was performed. Kinetic parameters were estimated utilizing product distributions from 27 mass balances. During the reporting period two kinetic models were employed: a comprehensive kinetic model of Dr. Li and co-workers (Yang et al., 2003) and a hydrocarbon selectivity model of Van der Laan and Beenackers (1998, 1999) The kinetic model of Yang et al. (2003) has 24 parameters (20 parameters for hydrocarbon formation, and 4 parameters for the water-gas-shift (WGS) reaction). Kinetic parameters for the WGS reaction and FTS synthesis were estimated first separately, and then simultaneously. The estimation of these kinetic parameters employed the Levenberg-Marquardt (LM) method and the trust-region reflective Newton large-scale (LS) method. A genetic algorithm (GA) was incorporated into estimation of parameters for FTS reaction to provide initial estimates of model parameters. All reaction rate constants and activation energies were found to be positive, but at the 95% confidence level the intervals were large. Agreement between predicted and experimental reaction rates has been fair to good. Light hydrocarbons are predicted fairly accurately, whereas the model underpredicts values of higher molecular weight

  12. Kinetics and Hydrodynamics of Silver Ion Flotation

    OpenAIRE

    2012-01-01

    This paper studies and determines the dispersion properties (Jg, Eg and Db), kinetics parameters and hydrodynamics of the process and its effect on the recovery of silver contained in spent diluted fixers by techniques of ion flotation in columns. The experimental results show silver recoveries of 97 % using sodium isopropyl xanthate (SIX) 0.06 g·L-1 and 0.04 g·L-1 of frother, at a Jg of 1.0 cm·s-1 and Jl of 0.72 cm·s-1. Xanthate-promoter combinations do not improve the separation; however, r...

  13. Parameter estimation in tree graph metabolic networks

    Directory of Open Access Journals (Sweden)

    Laura Astola

    2016-09-01

    Full Text Available We study the glycosylation processes that convert initially toxic substrates to nutritionally valuable metabolites in the flavonoid biosynthesis pathway of tomato (Solanum lycopersicum seedlings. To estimate the reaction rates we use ordinary differential equations (ODEs to model the enzyme kinetics. A popular choice is to use a system of linear ODEs with constant kinetic rates or to use Michaelis–Menten kinetics. In reality, the catalytic rates, which are affected among other factors by kinetic constants and enzyme concentrations, are changing in time and with the approaches just mentioned, this phenomenon cannot be described. Another problem is that, in general these kinetic coefficients are not always identifiable. A third problem is that, it is not precisely known which enzymes are catalyzing the observed glycosylation processes. With several hundred potential gene candidates, experimental validation using purified target proteins is expensive and time consuming. We aim at reducing this task via mathematical modeling to allow for the pre-selection of most potential gene candidates. In this article we discuss a fast and relatively simple approach to estimate time varying kinetic rates, with three favorable properties: firstly, it allows for identifiable estimation of time dependent parameters in networks with a tree-like structure. Secondly, it is relatively fast compared to usually applied methods that estimate the model derivatives together with the network parameters. Thirdly, by combining the metabolite concentration data with a corresponding microarray data, it can help in detecting the genes related to the enzymatic processes. By comparing the estimated time dynamics of the catalytic rates with time series gene expression data we may assess potential candidate genes behind enzymatic reactions. As an example, we show how to apply this method to select prominent glycosyltransferase genes in tomato seedlings.

  14. Electrochemical kinetics of gold dissolving in alkaline thiourea solution

    Institute of Scientific and Technical Information of China (English)

    CHAI Li-yuan; WANG Yun-yan

    2006-01-01

    Kinetic parameters of the electrode reactions were measured by investigating steady-state current-potential behaviors. The results show that the apparent transfer coefficient of anodic process is 0.058 2, diffusion coefficient of thiourea gold complex is 6.04 × 10-6 cm2/s,anodic reaction order of thiourea is 2. 018 3, and anodic reaction order of OH- is 0. 016 6. The theoretical kinetics equation of gold dissolving in alkaline thiourea solution is deduced,which indicates that anodic reaction order of thiourea is 2, and anodic reaction order of OH- is 0. The theoretical values of the kinetic parameters are consistent with experimental values very well. The correctness of the mechanism is further demonstrated using apparent transfer coefficient according to the electrochemical dynamic equation of multi-electron reaction.

  15. Modeling Biodegradation Kinetics on Benzene and Toluene and Their Mixture

    Directory of Open Access Journals (Sweden)

    Aparecido N. Módenes

    2007-10-01

    Full Text Available The objective of this work was to model the biodegradation kinetics of toxic compounds toluene and benzene as pure substrates and in a mixture. As a control, Monod and Andrews models were used. To predict substrates interactions, more sophisticated models of inhibition and competition, and SKIP (sum kinetics interactions parameters model were applied. The models evaluation was performed based on the experimental data from Pseudomonas putida F1 activities published in the literature. In parameter identification procedure, the global method of particle swarm optimization (PSO was applied. The simulation results show that the better description of the biodegradation process of pure toxic substrate can be achieved by Andrews' model. The biodegradation process of a mixture of toxic substrates is modeled the best when modified competitive inhibition and SKIP models are used. The developed software can be used as a toolbox of a kinetics model catalogue of industrial wastewater treatment for process design and optimization.

  16. Enzyme kinetics in drug metabolism: fundamentals and applications.

    Science.gov (United States)

    Nagar, Swati; Argikar, Upendra A; Tweedie, Donald J

    2014-01-01

    Enzymes are protein catalysts that lower the energy barrier for a reaction and speed the rate of a chemical change. The kinetics of reactions catalyzed by enzymes, as well as several mechanisms underlying the kinetics, have been comprehensively studied and written in textbooks (1, 2). The importance of quantitative evaluation of enzymatic processes has been recognized in many fields of study, including biochemistry, molecular biology, and pharmaceutical sciences to name a few. In pharmaceutical sciences, the applications of enzyme kinetics range from hit finding efforts for new chemical entities on a pharmacological target to concentration effect relationships to large-scale biosynthesis. The study of the science of drug metabolism has two principal concepts-rate and extent. While understanding disposition pathways and identification of metabolites provides an insight into the extent of metabolism, kinetics of depletion of substrates (endogenous or exogenous) and formation of metabolites deals with the rate of metabolism. The current textbook specifically focuses on kinetics of drug-metabolizing enzymes, detailing specific enzyme classes, and discusses kinetics as they apply to drug transporters. This textbook also outlines additional factors that contribute to the kinetics of reactions catalyzed by these proteins such as variability in isoforms (pharmacogenomics) and experimental factors including key concepts such as alterations of substrate concentrations due to binding. Applications of these approaches in predicting kinetic parameters and alternative approaches for enzymes (systems biology) and transporters are also discussed. The final section focuses on real-life examples (case studies) to try and exemplify the applications of enzyme kinetic principles. This chapter provides a brief overview outlining some key concepts within each of the sections and the chapters within this textbook.

  17. Utilization of Integrated Michaelis-Menten Equation to Determine Kinetic Constants

    Science.gov (United States)

    Bezerra, Rui M. F.; Dias, Albino A.

    2007-01-01

    Students of biochemistry and related biosciences are urged to solve problems where kinetic parameters are calculated from initial rates obtained at different substrate concentrations. Troubles begin when they go to the laboratory to perform kinetic experiments and realize that usual laboratory instruments do not measure initial rates but only…

  18. Measurement of Enzyme Kinetics by Use of a Blood Glucometer: Hydrolysis of Sucrose and Lactose

    Science.gov (United States)

    Heinzerling, Peter; Schrader, Frank; Schanze, Sascha

    2012-01-01

    An alternative analytical method for measuring the kinetic parameters of the enzymes invertase and lactase is described. Invertase hydrolyzes sucrose to glucose and fructose and lactase hydrolyzes lactose to glucose and galactose. In most enzyme kinetics studies, photometric methods or test strips are used to quantify the derivates of the…

  19. STUDY ON THE PHASE TRANSITION KINETICS OF THERMOTROPIC LIQUID CRYSTALLINE AROMATIC-ALIPHATIC COPOLYESTER

    Institute of Scientific and Technical Information of China (English)

    LI Minhui; WANG Xiaogong; LIU Deshan; ZHOU Qixiang

    1991-01-01

    The phase transition kinetics of thermotropic liquid crystalline aromatic-aliphatic regular copolyester:(X) were studied by DSC. By means of Kissinger's method the kinetic equation and parameters including activation energy, rate order and preexponential factor for phase transition from nematic to isotropic were obtained. The activation energy from crystal to nematic was also presented.

  20. Utilization of Integrated Michaelis-Menten Equation to Determine Kinetic Constants

    Science.gov (United States)

    Bezerra, Rui M. F.; Dias, Albino A.

    2007-01-01

    Students of biochemistry and related biosciences are urged to solve problems where kinetic parameters are calculated from initial rates obtained at different substrate concentrations. Troubles begin when they go to the laboratory to perform kinetic experiments and realize that usual laboratory instruments do not measure initial rates but only…