Sample records for obtain kinetic parameters

  1. Model-based analysis of coupled equilibrium-kinetic processes: indirect kinetic studies of thermodynamic parameters using the dynamic data.

    PubMed

    Emami, Fereshteh; Maeder, Marcel; Abdollahi, Hamid

    2015-05-07

    Thermodynamic studies of equilibrium chemical reactions linked with kinetic procedures are mostly impossible by traditional approaches. In this work, the new concept of generalized kinetic study of thermodynamic parameters is introduced for dynamic data. The examples of equilibria intertwined with kinetic chemical mechanisms include molecular charge transfer complex formation reactions, pH-dependent degradation of chemical compounds and tautomerization kinetics in micellar solutions. Model-based global analysis with the possibility of calculating and embedding the equilibrium and kinetic parameters into the fitting algorithm has allowed the complete analysis of the complex reaction mechanisms. After the fitting process, the optimal equilibrium and kinetic parameters together with an estimate of their standard deviations have been obtained. This work opens up a promising new avenue for obtaining equilibrium constants through the kinetic data analysis for the kinetic reactions that involve equilibrium processes.

  2. qPIPSA: Relating enzymatic kinetic parameters and interaction fields

    PubMed Central

    Gabdoulline, Razif R; Stein, Matthias; Wade, Rebecca C

    2007-01-01

    Background The simulation of metabolic networks in quantitative systems biology requires the assignment of enzymatic kinetic parameters. Experimentally determined values are often not available and therefore computational methods to estimate these parameters are needed. It is possible to use the three-dimensional structure of an enzyme to perform simulations of a reaction and derive kinetic parameters. However, this is computationally demanding and requires detailed knowledge of the enzyme mechanism. We have therefore sought to develop a general, simple and computationally efficient procedure to relate protein structural information to enzymatic kinetic parameters that allows consistency between the kinetic and structural information to be checked and estimation of kinetic constants for structurally and mechanistically similar enzymes. Results We describe qPIPSA: quantitative Protein Interaction Property Similarity Analysis. In this analysis, molecular interaction fields, for example, electrostatic potentials, are computed from the enzyme structures. Differences in molecular interaction fields between enzymes are then related to the ratios of their kinetic parameters. This procedure can be used to estimate unknown kinetic parameters when enzyme structural information is available and kinetic parameters have been measured for related enzymes or were obtained under different conditions. The detailed interaction of the enzyme with substrate or cofactors is not modeled and is assumed to be similar for all the proteins compared. The protein structure modeling protocol employed ensures that differences between models reflect genuine differences between the protein sequences, rather than random fluctuations in protein structure. Conclusion Provided that the experimental conditions and the protein structural models refer to the same protein state or conformation, correlations between interaction fields and kinetic parameters can be established for sets of related enzymes

  3. Estimation of kinetic parameters from list-mode data using an indirect apporach

    NASA Astrophysics Data System (ADS)

    Ortiz, Joseph Christian

    This dissertation explores the possibility of using an imaging approach to model classical pharmacokinetic (PK) problems. The kinetic parameters which describe the uptake rates of a drug within a biological system, are parameters of interest. Knowledge of the drug uptake in a system is useful in expediting the drug development process, as well as providing a dosage regimen for patients. Traditionally, the uptake rate of a drug in a system is obtained via sampling the concentration of the drug in a central compartment, usually the blood, and fitting the data to a curve. In a system consisting of multiple compartments, the number of kinetic parameters is proportional to the number of compartments, and in classical PK experiments, the number of identifiable parameters is less than the total number of parameters. Using an imaging approach to model classical PK problems, the support region of each compartment within the system will be exactly known, and all the kinetic parameters are uniquely identifiable. To solve for the kinetic parameters, an indirect approach, which is a two part process, was used. First the compartmental activity was obtained from data, and next the kinetic parameters were estimated. The novel aspect of the research is using listmode data to obtain the activity curves from a system as opposed to a traditional binned approach. Using techniques from information theoretic learning, particularly kernel density estimation, a non-parametric probability density function for the voltage outputs on each photo-multiplier tube, for each event, was generated on the fly, which was used in a least squares optimization routine to estimate the compartmental activity. The estimability of the activity curves for varying noise levels as well as time sample densities were explored. Once an estimate for the activity was obtained, the kinetic parameters were obtained using multiple cost functions, and the compared to each other using the mean squared error as the figure

  4. Estimation of beech pyrolysis kinetic parameters by Shuffled Complex Evolution.

    PubMed

    Ding, Yanming; Wang, Changjian; Chaos, Marcos; Chen, Ruiyu; Lu, Shouxiang

    2016-01-01

    The pyrolysis kinetics of a typical biomass energy feedstock, beech, was investigated based on thermogravimetric analysis over a wide heating rate range from 5K/min to 80K/min. A three-component (corresponding to hemicellulose, cellulose and lignin) parallel decomposition reaction scheme was applied to describe the experimental data. The resulting kinetic reaction model was coupled to an evolutionary optimization algorithm (Shuffled Complex Evolution, SCE) to obtain model parameters. To the authors' knowledge, this is the first study in which SCE has been used in the context of thermogravimetry. The kinetic parameters were simultaneously optimized against data for 10, 20 and 60K/min heating rates, providing excellent fits to experimental data. Furthermore, it was shown that the optimized parameters were applicable to heating rates (5 and 80K/min) beyond those used to generate them. Finally, the predicted results based on optimized parameters were contrasted with those based on the literature. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Determination of Kinetic Parameters for the Thermal Decomposition of Parthenium hysterophorus

    NASA Astrophysics Data System (ADS)

    Dhaundiyal, Alok; Singh, Suraj B.; Hanon, Muammel M.; Rawat, Rekha

    2018-02-01

    A kinetic study of pyrolysis process of Parthenium hysterophorous is carried out by using thermogravimetric analysis (TGA) equipment. The present study investigates the thermal degradation and determination of the kinetic parameters such as activation E and the frequency factor A using model-free methods given by Flynn Wall and Ozawa (FWO), Kissinger-Akahira-Sonuse (KAS) and Kissinger, and model-fitting (Coats Redfern). The results derived from thermal decomposition process demarcate decomposition of Parthenium hysterophorous among the three main stages, such as dehydration, active and passive pyrolysis. It is shown through DTG thermograms that the increase in the heating rate caused temperature peaks at maximum weight loss rate to shift towards higher temperature regime. The results are compared with Coats Redfern (Integral method) and experimental results have shown that values of kinetic parameters obtained from model-free methods are in good agreement. Whereas the results obtained through Coats Redfern model at different heating rates are not promising, however, the diffusion models provided the good fitting with the experimental data.

  6. Effect of experimental and sample factors on dehydration kinetics of mildronate dihydrate: mechanism of dehydration and determination of kinetic parameters.

    PubMed

    Bērziņš, Agris; Actiņš, Andris

    2014-06-01

    The dehydration kinetics of mildronate dihydrate [3-(1,1,1-trimethylhydrazin-1-ium-2-yl)propionate dihydrate] was analyzed in isothermal and nonisothermal modes. The particle size, sample preparation and storage, sample weight, nitrogen flow rate, relative humidity, and sample history were varied in order to evaluate the effect of these factors and to more accurately interpret the data obtained from such analysis. It was determined that comparable kinetic parameters can be obtained in both isothermal and nonisothermal mode. However, dehydration activation energy values obtained in nonisothermal mode showed variation with conversion degree because of different rate-limiting step energy at higher temperature. Moreover, carrying out experiments in this mode required consideration of additional experimental complications. Our study of the different sample and experimental factor effect revealed information about changes of the dehydration rate-limiting step energy, variable contribution from different rate limiting steps, as well as clarified the dehydration mechanism. Procedures for convenient and fast determination of dehydration kinetic parameters were offered. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

  7. Parameter Balancing in Kinetic Models of Cell Metabolism†

    PubMed Central

    2010-01-01

    Kinetic modeling of metabolic pathways has become a major field of systems biology. It combines structural information about metabolic pathways with quantitative enzymatic rate laws. Some of the kinetic constants needed for a model could be collected from ever-growing literature and public web resources, but they are often incomplete, incompatible, or simply not available. We address this lack of information by parameter balancing, a method to complete given sets of kinetic constants. Based on Bayesian parameter estimation, it exploits the thermodynamic dependencies among different biochemical quantities to guess realistic model parameters from available kinetic data. Our algorithm accounts for varying measurement conditions in the input data (pH value and temperature). It can process kinetic constants and state-dependent quantities such as metabolite concentrations or chemical potentials, and uses prior distributions and data augmentation to keep the estimated quantities within plausible ranges. An online service and free software for parameter balancing with models provided in SBML format (Systems Biology Markup Language) is accessible at www.semanticsbml.org. We demonstrate its practical use with a small model of the phosphofructokinase reaction and discuss its possible applications and limitations. In the future, parameter balancing could become an important routine step in the kinetic modeling of large metabolic networks. PMID:21038890

  8. Determining Kinetic Parameters for Isothermal Crystallization of Glasses

    NASA Technical Reports Server (NTRS)

    Ray, C. S.; Zhang, T.; Reis, S. T.; Brow, R. K.

    2006-01-01

    Non-isothermal crystallization techniques are frequently used to determine the kinetic parameters for crystallization in glasses. These techniques are experimentally simple and quick compared to the isothermal techniques. However, the analytical models used for non-isothermal data analysis, originally developed for describing isothermal transformation kinetics, are fundamentally flawed. The present paper describes a technique for determining the kinetic parameters for isothermal crystallization in glasses, which eliminates most of the common problems that generally make the studies of isothermal crystallization laborious and time consuming. In this technique, the volume fraction of glass that is crystallized as a function of time during an isothermal hold was determined using differential thermal analysis (DTA). The crystallization parameters for the lithium-disilicate (Li2O.2SiO2) model glass were first determined and compared to the same parameters determined by other techniques to establish the accuracy and usefulness of the present technique. This technique was then used to describe the crystallization kinetics of a complex Ca-Sr-Zn-silicate glass developed for sealing solid oxide fuel cells.

  9. Kinetics of bacterial phospholipase C activity at micellar interfaces: effect of substrate aggregate microstructure and a model for the kinetic parameters.

    PubMed

    Singh, Jasmeet; Ranganathan, Radha; Hajdu, Joseph

    2008-12-25

    Activity at micellar interfaces of bacterial phospholipase C from Bacillus cereus on phospholipids solubilized in micelles was investigated with the goal of elucidating the role of the interface microstructure and developing further an existing kinetic model. Enzyme kinetics and physicochemical characterization of model substrate aggregates were combined, thus enabling the interpretation of kinetics in the context of the interface. Substrates were diacylphosphatidylcholine of different acyl chain lengths in the form of mixed micelles with dodecyldimethylammoniopropanesulfonate. An early kinetic model, reformulated to reflect the interfacial nature of the kinetics, was applied to the kinetic data. A better method of data treatment is proposed, use of which makes the presence of microstructure effects quite transparent. Models for enzyme-micelle binding and enzyme-lipid binding are developed, and expressions incorporating the microstructural properties are derived for the enzyme-micelle dissociation constant K(s) and the interface Michaelis-Menten constant, K(M). Use of these expressions in the interface kinetic model brings excellent agreement between the kinetic data and the model. Numerical values for the thermodynamic and kinetic parameters are determined. Enzyme-lipid binding is found to be an activated process with an acyl chain length dependent free energy of activation that decreases with micelle lipid molar fraction with a coefficient of about -15RT and correlates with the tightness of molecular packing in the substrate aggregate. Thus, the physical insight obtained includes a model for the kinetic parameters that shows that these parameters depend on the substrate concentration and acyl chain length of the lipid. Enzyme-micelle binding is indicated to be hydrophobic and solvent mediated with a dissociation constant of 1.2 mM.

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

    NASA Astrophysics Data System (ADS)

    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.

  11. Kinetic Parameter Measurements in the MINERVE Reactor

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

  15. Parameter estimation of kinetic models from metabolic profiles: two-phase dynamic decoupling method.

    PubMed

    Jia, Gengjie; Stephanopoulos, Gregory N; Gunawan, Rudiyanto

    2011-07-15

    Time-series measurements of metabolite concentration have become increasingly more common, providing data for building kinetic models of metabolic networks using ordinary differential equations (ODEs). In practice, however, such time-course data are usually incomplete and noisy, and the estimation of kinetic parameters from these data is challenging. Practical limitations due to data and computational aspects, such as solving stiff ODEs and finding global optimal solution to the estimation problem, give motivations to develop a new estimation procedure that can circumvent some of these constraints. In this work, an incremental and iterative parameter estimation method is proposed that combines and iterates between two estimation phases. One phase involves a decoupling method, in which a subset of model parameters that are associated with measured metabolites, are estimated using the minimization of slope errors. Another phase follows, in which the ODE model is solved one equation at a time and the remaining model parameters are obtained by minimizing concentration errors. The performance of this two-phase method was tested on a generic branched metabolic pathway and the glycolytic pathway of Lactococcus lactis. The results showed that the method is efficient in getting accurate parameter estimates, even when some information is missing.

  16. Estimation of fundamental kinetic parameters of polyhydroxybutyrate fermentation process of Azohydromonas australica using statistical approach of media optimization.

    PubMed

    Gahlawat, Geeta; Srivastava, Ashok K

    2012-11-01

    Polyhydroxybutyrate or PHB is a biodegradable and biocompatible thermoplastic with many interesting applications in medicine, food packaging, and tissue engineering materials. The present study deals with the enhanced production of PHB by Azohydromonas australica using sucrose and the estimation of fundamental kinetic parameters of PHB fermentation process. The preliminary culture growth inhibition studies were followed by statistical optimization of medium recipe using response surface methodology to increase the PHB production. Later on batch cultivation in a 7-L bioreactor was attempted using optimum concentration of medium components (process variables) obtained from statistical design to identify the batch growth and product kinetics parameters of PHB fermentation. A. australica exhibited a maximum biomass and PHB concentration of 8.71 and 6.24 g/L, respectively in bioreactor with an overall PHB production rate of 0.75 g/h. Bioreactor cultivation studies demonstrated that the specific biomass and PHB yield on sucrose was 0.37 and 0.29 g/g, respectively. The kinetic parameters obtained in the present investigation would be used in the development of a batch kinetic mathematical model for PHB production which will serve as launching pad for further process optimization studies, e.g., design of several bioreactor cultivation strategies to further enhance the biopolymer production.

  17. Improved Parameter-Estimation With MRI-Constrained PET Kinetic Modeling: A Simulation Study

    NASA Astrophysics Data System (ADS)

    Erlandsson, Kjell; Liljeroth, Maria; Atkinson, David; Arridge, Simon; Ourselin, Sebastien; Hutton, Brian F.

    2016-10-01

    Kinetic analysis can be applied both to dynamic PET and dynamic contrast enhanced (DCE) MRI data. We have investigated the potential of MRI-constrained PET kinetic modeling using simulated [ 18F]2-FDG data for skeletal muscle. The volume of distribution, Ve, for the extra-vascular extra-cellular space (EES) is the link between the two models: It can be estimated by DCE-MRI, and then used to reduce the number of parameters to estimate in the PET model. We used a 3 tissue-compartment model with 5 rate constants (3TC5k), in order to distinguish between EES and the intra-cellular space (ICS). Time-activity curves were generated by simulation using the 3TC5k model for 3 different Ve values under basal and insulin stimulated conditions. Noise was added and the data were fitted with the 2TC3k model and with the 3TC5k model with and without Ve constraint. One hundred noise-realisations were generated at 4 different noise-levels. The results showed reductions in bias and variance with Ve constraint in the 3TC5k model. We calculated the parameter k3", representing the combined effect of glucose transport across the cellular membrane and phosphorylation, as an extra outcome measure. For k3", the average coefficient of variation was reduced from 52% to 9.7%, while for k3 in the standard 2TC3k model it was 3.4%. The accuracy of the parameters estimated with our new modeling approach depends on the accuracy of the assumed Ve value. In conclusion, we have shown that, by utilising information that could be obtained from DCE-MRI in the kinetic analysis of [ 18F]2-FDG-PET data, it is in principle possible to obtain better parameter estimates with a more complex model, which may provide additional information as compared to the standard model.

  18. Fast pyrolysis kinetics of alkali lignin: Evaluation of apparent rate parameters and product time evolution.

    PubMed

    Ojha, Deepak Kumar; Viju, Daniel; Vinu, R

    2017-10-01

    In this study, the apparent kinetics of fast pyrolysis of alkali lignin was evaluated by obtaining isothermal mass loss data in the timescale of 2-30s at 400-700°C in an analytical pyrolyzer. The data were analyzed using different reaction models to determine the rate constants and apparent rate parameters. First order and one dimensional diffusion models resulted in good fits with experimental data with apparent activation energy of 23kJmol -1 . Kinetic compensation effect was established using a large number of kinetic parameters reported in the literature for pyrolysis of different lignins. The time evolution of the major functional groups in the pyrolysate was analyzed using in situ Fourier transform infrared spectroscopy. Maximum production of the volatiles occurred around 10-12s. A clear transformation of guaiacols to phenol, catechol and their derivatives, and aromatic hydrocarbons was observed with increasing temperature. The plausible reaction steps involved in various transformations are discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Kinetic parameter estimation model for anaerobic co-digestion of waste activated sludge and microalgae.

    PubMed

    Lee, Eunyoung; Cumberbatch, Jewel; Wang, Meng; Zhang, Qiong

    2017-03-01

    Anaerobic co-digestion has a potential to improve biogas production, but limited kinetic information is available for co-digestion. This study introduced regression-based models to estimate the kinetic parameters for the co-digestion of microalgae and Waste Activated Sludge (WAS). The models were developed using the ratios of co-substrates and the kinetic parameters for the single substrate as indicators. The models were applied to the modified first-order kinetics and Monod model to determine the rate of hydrolysis and methanogenesis for the co-digestion. The results showed that the model using a hyperbola function was better for the estimation of the first-order kinetic coefficients, while the model using inverse tangent function closely estimated the Monod kinetic parameters. The models can be used for estimating kinetic parameters for not only microalgae-WAS co-digestion but also other substrates' co-digestion such as microalgae-swine manure and WAS-aquatic plants. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. 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

    PubMed Central

    Tosun, İsmail

    2012-01-01

    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 (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. PMID:22690177

  1. 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.

    PubMed

    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.

  2. Non-Isothermic Chemical Kinetics in the Undergraduate Laboratory: Arrhenius Parameters from Experiments with Hyperbolic Temperature Variation.

    ERIC Educational Resources Information Center

    Salvador, F.; And Others

    1984-01-01

    Describes a method which adapts itself to the characteristics of the kinetics of a chemical reaction in solution, enabling students to determine the Arrhenius parameters with satisfactory accuracy by means of a single non-isothermic experiment. Both activation energy and the preexponential factor values can be obtained by the method. (JN)

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

    PubMed

    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.

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

    PubMed

    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

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

    PubMed Central

    2013-01-01

    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 yield and identify potential

  6. Methods for Calibration of Prout-Tompkins Kinetics Parameters Using EZM Iteration and GLO

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wemhoff, A P; Burnham, A K; de Supinski, B

    2006-11-07

    This document contains information regarding the standard procedures used to calibrate chemical kinetics parameters for the extended Prout-Tompkins model to match experimental data. Two methods for calibration are mentioned: EZM calibration and GLO calibration. EZM calibration matches kinetics parameters to three data points, while GLO calibration slightly adjusts kinetic parameters to match multiple points. Information is provided regarding the theoretical approach and application procedure for both of these calibration algorithms. It is recommended that for the calibration process, the user begin with EZM calibration to provide a good estimate, and then fine-tune the parameters using GLO. Two examples have beenmore » provided to guide the reader through a general calibrating process.« less

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

    PubMed

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    PubMed Central

    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. PMID:26910830

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

    PubMed

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

    PubMed

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

    2018-02-05

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

  11. Dry mechanochemical synthesis of hydroxyapatites from DCPD and CaO: influence of instrumental parameters on the reaction kinetics.

    PubMed

    Mochales, Carolina; El Briak-BenAbdeslam, Hassane; Ginebra, Maria Pau; Terol, Alain; Planell, Josep A; Boudeville, Philippe

    2004-01-01

    Mechanochemistry is a possible route to synthesize calcium deficient hydroxyapatite (CDHA) with an expected molar calcium-to-phosphate (Ca/P) ratio +/-0.01. To optimize the experimental conditions of CDHA preparation from dicalcium phosphate dihydrate (DCPD) and calcium oxide by dry mechanosynthesis reaction, we performed the kinetic study varying some experimental parameters. This kinetic study was carried out with two different planetary ball mills (Retsch or Fritsch Instuments). Results obtained with the two mills led to the same conclusions although the values of the rate constants of DCPD disappearance and times for complete reaction were very different. Certainly, the origin of these differences was from the mills used, thus we investigated the influence of instrumental parameters such as the mass and the surface area of the balls or the rotation velocity on the mechanochemical reaction kinetics of DCPD with CaO. Results show that the DCPD reaction rate constant and the inverse of the time for complete disappearance of CaO both vary linearly with (i) the square of the rotation velocity, (ii) the square of eccentricity of the vial on the rotating disc and (iii) the product of the mass by the surface area of the balls. These observations comply with theoretical models developed for mechanical alloying. The consideration of these four parameters allows the transposition of experimental conditions from one mill to another or the comparison between results obtained with different planetary ball mills. These instrumental parameters have to be well described in papers concerning mechanochemistry or when grinding is an important stage in a process.

  12. Simultaneous versus sequential optimal experiment design for the identification of multi-parameter microbial growth kinetics as a function of temperature.

    PubMed

    Van Derlinden, E; Bernaerts, K; Van Impe, J F

    2010-05-21

    Optimal experiment design for parameter estimation (OED/PE) has become a popular tool for efficient and accurate estimation of kinetic model parameters. When the kinetic model under study encloses multiple parameters, different optimization strategies can be constructed. The most straightforward approach is to estimate all parameters simultaneously from one optimal experiment (single OED/PE strategy). However, due to the complexity of the optimization problem or the stringent limitations on the system's dynamics, the experimental information can be limited and parameter estimation convergence problems can arise. As an alternative, we propose to reduce the optimization problem to a series of two-parameter estimation problems, i.e., an optimal experiment is designed for a combination of two parameters while presuming the other parameters known. Two different approaches can be followed: (i) all two-parameter optimal experiments are designed based on identical initial parameter estimates and parameters are estimated simultaneously from all resulting experimental data (global OED/PE strategy), and (ii) optimal experiments are calculated and implemented sequentially whereby the parameter values are updated intermediately (sequential OED/PE strategy). This work exploits OED/PE for the identification of the Cardinal Temperature Model with Inflection (CTMI) (Rosso et al., 1993). This kinetic model describes the effect of temperature on the microbial growth rate and encloses four parameters. The three OED/PE strategies are considered and the impact of the OED/PE design strategy on the accuracy of the CTMI parameter estimation is evaluated. Based on a simulation study, it is observed that the parameter values derived from the sequential approach deviate more from the true parameters than the single and global strategy estimates. The single and global OED/PE strategies are further compared based on experimental data obtained from design implementation in a bioreactor

  13. Kinetic and temporospatial gait parameters in a heterogeneous group of dogs.

    PubMed

    Kano, Washington T; Rahal, Sheila C; Agostinho, Felipe S; Mesquita, Luciane R; Santos, Rogerio R; Monteiro, Frederico O B; Castilho, Maira S; Melchert, Alessandra

    2016-01-04

    A prime concern of the gait analysis in a heterogeneous group of dogs is the potential influence of factors such as individual body size, body mass, type of gait, and velocity. Thus, this study aimed to evaluate in a heterogeneous group of dogs a possible correlation of the stride frequency with kinetic and temporospatial variables, as well as the percentage of body weight distribution (%BWD), and compare symmetry index (SI) between trotting and walking dogs. Twenty-nine clinically healthy dogs moving in a controlled velocity were used. The dogs were organized into two groups based on duty factor. Group 1 comprised 15 walking dogs, aged from 9 months to 8 years and weighing about 22.3 kg. Group 2 had 14 trotting dogs, aged from 1 to 6 years and weighing about 6.5 kg. The kinetic data and temporospatial parameters were obtained using a pressure-sensing walkway. The velocity was 0.9-1.1 m/s. The peak vertical force (PVF), vertical impulse (VI), gait cycle time, stance time, swing time, stride length, and percentages of body weight distribution among the four limbs were determined. For each variable, the SIs were calculated. Pearson's coefficient was used to evaluate correlation between stride frequency and other variables, initially in each group and after including all animals. Except for the %BWD (approximately 60% for the forelimbs and 40% for the hind limbs), all other parameters differed between groups. Considering each Group individually a strong correlation was observed for most of the temporospatial parameters, but no significant correlation occurred between stride frequency and PVF, and stride frequency and %BWD. However, including all dogs a strong correlation was observed in all temporospatial parameters, and moderate correlation between stride frequency and VI, and weak correlation between stride frequency and PVF. There was no correlation between stride frequency and %BWD. Groups 1 and 2 did not differ statistically in SIs. In a heterogeneous group of

  14. Blind identification of the kinetic parameters in three-compartment models

    NASA Astrophysics Data System (ADS)

    Riabkov, Dmitri Y.; Di Bella, Edward V. R.

    2004-03-01

    Quantified knowledge of tissue kinetic parameters in the regions of the brain and other organs can offer information useful in clinical and research applications. Dynamic medical imaging with injection of radioactive or paramagnetic tracer can be used for this measurement. The kinetics of some widely used tracers such as [18F]2-fluoro-2-deoxy-D-glucose can be described by a three-compartment physiological model. The kinetic parameters of the tissue can be estimated from dynamically acquired images. Feasibility of estimation by blind identification, which does not require knowledge of the blood input, is considered analytically and numerically in this work for the three-compartment type of tissue response. The non-uniqueness of the two-region case for blind identification of kinetic parameters in three-compartment model is shown; at least three regions are needed for the blind identification to be unique. Numerical results for the accuracy of these blind identification methods in different conditions were considered. Both a separable variables least-squares (SLS) approach and an eigenvector-based algorithm for multichannel blind deconvolution approach were used. The latter showed poor accuracy. Modifications for non-uniform time sampling were also developed. Also, another method which uses a model for the blood input was compared. Results for the macroparameter K, which reflects the metabolic rate of glucose usage, using three regions with noise showed comparable accuracy for the separable variables least squares method and for the input model-based method, and slightly worse accuracy for SLS with the non-uniform sampling modification.

  15. Novel methods to estimate the enantiomeric ratio and the kinetic parameters of enantiospecific enzymatic reactions.

    PubMed

    Machado, G D.C.; Paiva, L M.C.; Pinto, G F.; Oestreicher, E G.

    2001-03-08

    1The Enantiomeric Ratio (E) of the enzyme, acting as specific catalysts in resolution of enantiomers, is an important parameter in the quantitative description of these chiral resolution processes. In the present work, two novel methods hereby called Method I and II, for estimating E and the kinetic parameters Km and Vm of enantiomers were developed. These methods are based upon initial rate (v) measurements using different concentrations of enantiomeric mixtures (C) with several molar fractions of the substrate (x). Both methods were tested using simulated "experimental data" and actual experimental data. Method I is easier to use than Method II but requires that one of the enantiomers is available in pure form. Method II, besides not requiring the enantiomers in pure form shown better results, as indicated by the magnitude of the standard errors of estimates. The theoretical predictions were experimentally confirmed by using the oxidation of 2-butanol and 2-pentanol catalyzed by Thermoanaerobium brockii alcohol dehydrogenase as reaction models. The parameters E, Km and Vm were estimated by Methods I and II with precision and were not significantly different from those obtained experimentally by direct estimation of E from the kinetic parameters of each enantiomer available in pure form.

  16. Simultaneous determination of thermodynamic and kinetic parameters of aminopolycarbonate complexes of cobalt(II) and nickel(II) based on isothermal titration calorimetry data.

    PubMed

    Tesmar, Aleksandra; Wyrzykowski, Dariusz; Muñoz, Eva; Pilarski, Bogusław; Pranczk, Joanna; Jacewicz, Dagmara; Chmurzyński, Lech

    2017-04-01

    The influence of the different side chain residues on the thermodynamic and kinetic parameters for complexation reactions of the Co 2 + and Ni 2 + ions has been investigated by using the isothermal titration calorimetry (ITC) technique supported by potentiometric titration data. The study was concerned with the 2 common tripodal aminocarboxylate ligands, namely, nitrilotriacetic acid and N-(2-hydroxyethyl) iminodiacetic acid. Calorimetric measurements (ITC) were run in the 2-(N-morpholino)ethanesulfonic acid hydrate (2-(N-morpholino) ethanesulfonic acid), piperazine-N,N'-bis(2-ethanesulfonic acid), and dimethylarsenic acid buffers (0.1 mol L -1 , pH 6) at 298.15 K. The quantification of the metal-buffer interactions and their incorporation into the ITC data analysis enabled to obtain the pH-independent and buffer-independent thermodynamic parameters (K, ΔG, ΔH, and ΔS) for the reactions under study. Furthermore, the kinITC method was applied to obtain kinetic information on complexation reactions from the ITC data. Correlations, based on kinetic and thermodynamic data, between the kinetics of formation of Co 2 + and Ni 2 + complexes and their thermodynamic stabilities are discussed. Copyright © 2016 John Wiley & Sons, Ltd.

  17. Estimation of kinetics parameters for the adsorption of human serum albumin onto hydroxyapatite-modified silver electrodes by piezoelectric quartz crystal impedance analysis.

    PubMed

    Tian, Lu; Wei, Wan-Zhi; Mao, You-An

    2004-04-01

    The adsorption of human serum albumin onto hydroxyapatite-modified silver electrodes has been in situ investigated by utilizing the piezoelectric quartz crystal impedance technique. The changes of equivalent circuit parameters were used to interpret the adsorption process. A kinetic model of two consecutive steps was derived to describe the process and compared with a first-order kinetic model by using residual analysis. The experimental data of frequency shift fitted to the model and kinetics parameters, k1, k2, psi1, psi2 and qr, were obtained. All fitted results were in reasonable agreement with the corresponding experimental results. Two adsorption constants (7.19 kJ mol(-1) and 22.89 kJ mol(-1)) were calculated according to the Arrhenius formula.

  18. Application of lab derived kinetic biodegradation parameters at the field scale

    NASA Astrophysics Data System (ADS)

    Schirmer, M.; Barker, J. F.; Butler, B. J.; Frind, E. O.

    2003-04-01

    Estimating the intrinsic remediation potential of an aquifer typically requires the accurate assessment of the biodegradation kinetics, the level of available electron acceptors and the flow field. Zero- and first-order degradation rates derived at the laboratory scale generally overpredict the rate of biodegradation when applied to the field scale, because limited electron acceptor availability and microbial growth are typically not considered. On the other hand, field estimated zero- and first-order rates are often not suitable to forecast plume development because they may be an oversimplification of the processes at the field scale and ignore several key processes, phenomena and characteristics of the aquifer. This study uses the numerical model BIO3D to link the laboratory and field scale by applying laboratory derived Monod kinetic degradation parameters to simulate a dissolved gasoline field experiment at Canadian Forces Base (CFB) Borden. All additional input parameters were derived from laboratory and field measurements or taken from the literature. The simulated results match the experimental results reasonably well without having to calibrate the model. An extensive sensitivity analysis was performed to estimate the influence of the most uncertain input parameters and to define the key controlling factors at the field scale. It is shown that the most uncertain input parameters have only a minor influence on the simulation results. Furthermore it is shown that the flow field, the amount of electron acceptor (oxygen) available and the Monod kinetic parameters have a significant influence on the simulated results. Under the field conditions modelled and the assumptions made for the simulations, it can be concluded that laboratory derived Monod kinetic parameters can adequately describe field scale degradation processes, if all controlling factors are incorporated in the field scale modelling that are not necessarily observed at the lab scale. In this way

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Geslot, Benoit; Pepino, Alexandra; Blaise, Patrick

    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 onesmore » 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)« less

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

    PubMed

    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. Copyright © 2014. Published by Elsevier B.V.

  1. Effect of heating rate on kinetic parameters of β-irradiated Li2B4O7:Cu,Ag,P in TSL measurements

    NASA Astrophysics Data System (ADS)

    Türkler Ege, A.; Ekdal, E.; Karali, T.; Can, N.; Prokic, M.

    2007-03-01

    The effect of heating rate on the thermally stimulated luminescence (TSL) emission due to the temperature lag (TLA) between the TSL material and the heating element has been investigated using Li2B4O7:Cu,Ag,P dosimetric materials. The TLA becomes significant when the material is heated at high heating rates. TSL glow curves of Li2B4O7:Cu,Ag,P material showed two main peaks after β-irradiation. The kinetic parameters, namely activation energy (E) and frequency factor (s) associated with the high temperature main peak of Li2B4O7:Cu,Ag,P were determined using the method of various heating rates (VHR), in which heating rates from 1 to 40 K s-1 were used. It is assumed that non-ideal heat transfer between the heater and the material may cause significant inconsistency of kinetic parameter values obtained with different methods. The effect of TLA on kinetic parameters of the dosimeter was examined.

  2. One-step global parameter estimation of kinetic inactivation parameters for Bacillus sporothermodurans spores under static and dynamic thermal processes.

    PubMed

    Cattani, F; Dolan, K D; Oliveira, S D; Mishra, D K; Ferreira, C A S; Periago, P M; Aznar, A; Fernandez, P S; Valdramidis, V P

    2016-11-01

    Bacillus sporothermodurans produces highly heat-resistant endospores, that can survive under ultra-high temperature. High heat-resistant sporeforming bacteria are one of the main causes for spoilage and safety of low-acid foods. They can be used as indicators or surrogates to establish the minimum requirements for heat processes, but it is necessary to understand their thermal inactivation kinetics. The aim of the present work was to study the inactivation kinetics under both static and dynamic conditions in a vegetable soup. Ordinary least squares one-step regression and sequential procedures were applied for estimating these parameters. Results showed that multiple dynamic heating profiles, when analyzed simultaneously, can be used to accurately estimate the kinetic parameters while significantly reducing estimation errors and data collection. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

    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.

  4. Improved accuracy and precision of tracer kinetic parameters by joint fitting to variable flip angle and dynamic contrast enhanced MRI data.

    PubMed

    Dickie, Ben R; Banerji, Anita; Kershaw, Lucy E; McPartlin, Andrew; Choudhury, Ananya; West, Catharine M; Rose, Chris J

    2016-10-01

    To improve the accuracy and precision of tracer kinetic model parameter estimates for use in dynamic contrast enhanced (DCE) MRI studies of solid tumors. Quantitative DCE-MRI requires an estimate of precontrast T1 , which is obtained prior to fitting a tracer kinetic model. As T1 mapping and tracer kinetic signal models are both a function of precontrast T1 it was hypothesized that its joint estimation would improve the accuracy and precision of both precontrast T1 and tracer kinetic model parameters. Accuracy and/or precision of two-compartment exchange model (2CXM) parameters were evaluated for standard and joint fitting methods in well-controlled synthetic data and for 36 bladder cancer patients. Methods were compared under a number of experimental conditions. In synthetic data, joint estimation led to statistically significant improvements in the accuracy of estimated parameters in 30 of 42 conditions (improvements between 1.8% and 49%). Reduced accuracy was observed in 7 of the remaining 12 conditions. Significant improvements in precision were observed in 35 of 42 conditions (between 4.7% and 50%). In clinical data, significant improvements in precision were observed in 18 of 21 conditions (between 4.6% and 38%). Accuracy and precision of DCE-MRI parameter estimates are improved when signal models are fit jointly rather than sequentially. Magn Reson Med 76:1270-1281, 2016. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    McKenzie, IV, George Espy; Goda, Joetta Marie; Grove, Travis Justin

    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).

  6. Parameters and kinetics of olive mill wastewater dephenolization by immobilized Rhodotorula glutinis cells.

    PubMed

    Bozkoyunlu, Gaye; Takaç, Serpil

    2014-01-01

    Olive mill wastewater (OMW) with total phenol (TP) concentration range of 300-1200 mg/L was treated with alginate-immobilized Rhodotorula glutinis cells in batch system. The effects of pellet properties (diameter, alginate concentration and cell loading (CL)) and operational parameters (initial TP concentration, agitation rate and reusability of pellets) on dephenolization of OMW were studied. Up to 87% dephenolization was obtained after 120 h biodegradations. The utilization number of pellets increased with the addition of calcium ions into the biodegradation medium. The overall effectiveness factors calculated for different conditions showed that diffusional limitations arising from pellet size and pellet composition could be neglected. Mass transfer limitations appeared to be more effective at high substrate concentrations and low agitation rates. The parameters of logistic model for growth kinetics of R. glutinis in OMW were estimated at different initial phenol concentrations of OMW by curve-fitting of experimental data with the model.

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

    NASA Astrophysics Data System (ADS)

    Zhang, Hong; Zuo, Ran; Zhang, Guoyi

    2017-11-01

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

  8. Intrinsic kinetic parameters of substrate utilization by immobilized anaerobic sludge.

    PubMed

    Zaiat, M; Vieira, L G; Foresti, E

    1997-01-20

    This article presents a method for evaluating the intrinsic kinetic parameters of the specific substrate utilization rate (r) equation and discusses the results obtained for anaerobic sludge-bed samples taken from a horizontal-flow anaerobic immobilized sludge (HAIS) reactor. This method utilizes a differential reactor filled with polyurethane foam matrices containing immobilized anaerobic sludge which is subjected to a range of feeding substrate flow rates. The range of liquid superficial velocities thus obtained are used for generating data of observed specific substrate utilization rates (r(obs)) under a diversity of external mass transfer resistance conditions. The r(obs) curves are then adjusted to permit their extrapolation for the condition of no external mass transfer resistance, and the values determined are used as a test for the condition of absence of limitation of internal mass transfer. The intrinsic parameters r(max), the maximum specific substrate utilization rate, and K(s), the half-velocity coefficient, are evaluated from the r values under no external mass transfer resistance and no internal mass transfer limitation. The application of such a method for anaerobic sludge immobilized in polyurethane foam particles treating a glucose substrate at 30 degrees C resulted in intrinsic r(max) and K(s), respectively, of 0.330 mg chemical oxygen demand (COD) . mg(-1) volatile suspended solids (VSS) . h(-1) and 72 mg COD . L(-1). In comparison with the values found in the literature, intrinsic r(max) is significantly high and intrinsic K(s) is relatively low. (c) 1997 John Wiley & Sons, Inc.

  9. Derivation of hydrous pyrolysis kinetic parameters from open-system pyrolysis

    NASA Astrophysics Data System (ADS)

    Tseng, Yu-Hsin; Huang, Wuu-Liang

    2010-05-01

    Kinetic information is essential to predict the temperature, timing or depth of hydrocarbon generation within a hydrocarbon system. The most common experiments for deriving kinetic parameters are mainly by open-system pyrolysis. However, it has been shown that the conditions of open-system pyrolysis are deviant from nature by its low near-ambient pressure and high temperatures. Also, the extrapolation of heating rates in open-system pyrolysis to geological conditions may be questionable. Recent study of Lewan and Ruble shows hydrous-pyrolysis conditions can simulate the natural conditions better and its applications are supported by two case studies with natural thermal-burial histories. Nevertheless, performing hydrous pyrolysis experiment is really tedious and requires large amount of sample, while open-system pyrolysis is rather convenient and efficient. Therefore, the present study aims at the derivation of convincing distributed hydrous pyrolysis Ea with only routine open-system Rock-Eval data. Our results unveil that there is a good correlation between open-system Rock-Eval parameter Tmax and the activation energy (Ea) derived from hydrous pyrolysis. The hydrous pyrolysis single Ea can be predicted from Tmax based on the correlation, while the frequency factor (A0) is estimated based on the linear relationship between single Ea and log A0. Because the Ea distribution is more rational than single Ea, we modify the predicted single hydrous pyrolysis Ea into distributed Ea by shifting the pattern of Ea distribution from open-system pyrolysis until the weight mean Ea distribution equals to the single hydrous pyrolysis Ea. Moreover, it has been shown that the shape of the Ea distribution is very much alike the shape of Tmax curve. Thus, in case of the absence of open-system Ea distribution, we may use the shape of Tmax curve to get the distributed hydrous pyrolysis Ea. The study offers a new approach as a simple method for obtaining distributed hydrous pyrolysis

  10. Modification of the kinetic parameters of aldolase on binding to the actin-containing filaments of skeletal muscle.

    PubMed Central

    Walsh, T P; Clarke, F M; Masters, C J

    1977-01-01

    The kinetic parameters of fructose bisphosphate aldolase (EC 4.1.2.13) were shown to be modified on binding of the enzyme to the actin-containing filaments of skeletal muscle. Although binding to F-actin or F-actin-tropomyosin filaments results in relative minor changes in kinetic properties, binding to F-actin-tropomyosin-troponin filaments produces major alterations in the kinetic parameters, and, in addition, renders them Ca2+-sensitive. These observations may be relevant to an understanding of the function of this enzyme within the muscle fibre. PMID:889571

  11. Analytical Expressions for the Mixed-Order Kinetics Parameters of TL Glow Peaks Based on the two Heating Rates Method.

    PubMed

    Maghrabi, Mufeed; Al-Abdullah, Tariq; Khattari, Ziad

    2018-03-24

    The two heating rates method (originally developed for first-order glow peaks) was used for the first time to evaluate the activation energy (E) from glow peaks obeying mixed-order (MO) kinetics. The derived expression for E has an insignificant additional term (on the scale of a few meV) when compared with the first-order case. Hence, the original expression for E using the two heating rates method can be used with excellent accuracy in the case of MO glow peaks. In addition, we derived a simple analytical expression for the MO parameter. The present procedure has the advantage that the MO parameter can now be evaluated using analytical expression instead of using the graphical representation between the geometrical factor and the MO parameter as given by the existing peak shape methods. The applicability of the derived expressions for real samples was demonstrated for the glow curve of Li 2 B 4 O 7 :Mn single crystal. The obtained parameters compare very well with those obtained by glow curve fitting and with the available published data.

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

    PubMed Central

    2011-01-01

    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. PMID:21989173

  13. Validation of Bayesian analysis of compartmental kinetic models in medical imaging.

    PubMed

    Sitek, Arkadiusz; Li, Quanzheng; El Fakhri, Georges; Alpert, Nathaniel M

    2016-10-01

    Kinetic compartmental analysis is frequently used to compute physiologically relevant quantitative values from time series of images. In this paper, a new approach based on Bayesian analysis to obtain information about these parameters is presented and validated. The closed-form of the posterior distribution of kinetic parameters is derived with a hierarchical prior to model the standard deviation of normally distributed noise. Markov chain Monte Carlo methods are used for numerical estimation of the posterior distribution. Computer simulations of the kinetics of F18-fluorodeoxyglucose (FDG) are used to demonstrate drawing statistical inferences about kinetic parameters and to validate the theory and implementation. Additionally, point estimates of kinetic parameters and covariance of those estimates are determined using the classical non-linear least squares approach. Posteriors obtained using methods proposed in this work are accurate as no significant deviation from the expected shape of the posterior was found (one-sided P>0.08). It is demonstrated that the results obtained by the standard non-linear least-square methods fail to provide accurate estimation of uncertainty for the same data set (P<0.0001). The results of this work validate new methods for a computer simulations of FDG kinetics. Results show that in situations where the classical approach fails in accurate estimation of uncertainty, Bayesian estimation provides an accurate information about the uncertainties in the parameters. Although a particular example of FDG kinetics was used in the paper, the methods can be extended for different pharmaceuticals and imaging modalities. Copyright © 2016 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

  14. The combination of kinetic and flow cytometric semen parameters as a tool to predict fertility in cryopreserved bull semen.

    PubMed

    Gliozzi, T M; Turri, F; Manes, S; Cassinelli, C; Pizzi, F

    2017-11-01

    Within recent years, there has been growing interest in the prediction of bull fertility through in vitro assessment of semen quality. A model for fertility prediction based on early evaluation of semen quality parameters, to exclude sires with potentially low fertility from breeding programs, would therefore be useful. The aim of the present study was to identify the most suitable parameters that would provide reliable prediction of fertility. Frozen semen from 18 Italian Holstein-Friesian proven bulls was analyzed using computer-assisted semen analysis (CASA) (motility and kinetic parameters) and flow cytometry (FCM) (viability, acrosomal integrity, mitochondrial function, lipid peroxidation, plasma membrane stability and DNA integrity). Bulls were divided into two groups (low and high fertility) based on the estimated relative conception rate (ERCR). Significant differences were found between fertility groups for total motility, active cells, straightness, linearity, viability and percentage of DNA fragmented sperm. Correlations were observed between ERCR and some kinetic parameters, and membrane instability and some DNA integrity indicators. In order to define a model with high relation between semen quality parameters and ERCR, backward stepwise multiple regression analysis was applied. Thus, we obtained a prediction model that explained almost half (R 2=0.47, P<0.05) of the variation in the conception rate and included nine variables: five kinetic parameters measured by CASA (total motility, active cells, beat cross frequency, curvilinear velocity and amplitude of lateral head displacement) and four parameters related to DNA integrity evaluated by FCM (degree of chromatin structure abnormality Alpha-T, extent of chromatin structure abnormality (Alpha-T standard deviation), percentage of DNA fragmented sperm and percentage of sperm with high green fluorescence representative of immature cells). A significant relationship (R 2=0.84, P<0.05) was observed between

  15. Estimating the kinetic parameters of activated sludge storage using weighted non-linear least-squares and accelerating genetic algorithm.

    PubMed

    Fang, Fang; Ni, Bing-Jie; Yu, Han-Qing

    2009-06-01

    In this study, weighted non-linear least-squares analysis and accelerating genetic algorithm are integrated to estimate the kinetic parameters of substrate consumption and storage product formation of activated sludge. A storage product formation equation is developed and used to construct the objective function for the determination of its production kinetics. The weighted least-squares analysis is employed to calculate the differences in the storage product concentration between the model predictions and the experimental data as the sum of squared weighted errors. The kinetic parameters for the substrate consumption and the storage product formation are estimated to be the maximum heterotrophic growth rate of 0.121/h, the yield coefficient of 0.44 mg CODX/mg CODS (COD, chemical oxygen demand) and the substrate half saturation constant of 16.9 mg/L, respectively, by minimizing the objective function using a real-coding-based accelerating genetic algorithm. Also, the fraction of substrate electrons diverted to the storage product formation is estimated to be 0.43 mg CODSTO/mg CODS. The validity of our approach is confirmed by the results of independent tests and the kinetic parameter values reported in literature, suggesting that this approach could be useful to evaluate the product formation kinetics of mixed cultures like activated sludge. More importantly, as this integrated approach could estimate the kinetic parameters rapidly and accurately, it could be applied to other biological processes.

  16. Parameter estimation and order selection for an empirical model of VO2 on-kinetics.

    PubMed

    Alata, O; Bernard, O

    2007-04-27

    In humans, VO2 on-kinetics are noisy numerical signals that reflect the pulmonary oxygen exchange kinetics at the onset of exercise. They are empirically modelled as a sum of an offset and delayed exponentials. The number of delayed exponentials; i.e. the order of the model, is commonly supposed to be 1 for low-intensity exercises and 2 for high-intensity exercises. As no ground truth has ever been provided to validate these postulates, physiologists still need statistical methods to verify their hypothesis about the number of exponentials of the VO2 on-kinetics especially in the case of high-intensity exercises. Our objectives are first to develop accurate methods for estimating the parameters of the model at a fixed order, and then, to propose statistical tests for selecting the appropriate order. In this paper, we provide, on simulated Data, performances of Simulated Annealing for estimating model parameters and performances of Information Criteria for selecting the order. These simulated Data are generated with both single-exponential and double-exponential models, and noised by white and Gaussian noise. The performances are given at various Signal to Noise Ratio (SNR). Considering parameter estimation, results show that the confidences of estimated parameters are improved by increasing the SNR of the response to be fitted. Considering model selection, results show that Information Criteria are adapted statistical criteria to select the number of exponentials.

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

    USDA-ARS?s Scientific Manuscript database

    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...

  18. A Comprehensive Enzyme Kinetic Exercise for Biochemistry

    ERIC Educational Resources Information Center

    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…

  19. Understanding system dynamics of an adaptive enzyme network from globally profiled kinetic parameters.

    PubMed

    Chiang, Austin W T; Liu, Wei-Chung; Charusanti, Pep; Hwang, Ming-Jing

    2014-01-15

    A major challenge in mathematical modeling of biological systems is to determine how model parameters contribute to systems dynamics. As biological processes are often complex in nature, it is desirable to address this issue using a systematic approach. Here, we propose a simple methodology that first performs an enrichment test to find patterns in the values of globally profiled kinetic parameters with which a model can produce the required system dynamics; this is then followed by a statistical test to elucidate the association between individual parameters and different parts of the system's dynamics. We demonstrate our methodology on a prototype biological system of perfect adaptation dynamics, namely the chemotaxis model for Escherichia coli. Our results agreed well with those derived from experimental data and theoretical studies in the literature. Using this model system, we showed that there are motifs in kinetic parameters and that these motifs are governed by constraints of the specified system dynamics. A systematic approach based on enrichment statistical tests has been developed to elucidate the relationships between model parameters and the roles they play in affecting system dynamics of a prototype biological network. The proposed approach is generally applicable and therefore can find wide use in systems biology modeling research.

  20. Kinetic parameters and structural variations in Cu-Al-Mn and Cu-Al-Mn-Mg shape memory alloys

    NASA Astrophysics Data System (ADS)

    Canbay, Canan Aksu

    2017-02-01

    In this work polycrystalline Cu-Al-Mn and Cu-Al-Mn-Mg SMAs were fabricated by arc melting. The thermal analysis was made to determine the characteristic transformation temperatures of the samples and kinetic parameters. Also the effect of Mg on transformation temperatures and kinetic parameters detected. The structural analysis was made to designate the diffraction planes of martensite phase at room temperature and this was supported by optical measurement observations.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    La Fontaine, M; Bradshaw, T; Kubicek, L

    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})more » 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

  2. Study of the kinetic parameters for synthesis and hydrolysis of pharmacologically active salicin isomer catalyzed by baker's yeast maltase

    NASA Astrophysics Data System (ADS)

    Veličković, D. V.; Dimitrijević, A. S.; Bihelović, F. J.; Jankov, R. M.; Milosavić, N.

    2011-12-01

    One of the key elements for understanding enzyme reactions is determination of its kinetic parameters. Since transglucosylation is kinetically controlled reaction, besides the reaction of synthesis, very important is the reaction of enzymatic hydrolysis of created product. Therefore, in this study, kinetic parameters for synthesis and secondary hydrolysis of pharmacologically active α isosalicin by baker's yeast maltase were calculated, and it was shown that specifity of maltase for hydrolysis is approximately 150 times higher then for synthesis.

  3. Optimization of kinetic parameters for the degradation of plasmid DNA in rat plasma

    NASA Astrophysics Data System (ADS)

    Chaudhry, Q. A.

    2014-12-01

    Biotechnology is a rapidly growing area of research work in the field of pharmaceutical sciences. The study of pharmacokinetics of plasmid DNA (pDNA) is an important area of research work. It has been observed that the process of gene delivery faces many troubles on the transport of pDNA towards their target sites. The topoforms of pDNA has been termed as super coiled (S-C), open circular (O-C) and linear (L), the kinetic model of which will be presented in this paper. The kinetic model gives rise to system of ordinary differential equations (ODEs), the exact solution of which has been found. The kinetic parameters, which are responsible for the degradation of super coiled, and the formation of open circular and linear topoforms have a great significance not only in vitro but for modeling of further processes as well, therefore need to be addressed in great detail. For this purpose, global optimization techniques have been adopted, thus finding the optimal results for the said model. The results of the model, while using the optimal parameters, were compared against the measured data, which gives a nice agreement.

  4. Solid State Kinetic Parameters and Chemical Mechanism of the Dehydration of CoCl2.6H2O.

    ERIC Educational Resources Information Center

    Ribas, Joan; And Others

    1988-01-01

    Presents an experimental example illustrating the most common methods for the determination of kinetic parameters. Discusses the different theories and equations to be applied and the mechanism derived from the kinetic results. (CW)

  5. Kinetic parameters of grinding media in ball mills with various liner design and mill speed based on DEM modeling

    NASA Astrophysics Data System (ADS)

    Khakhalev, P. A.; Bogdanov, VS; Kovshechenko, V. M.

    2018-03-01

    The article presents analysis of the experiments in the ball mill of 0.5x0.3 m with four different liner types based on DEM modeling. The numerical experiment always complements laboratory research and allow obtaining high accuracy output data. An important property of the numerical experiment is the possibility of visualization of the results. The EDEM software allows calculating trajectory of the grinding bodies and kinetic parameters of each ball for the relative mill speed and the different types of mill’s liners.

  6. An improved hybrid of particle swarm optimization and the gravitational search algorithm to produce a kinetic parameter estimation of aspartate biochemical pathways.

    PubMed

    Ismail, Ahmad Muhaimin; Mohamad, Mohd Saberi; Abdul Majid, Hairudin; Abas, Khairul Hamimah; Deris, Safaai; Zaki, Nazar; Mohd Hashim, Siti Zaiton; Ibrahim, Zuwairie; Remli, Muhammad Akmal

    2017-12-01

    Mathematical modelling is fundamental to understand the dynamic behavior and regulation of the biochemical metabolisms and pathways that are found in biological systems. Pathways are used to describe complex processes that involve many parameters. It is important to have an accurate and complete set of parameters that describe the characteristics of a given model. However, measuring these parameters is typically difficult and even impossible in some cases. Furthermore, the experimental data are often incomplete and also suffer from experimental noise. These shortcomings make it challenging to identify the best-fit parameters that can represent the actual biological processes involved in biological systems. Computational approaches are required to estimate these parameters. The estimation is converted into multimodal optimization problems that require a global optimization algorithm that can avoid local solutions. These local solutions can lead to a bad fit when calibrating with a model. Although the model itself can potentially match a set of experimental data, a high-performance estimation algorithm is required to improve the quality of the solutions. This paper describes an improved hybrid of particle swarm optimization and the gravitational search algorithm (IPSOGSA) to improve the efficiency of a global optimum (the best set of kinetic parameter values) search. The findings suggest that the proposed algorithm is capable of narrowing down the search space by exploiting the feasible solution areas. Hence, the proposed algorithm is able to achieve a near-optimal set of parameters at a fast convergence speed. The proposed algorithm was tested and evaluated based on two aspartate pathways that were obtained from the BioModels Database. The results show that the proposed algorithm outperformed other standard optimization algorithms in terms of accuracy and near-optimal kinetic parameter estimation. Nevertheless, the proposed algorithm is only expected to work well in

  7. Influence of external mass transfer limitation on apparent kinetic parameters of penicillin G acylase immobilized on nonporous ultrafine silica particles.

    PubMed

    Kheirolomoom, Azadeh; Khorasheh, Farhad; Fazelinia, Hossein

    2002-01-01

    Immobilization of enzymes on nonporous supports provides a suitable model for investigating the effect of external mass transfer limitation on the reaction rate in the absence of internal diffusional resistance. In this study, deacylation of penicillin G was investigated using penicillin acylase immobilized on ultrafine silica particles. Kinetic studies were performed within the low-substrate-concentration region, where the external mass transfer limitation becomes significant. To predict the apparent kinetic parameters and the overall effectiveness factor, knowledge of the external mass transfer coefficient, k(L)a, is necessary. Although various correlations exist for estimation of k(L)a, in this study, an optimization scheme was utilized to obtain this coefficient. Using the optimum values of k(L)a, the initial reaction rates were predicted and found to be in good agreement with the experimental data.

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

    PubMed

    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

  9. Effects of correlated parameters and uncertainty in electronic-structure-based chemical kinetic modelling

    NASA Astrophysics Data System (ADS)

    Sutton, Jonathan E.; Guo, Wei; Katsoulakis, Markos A.; Vlachos, Dionisios G.

    2016-04-01

    Kinetic models based on first principles are becoming common place in heterogeneous catalysis because of their ability to interpret experimental data, identify the rate-controlling step, guide experiments and predict novel materials. To overcome the tremendous computational cost of estimating parameters of complex networks on metal catalysts, approximate quantum mechanical calculations are employed that render models potentially inaccurate. Here, by introducing correlative global sensitivity analysis and uncertainty quantification, we show that neglecting correlations in the energies of species and reactions can lead to an incorrect identification of influential parameters and key reaction intermediates and reactions. We rationalize why models often underpredict reaction rates and show that, despite the uncertainty being large, the method can, in conjunction with experimental data, identify influential missing reaction pathways and provide insights into the catalyst active site and the kinetic reliability of a model. The method is demonstrated in ethanol steam reforming for hydrogen production for fuel cells.

  10. Kinetics of suicide substrates. Practical procedures for determining parameters.

    PubMed Central

    Waley, S G

    1985-01-01

    Many clinically important or mechanistically interesting inhibitors react with enzymes by a branched pathway in which inactivation of the enzyme and formation of product are competing reactions. The steady-state kinetics for this pathway [Waley (1980) Biochem. J. 185, 771-773] gave equations for progress curves that were cumbersome. A convenient linear plot is now described. The time (t1/2) for 50% inactivation of the enzyme (this is also the time for 50% formation of product), or for 50% loss of substrate, is measured in a series of experiments in which the concentration of inhibitor, [I]0, is varied; in these experiments the ratio of the concentration of enzyme to the concentration of inhibitor is kept fixed. Then a plot of [I]0 X t1/2 against [I]0 is linear, and the kinetic parameters can be found from the slope and intercept. Furthermore, simplifications of the equations for progress curves are described that are valid when the concentration of inhibitors is high, or is low, or when the extent of reaction is low. The use of simulated data has shown that the recommended methods are not unduly sensitive to experimental error. PMID:4004802

  11. Two-order parameters theory of the metal-insulator phase transition kinetics in the magnetic field

    NASA Astrophysics Data System (ADS)

    Dubovskii, L. B.

    2018-05-01

    The metal-insulator phase transition is considered within the framework of the Ginzburg-Landau approach for the phase transition described with two coupled order parameters. One of the order parameters is the mass density which variation is responsible for the origin of nonzero overlapping of the two different electron bands and the appearance of free electron carriers. This transition is assumed to be a first-order phase one. The free electron carriers are described with the vector-function representing the second-order parameter responsible for the continuous phase transition. This order parameter determines mostly the physical properties of the metal-insulator transition and leads to a singularity of the surface tension at the metal-insulator interface. The magnetic field is involved into the consideration of the system. The magnetic field leads to new singularities of the surface tension at the metal-insulator interface and results in a drastic variation of the phase transition kinetics. A strong singularity in the surface tension results from the Landau diamagnetism and determines anomalous features of the metal-insulator transition kinetics.

  12. Inter-trial and test–retest reliability of kinematic and kinetic gait parameters among subjects with adolescent idiopathic scoliosis

    PubMed Central

    Nadeau, Sylvie; Labelle, Hubert

    2007-01-01

    Gait analysis is actually used in subjects with scoliosis to determine the change in lower limb parameters after surgery, but the reliability of these parameters still remained unknown. The purpose of this study was to assess the repeatability of traditional gait parameters in subjects with adolescent idiopathic scoliosis (AIS) and to estimate the associated standard error of measurement (SEM). A test–retest design was used to assess the reliability of gait parameters at self-selected and fast speeds. A convenience sample of 20 girls aged from 12 to 17 years, with an idiopathic scoliosis (King classification: types I, II or III; Cobb angle 17–50°) participated in the study. Five good trials were recorded on two occasions. The time-distance, kinematic, and kinetic gait parameters were recorded using foot-switches in combination with a three-dimensional motion analysis system (Optotrak) and Advanced Mechanical Technologies Inc., (AMTI) Watertown, MA, USA; force plates. The coefficients of dependability and SEM derived from the generalizability theory were used to assess the reliability. Inter-trial reliability was good for time-distance, kinematic, and kinetic (absolute and normalized) gait parameters except for the medio-lateral ground reaction force (GRF) component and the ankle dorsiflexor moment (ϕ = 0.60–0.77). Test–retest reliability was higher for the kinetic than for the kinematic parameters. These coefficients ranged from 0.42 to 0.58 for the time-distance parameters; from 0.55 to 0.88 for the angular displacements and from 0.25 to 0.99 for the kinetic parameters. The SEMs were lower than 3.3° for the angular displacements and lower than 8 Nm (0.15 Nm/kg) and 36 W (0.54 W/Kg) for the joint moments and powers regardless of the speed. Several gait parameters are reliable among subjects with AIS and can be used to assess the evolution of the spinal modifications and the impact of treatment on their lower limb gait pattern. PMID:17891424

  13. Comparative kinetic analysis on thermal degradation of some cephalosporins using TG and DSC data

    PubMed Central

    2013-01-01

    Background The thermal decomposition of cephalexine, cefadroxil and cefoperazone under non-isothermal conditions using the TG, respectively DSC methods, was studied. In case of TG, a hyphenated technique, including EGA, was used. Results The kinetic analysis was performed using the TG and DSC data in air for the first step of cephalosporin’s decomposition at four heating rates. The both TG and DSC data were processed according to an appropriate strategy to the following kinetic methods: Kissinger-Akahira-Sunose, Friedman, and NPK, in order to obtain realistic kinetic parameters, even if the decomposition process is a complex one. The EGA data offer some valuable indications about a possible decomposition mechanism. The obtained data indicate a rather good agreement between the activation energy’s values obtained by different methods, whereas the EGA data and the chemical structures give a possible explanation of the observed differences on the thermal stability. A complete kinetic analysis needs a data processing strategy using two or more methods, but the kinetic methods must also be applied to the different types of experimental data (TG and DSC). Conclusion The simultaneous use of DSC and TG data for the kinetic analysis coupled with evolved gas analysis (EGA) provided us a more complete picture of the degradation of the three cephalosporins. It was possible to estimate kinetic parameters by using three different kinetic methods and this allowed us to compare the Ea values obtained from different experimental data, TG and DSC. The thermodegradation being a complex process, the both differential and integral methods based on the single step hypothesis are inadequate for obtaining believable kinetic parameters. Only the modified NPK method allowed an objective separation of the temperature, respective conversion influence on the reaction rate and in the same time to ascertain the existence of two simultaneous steps. PMID:23594763

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Nandipati, Giridhar; Setyawan, Wahyu; Heinisch, Howard L.

    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, 1025more » 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.« less

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

    PubMed

    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

  16. Kinetic energy budgets in areas of intense convection

    NASA Technical Reports Server (NTRS)

    Fuelberg, H. E.; Berecek, E. M.; Ebel, D. M.; Jedlovec, G. J.

    1980-01-01

    A kinetic energy budget analysis of the AVE-SESAME 1 period which coincided with the deadly Red River Valley tornado outbreak is presented. Horizontal flux convergence was found to be the major kinetic energy source to the region, while cross contour destruction was the major sink. Kinetic energy transformations were dominated by processes related to strong jet intrusion into the severe storm area. A kinetic energy budget of the AVE 6 period also is presented. The effects of inherent rawinsonde data errors on widely used basic kinematic parameters, including velocity divergence, vorticity advection, and kinematic vertical motion are described. In addition, an error analysis was performed in terms of the kinetic energy budget equation. Results obtained from downward integration of the continuity equation to obtain kinematic values of vertical motion are described. This alternate procedure shows promising results in severe storm situations.

  17. Plyometric Long Jump Training With Progressive Loading Improves Kinetic and Kinematic Swimming Start Parameters.

    PubMed

    Rebutini, Vanessa Z; Pereira, Gleber; Bohrer, Roberta C D; Ugrinowitsch, Carlos; Rodacki, André L F

    2016-09-01

    Rebutini, VZ, Pereira, G, Bohrer, RCD, Ugrinowitsch, C, and Rodacki, ALF. Plyometric long jump training with progressive loading improves kinetic and kinematic swimming start parameters. J Strength Cond Res 30(9): 2392-2398, 2016-This study was aimed to determine the effects of a plyometric long jump training program on torque around the lower limb joints and kinetic and kinematics parameters during the swimming jump start. Ten swimmers performed 3 identical assessment sessions, measuring hip and knee muscle extensors during maximal voluntary isometric contraction and kinetic and kinematics parameters during the swimming jump start, at 3 instants: INI (2 weeks before the training program, control period), PRE (2 weeks after INI measurements), and POST (24-48 hours after 9 weeks of training). There were no significant changes from INI to PRE measurements. However, the peak torque and rate of torque development increased significantly from PRE to POST measurements for both hip (47 and 108%) and knee (24 and 41%) joints. There were significant improvements to the horizontal force (7%), impulse (9%), and angle of resultant force (19%). In addition, there were significant improvements to the center of mass displacement (5%), horizontal takeoff velocity (16%), horizontal velocity at water entrance (22%), and peak angle velocity for the knee (15%) and hip joints (16%). Therefore, the plyometric long jump training protocol was effective to enhance torque around the lower limb joints and to control the resultant vector direction, to increase the swimming jump start performance. These findings suggest that coaches should use long jump training instead of vertical jump training to improve swimming start performance.

  18. Modeling the degradation kinetics of ascorbic acid.

    PubMed

    Peleg, Micha; Normand, Mark D; Dixon, William R; Goulette, Timothy R

    2018-06-13

    Most published reports on ascorbic acid (AA) degradation during food storage and heat preservation suggest that it follows first-order kinetics. Deviations from this pattern include Weibullian decay, and exponential drop approaching finite nonzero retention. Almost invariably, the degradation rate constant's temperature-dependence followed the Arrhenius equation, and hence the simpler exponential model too. A formula and freely downloadable interactive Wolfram Demonstration to convert the Arrhenius model's energy of activation, E a , to the exponential model's c parameter, or vice versa, are provided. The AA's isothermal and non-isothermal degradation can be simulated with freely downloadable interactive Wolfram Demonstrations in which the model's parameters can be entered and modified by moving sliders on the screen. Where the degradation is known a priori to follow first or other fixed order kinetics, one can use the endpoints method, and in principle the successive points method too, to estimate the reaction's kinetic parameters from considerably fewer AA concentration determinations than in the traditional manner. Freeware to do the calculations by either method has been recently made available on the Internet. Once obtained in this way, the kinetic parameters can be used to reconstruct the entire degradation curves and predict those at different temperature profiles, isothermal or dynamic. Comparison of the predicted concentration ratios with experimental ones offers a way to validate or refute the kinetic model and the assumptions on which it is based.

  19. Development of a Kinetic Assay for Late Endosome Movement.

    PubMed

    Esner, Milan; Meyenhofer, Felix; Kuhn, Michael; Thomas, Melissa; Kalaidzidis, Yannis; Bickle, Marc

    2014-08-01

    Automated imaging screens are performed mostly on fixed and stained samples to simplify the workflow and increase throughput. Some processes, such as the movement of cells and organelles or measuring membrane integrity and potential, can be measured only in living cells. Developing such assays to screen large compound or RNAi collections is challenging in many respects. Here, we develop a live-cell high-content assay for tracking endocytic organelles in medium throughput. We evaluate the added value of measuring kinetic parameters compared with measuring static parameters solely. We screened 2000 compounds in U-2 OS cells expressing Lamp1-GFP to label late endosomes. All hits have phenotypes in both static and kinetic parameters. However, we show that the kinetic parameters enable better discrimination of the mechanisms of action. Most of the compounds cause a decrease of motility of endosomes, but we identify several compounds that increase endosomal motility. In summary, we show that kinetic data help to better discriminate phenotypes and thereby obtain more subtle phenotypic clustering. © 2014 Society for Laboratory Automation and Screening.

  20. Thermal oxidative degradation kinetics of agricultural residues using distributed activation energy model and global kinetic model.

    PubMed

    Ren, Xiu'e; Chen, Jianbiao; Li, Gang; Wang, Yanhong; Lang, Xuemei; Fan, Shuanshi

    2018-08-01

    The study concerned the thermal oxidative degradation kinetics of agricultural residues, peanut shell (PS) and sunflower shell (SS). The thermal behaviors were evaluated via thermogravimetric analysis and the kinetic parameters were determined by using distributed activation energy model (DAEM) and global kinetic model (GKM). Results showed that thermal oxidative decomposition of two samples processed in three zones; the ignition, burnout, and comprehensive combustibility between two agricultural residues were of great difference; and the combustion performance could be improved by boosting heating rate. The activation energy ranges calculated by the DAEM for the thermal oxidative degradation of PS and SS were 88.94-145.30 kJ mol -1 and 94.86-169.18 kJ mol -1 , respectively. The activation energy obtained by the GKM for the oxidative decomposition of hemicellulose and cellulose was obviously lower than that for the lignin oxidation at identical heating rate. To some degree, the determined kinetic parameters could acceptably simulate experimental data. Copyright © 2018 Elsevier Ltd. All rights reserved.

  1. The influence of pH adjustment on kinetics parameters in tapioca wastewater treatment using aerobic sequencing batch reactor system

    NASA Astrophysics Data System (ADS)

    Mulyani, Happy; Budianto, Gregorius Prima Indra; Margono, Kaavessina, Mujtahid

    2018-02-01

    The present investigation deals with the aerobic sequencing batch reactor system of tapioca wastewater treatment with varying pH influent conditions. This project was carried out to evaluate the effect of pH on kinetics parameters of system. It was done by operating aerobic sequencing batch reactor system during 8 hours in many tapioca wastewater conditions (pH 4.91, pH 7, pH 8). The Chemical Oxygen Demand (COD) and Mixed Liquor Volatile Suspended Solids (MLVSS) of the aerobic sequencing batch reactor system effluent at steady state condition were determined at interval time of two hours to generate data for substrate inhibition kinetics parameters. Values of the kinetics constants were determined using Monod and Andrews models. There was no inhibition constant (Ki) detected in all process variation of aerobic sequencing batch reactor system for tapioca wastewater treatment in this study. Furthermore, pH 8 was selected as the preferred aerobic sequencing batch reactor system condition in those ranging pH investigated due to its achievement of values of kinetics parameters such µmax = 0.010457/hour and Ks = 255.0664 mg/L COD.

  2. Growth kinetic and fuel quality parameters as selective criterion for screening biodiesel producing cyanobacterial strains.

    PubMed

    Gayathri, Manickam; Shunmugam, Sumathy; Mugasundari, Arumugam Vanmathi; Rahman, Pattanathu K S M; Muralitharan, Gangatharan

    2018-01-01

    The efficiency of cyanobacterial strains as biodiesel feedstock varies with the dwelling habitat. Fourteen indigenous heterocystous cyanobacterial strains from rice field ecosystem were screened based on growth kinetic and fuel parameters. The highest biomass productivity was obtained in Nostoc punctiforme MBDU 621 (19.22mg/L/day) followed by Calothrix sp. MBDU 701 (13.43mg/L/day). While lipid productivity and lipid content was highest in Nostoc spongiaeforme MBDU 704 (4.45mg/L/day and 22.5%dwt) followed by Calothrix sp. MBDU 701 (1.54mg/L/day and 10.75%dwt). Among the tested strains, Nostoc spongiaeforme MBDU 704 and Nostoc punctiforme MBDU 621 were selected as promising strains for good quality biodiesel production by Preference Ranking Organization Method for Enrichment Evaluation (PROMETHEE) and Graphical Analysis for Interactive Assistance (GAIA) analysis. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Second-order kinetic model for the sorption of cadmium onto tree fern: a comparison of linear and non-linear methods.

    PubMed

    Ho, Yuh-Shan

    2006-01-01

    A comparison was made of the linear least-squares method and a trial-and-error non-linear method of the widely used pseudo-second-order kinetic model for the sorption of cadmium onto ground-up tree fern. Four pseudo-second-order kinetic linear equations are discussed. Kinetic parameters obtained from the four kinetic linear equations using the linear method differed but they were the same when using the non-linear method. A type 1 pseudo-second-order linear kinetic model has the highest coefficient of determination. Results show that the non-linear method may be a better way to obtain the desired parameters.

  4. Optimizing Methods of Obtaining Stellar Parameters for the H3 Survey

    NASA Astrophysics Data System (ADS)

    Ivory, KeShawn; Conroy, Charlie; Cargile, Phillip

    2018-01-01

    The Stellar Halo at High Resolution with Hectochelle Survey (H3) is in the process of observing and collecting stellar parameters for stars in the Milky Way's halo. With a goal of measuring radial velocities for fainter stars, it is crucial that we have optimal methods of obtaining this and other parameters from the data from these stars.The method currently developed is The Payne, named after Cecilia Payne-Gaposchkin, a code that uses neural networks and Markov Chain Monte Carlo methods to utilize both spectra and photometry to obtain values for stellar parameters. This project was to investigate the benefit of fitting both spectra and spectral energy distributions (SED). Mock spectra using the parameters of the Sun were created and noise was inserted at various signal to noise values. The Payne then fit each mock spectrum with and without a mock SED also generated from solar parameters. The result was that at high signal to noise, the spectrum dominated and the effect of fitting the SED was minimal. But at low signal to noise, the addition of the SED greatly decreased the standard deviation of the data and resulted in more accurate values for temperature and metallicity.

  5. Kinetic study of olive oil degradation monitored by fourier transform infrared spectrometry. Application to oil characterization.

    PubMed

    Román Falcó, Iván P; Grané Teruel, Nuria; Prats Moya, Soledad; Martín Carratalá, M Luisa

    2012-11-28

    A new approach for the determination of kinetic parameters of the cis/trans isomerization during the oxidation process of 24 virgin olive oils belonging to 8 different varieties is presented. The accelerated process of degradation at 100 °C was monitored by recording the Fourier transform infrared spectra. The parameters obtained confirm pseudo-first-order kinetics for the degradation of cis and the appearance of trans double bonds. The kinetic approach affords the induction time and the rate coefficient; these parameters are related to the fatty acid profile of the fresh olive oils. The data obtained were used to compare the oil stability of the samples with the help of multivariate statistical techniques. Fatty acid allowed a classification of the samples in five groups, one of them constituted by the cultivars with higher stability. Meanwhile, the kinetic parameters showed greater ability for the characterization of olive oils, allowing the classification in seven groups.

  6. Reliability and Accuracy of Static Parameters Obtained From Ink and Pressure Platform Footprints.

    PubMed

    Zuil-Escobar, Juan Carlos; Martínez-Cepa, Carmen Belén; Martín-Urrialde, Jose Antonio; Gómez-Conesa, Antonia

    2016-09-01

    The purpose of this study was to evaluate the accuracy and the intrarater reliability of arch angle (AA), Staheli Index (SI), and Chippaux-Smirak Index (CSI) obtained from ink and pressure platform footprints. We obtained AA, SI, and CSI measurements from ink pedigraph footprints and pressure platform footprints in 40 healthy participants (aged 25.65 ± 5.187 years). Intrarater reliability was calculated for all parameters obtained using the 2 methods. Standard error of measurement and minimal detectable change were also calculated. A repeated-measure analysis of variance was used to identify differences between ink and pressure platform footprints. Intraclass correlation coefficient and Bland and Altman plots were used to assess similar parameters obtained using different methods. Intrarater reliability was >0.9 for all parameters and was slightly higher for the ink footprints. No statistical difference was reported in repeated-measure analysis of variance for any of the parameters. Intraclass correlation coefficient values from AA, SI, and CSI that were obtained using ink footprints and pressure platform footprints were excellent, ranging from 0.797 to 0.829. However, pressure platform overestimated AA and underestimated SI and CSI. Our study revealed that AA, SI, and CSI were similar regardless of whether the ink or pressure platform method was used. In addition, the parameters indicated high intrarater reliability and were reproducible. Copyright © 2016. Published by Elsevier Inc.

  7. A BAYESIAN METHOD OF ESTIMATING KINETIC PARAMETERS FOR THE INACTIVATION OF CRYPTOSPORIDIUM PARVUM OOCYSTS WITH CHLORINE DIOXIDE AND OZONE

    EPA Science Inventory

    The main objective of this paper is to use Bayesian methods to estimate the kinetic parameters for the inactivation kinetics of Cryptosporidium parvum oocysts with chlorine dioxide or ozone which are characterized by the delayed Chick-Watson model, i.e., a lag phase or shoulder f...

  8. Co-pyrolysis of biomass and plastic wastes: investigation of apparent kinetic parameters and stability of pyrolysis oils

    NASA Astrophysics Data System (ADS)

    Fekhar, B.; Miskolczi, N.; Bhaskar, T.; Kumar, J.; Dhyani, V.

    2018-05-01

    This work is dedicated to the co-pyrolysis of real waste high density polyethylene (HDPE) and biomass (rice straw) obtained from agriculture. Mixtures of raw materials were pyrolyzed in their 0%/100%, 30%/70%, 50%/50%, 70%/30%, 100%/0% ratios using a thermograph. The atmosphere was nitrogen, and a constant heating rate was used. Based on weight loss and DTG curves, the apparent reaction kinetic parameters (e.g., activation energy) were calculated using first-order kinetic approach and Arrhenius equation. It was found that decomposition of pure plastic has approximately 280 kJ/mol activation energy, while that of was considerably less in case of biomass. Furthermore, HDPE decomposition takes by one stage, while that of biomass was three stages. The larger amount of raw materials (100 g) were also pyrolyzed in the batch rig at 550°C to obtain products for analysis focussing to their long-term application. Pyrolysis oils were investigated by Fourier transformed infrared spectroscopy and standardized methods, such as density, viscosity, boiling range determination. It was concluded, that higher plastic ratio in raw material had the advantageous effect to the pyrolysis oil long-term application. E.g., the concentration of oxygenated compounds, such as aldehydes, ketones, carboxylic acids or even phenol and its derivate could be significantly decreased, which had an advantageous effect to their corrosion property. Lower average molecular weight, viscosity, and density were measured as a function of plastic content.

  9. Fuzzy C-mean clustering on kinetic parameter estimation with generalized linear least square algorithm in SPECT

    NASA Astrophysics Data System (ADS)

    Choi, Hon-Chit; Wen, Lingfeng; Eberl, Stefan; Feng, Dagan

    2006-03-01

    Dynamic Single Photon Emission Computed Tomography (SPECT) has the potential to quantitatively estimate physiological parameters by fitting compartment models to the tracer kinetics. The generalized linear least square method (GLLS) is an efficient method to estimate unbiased kinetic parameters and parametric images. However, due to the low sensitivity of SPECT, noisy data can cause voxel-wise parameter estimation by GLLS to fail. Fuzzy C-Mean (FCM) clustering and modified FCM, which also utilizes information from the immediate neighboring voxels, are proposed to improve the voxel-wise parameter estimation of GLLS. Monte Carlo simulations were performed to generate dynamic SPECT data with different noise levels and processed by general and modified FCM clustering. Parametric images were estimated by Logan and Yokoi graphical analysis and GLLS. The influx rate (K I), volume of distribution (V d) were estimated for the cerebellum, thalamus and frontal cortex. Our results show that (1) FCM reduces the bias and improves the reliability of parameter estimates for noisy data, (2) GLLS provides estimates of micro parameters (K I-k 4) as well as macro parameters, such as volume of distribution (Vd) and binding potential (BP I & BP II) and (3) FCM clustering incorporating neighboring voxel information does not improve the parameter estimates, but improves noise in the parametric images. These findings indicated that it is desirable for pre-segmentation with traditional FCM clustering to generate voxel-wise parametric images with GLLS from dynamic SPECT data.

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

    PubMed Central

    Alfaro-Cuevas-Villanueva, Ruth; Hidalgo-Vázquez, Aura Roxana; Cortés Penagos, Consuelo de Jesús; Cortés-Martínez, Raúl

    2014-01-01

    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 (K 2) 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. PMID:24587740

  11. Kinetics of hydrophobic organic contaminant extraction from sediment by granular activated carbon.

    PubMed

    Rakowska, M I; Kupryianchyk, D; Smit, M P J; Koelmans, A A; Grotenhuis, J T C; Rijnaarts, H H M

    2014-03-15

    Ex situ solid phase extraction with granular activated carbon (GAC) is a promising technique to remediate contaminated sediments. The methods' efficiency depends on the rate by which contaminants are transferred from the sediment to the surface of GAC. Here, we derive kinetic parameters for extraction of polycyclic aromatic hydrocarbons (PAH) from sediment by GAC, using a first-order multi-compartment kinetic model. The parameters were obtained by modeling sediment-GAC exchange kinetic data following a tiered model calibration approach. First, parameters for PAH desorption from sediment were calibrated using data from systems with 50% (by weight) GAC acting as an infinite sink. Second, the estimated parameters were used as fixed input to obtain GAC uptake kinetic parameters in sediment slurries with 4% GAC, representing the ex situ remediation scenario. PAH uptake rate constants (kGAC) by GAC ranged from 0.44 to 0.0005 d(-1), whereas GAC sorption coefficients (KGAC) ranged from 10(5.57) to 10(8.57) L kg(-1). These values are the first provided for GAC in the presence of sediment and show that ex situ extraction with GAC is sufficiently fast and effective to reduce the risks of the most available PAHs among those studied, such as fluorene, phenanthrene and anthracene. Copyright © 2013 Elsevier Ltd. All rights reserved.

  12. Sorption kinetics of diuron on volcanic ash derived soils.

    PubMed

    Cáceres-Jensen, Lizethly; Rodríguez-Becerra, Jorge; Parra-Rivero, Joselyn; Escudey, Mauricio; Barrientos, Lorena; Castro-Castillo, Vicente

    2013-10-15

    Diuron sorption kinetic was studied in Andisols, Inceptisol and Ultisols soils in view of their distinctive physical and chemical properties: acidic pH and variable surface charge. Two types of kinetic models were used to fit the experimental dates: those that allow to establish principal kinetic parameters and modeling of sorption process (pseudo-first-order, pseudo-second-order), and some ones frequently used to describe solute transport mechanisms of organic compounds on different sorbents intended for remediation purposes (Elovich equation, intraparticle diffusion, Boyd, and two-site nonequilibrium models). The best fit was obtained with the pseudo-second-order model. The rate constant and the initial rate constant values obtained through this model demonstrated the behavior of Diuron in each soil, in Andisols were observed the highest values for both parameters. The application of the models to describe solute transport mechanisms allowed establishing that in all soils the mass transfer controls the sorption kinetic across the boundary layer and intraparticle diffusion into macropores and micropores. The slowest sorption rate was observed on Ultisols, behavior which must be taken into account when the leaching potential of Diuron is considered. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Quantitative evaluation of dual-flip-angle T1 mapping on DCE-MRI kinetic parameter estimation in head and neck

    PubMed Central

    Chow, Steven Kwok Keung; Yeung, David Ka Wai; Ahuja, Anil T; King, Ann D

    2012-01-01

    Purpose To quantitatively evaluate the kinetic parameter estimation for head and neck (HN) dynamic contrast-enhanced (DCE) MRI with dual-flip-angle (DFA) T1 mapping. Materials and methods Clinical DCE-MRI datasets of 23 patients with HN tumors were included in this study. T1 maps were generated based on multiple-flip-angle (MFA) method and different DFA combinations. Tofts model parameter maps of kep, Ktrans and vp based on MFA and DFAs were calculated and compared. Fitted parameter by MFA and DFAs were quantitatively evaluated in primary tumor, salivary gland and muscle. Results T1 mapping deviations by DFAs produced remarkable kinetic parameter estimation deviations in head and neck tissues. In particular, the DFA of [2º, 7º] overestimated, while [7º, 12º] and [7º, 15º] underestimated Ktrans and vp, significantly (P<0.01). [2º, 15º] achieved the smallest but still statistically significant overestimation for Ktrans and vp in primary tumors, 32.1% and 16.2% respectively. kep fitting results by DFAs were relatively close to the MFA reference compared to Ktrans and vp. Conclusions T1 deviations induced by DFA could result in significant errors in kinetic parameter estimation, particularly Ktrans and vp, through Tofts model fitting. MFA method should be more reliable and robust for accurate quantitative pharmacokinetic analysis in head and neck. PMID:23289084

  14. Characterizing the kinetics of suspended cylindrical particles by polarization measurements

    NASA Astrophysics Data System (ADS)

    Liao, Ran; Ou, Xueheng; Ma, Hui

    2015-09-01

    Polarization has promising potential to retrieve the information of the steady samples, such as tissues. However, for the fast changing sample such as the suspended algae in the water, the kinetics of the particles also influence the scattered polarization. The present paper will show our recent results to extract the information about the kinetics of the suspended cylindrical particles by polarization measurements. The sample is the aqueous suspension of the glass fibers stirred by a magnetic stirrer. We measure the scattered polarization of the fibers by use of a simultaneous polarization measurement system and obtain the time series of two orthogonal polarization components. By use of correlation analysis, we obtain the time parameters from the auto-correlation functions of the polarization components, and observe the changes with the stirring speeds. Results show that these time parameters indicate the immigration of the fibers. After discussion, we find that they may further characterize the kinetics, including the translation and rotation, of the glass fibers in the fluid field.

  15. Kinetic and thermodynamic parameters for heat denaturation of human recombinant lactoferrin from rice.

    PubMed

    Castillo, Eduardo; Pérez, María Dolores; Franco, Indira; Calvo, Miguel; Sánchez, Lourdes

    2012-06-01

    Heat denaturation of recombinant human lactoferrin (rhLf) from rice with 3 different iron-saturation degrees, holo rhLf (iron-saturated), AsIs rhLf (60% iron saturation), and apo rhLf (iron-depleted), was studied. The 3 forms of rhLf were subjected to heat treatment, and the kinetic and thermodynamic parameters of the denaturation process were determined. Thermal denaturation of rhLf was assessed by measuring the loss of reactivity against specific antibodies. D(t) values (time to reduce 90% of immunoreactivity) decreased with increasing temperature of treatment for apo and holo rhLf, those values being higher for the iron-saturated form, which indicates that iron confers thermal stability to rhLf. However, AsIs rhLf showed a different behaviour with an increase in resistance to heat between 79 °C and 84 °C, so that the kinetic parameters could not be calculated. The heat denaturation process for apo and holo rhLf was best described assuming a reaction order of 1.5. The activation energy of the denaturation process was 648.20 kJ/mol for holo rhLf and 406.94 kJ/mol for apo rhLf, confirming that iron-depleted rhLf is more sensitive to heat treatment than iron-saturated rhLf.

  16. Determining the Kinetic Parameters Characteristic of Microalgal Growth.

    ERIC Educational Resources Information Center

    Martinez Sancho, Maria Eugenie; And Others

    1991-01-01

    An activity in which students obtain a growth curve for algae, identify the exponential and linear growth phases, and calculate the parameters which characterize both phases is described. The procedure, a list of required materials, experimental conditions, analytical technique, and a discussion of the interpretations of individual results are…

  17. Kinetic Parameters for the Noncatalyzed and Enzyme-Catalyzed Mutarotation of Glucose Using a Blood Glucometer

    ERIC Educational Resources Information Center

    Hardee, John R.; Delgado, Bryan; Jones, Wray

    2011-01-01

    The kinetic parameters for the conversion of alpha-D-glucose to beta-D-glucose were measured using a blood glucometer. The reaction order, rate constant, and Arrhenius activation energy are reported for the noncatalyzed reaction and turnover number and Michaelis constant are reported for the reaction catalyzed by porcine kidney mutarotase. The…

  18. Toxicity and kinetic parameters of the aerobic biodegradation of the phenol and alkylphenols by a mixed culture.

    PubMed

    Acuña-Argüelles, M E; Olguin-Lora, P; Razo-Flores, E

    2003-04-01

    A mixed culture aerobically metabolized phenol, cresol isomers (o-,m-,p-), 2-ethylphenol and xylenol isomers (2,5-DMP and 3,4-DMP) as the sole carbon and energy source. This culture had a high tolerance towards phenol with values of maximum degradation rate (Vmax) of 47 microM phenol mg-1 protein h-1 and inhibition substrate constant (Ki) of 10 mM. These kinetic parameters were considerably diminished and the toxicity increased with the alkylphenols. For example with 2,5-xylenol, Vmax and Ki values of 0.8 microM 2,5-xylenol mg-1 protein h-1 and 1.3 mM, respectively, were obtained. The cresols were 5-fold more toxic than phenol, whereas 2-ethylphenol and 3,4-xylenol were 11-fold more toxic, and 2,5-xylenol was 34-fold more toxic than phenol.

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

    PubMed

    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 (p<0.05) in Dyn-WU and Control compared to Neu-WU. No other significant (p>0.05) 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. © Georg Thieme Verlag KG Stuttgart · New York.

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

    PubMed

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

    2002-12-20

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

  1. Kinetics of thermophilic anaerobes in fixed-bed reactors.

    PubMed

    Perez, M; Romero, L I; Sales, D

    2001-08-01

    The main objective of this study is to estimate growth kinetic constants and the concentration of "active" attached biomass in two anaerobic thermophilic reactors which contain different initial sizes of immobilized anaerobic mixed cultures and decompose distillery wastewater. This paper studies the substrate decomposition in two lab-scale fixed-bed reactors operating at batch conditions with corrugated tubes as support media. It can be demonstrated that high micro-organisms-substrate ratios favor the degradation activity of the different anaerobic cultures, allowing the stable operation without lag-phases and giving better quality in effluent. The kinetic parameters obtained--maximum specific growth rates (mu(max)), non-biodegradable substrate (S(NB)) and "active or viable biomass" concentrations (X(V0))--were obtained by applying the Romero kinetic model [L.I. Romero, 1991. Desarrollo de un modelo matemático general para los procesos fermentativos, Cinética de la degradación anaerobia, Ph.D. Thesis, University of Cádiz (Spain), Serv. Pub. Univ. Cádiz], with COD as substrate and methane (CH4) as the main product of the anaerobic process. This method is suitable to calculate and to differentiate the main kinetic parameters of both the total anaerobic mixed culture and the methanogenic population. Comparison of experimental measured concentration of volatile attached solids (VS(att)) in both reactors with the estimated "active" biomass concentrations obtained by applying Romero kinetic model [L.I. Romero, 1991. Desarrollo de un modelo matemático general para los procesos fermentativos, Cinética de la degradación anaerobia, Ph.D. Thesis, University of Cádiz (Spain), Serv. Pub. Univ. Cádiz] shows that a large amount of inert matter is present in the fixed-bed reactor.

  2. Estimation of Transport and Kinetic Parameters of Vanadium Redox Batteries Using Static Cells

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lee, Seong Beom; Pratt, III, Harry D.; Anderson, Travis M.

    Mathematical models of Redox Flow Batteries (RFBs) can be used to analyze cell performance, optimize battery operation, and control the energy storage system efficiently. Among many other models, physics-based electrochemical models are capable of predicting internal states of the battery, such as temperature, state-of-charge, and state-of-health. In the models, estimating parameters is an important step that can study, analyze, and validate the models using experimental data. A common practice is to determine these parameters either through conducting experiments or based on the information available in the literature. However, it is not easy to investigate all proper parameters for the modelsmore » through this way, and there are occasions when important information, such as diffusion coefficients and rate constants of ions, has not been studied. Also, the parameters needed for modeling charge-discharge are not always available. In this paper, an efficient way to estimate parameters of physics-based redox battery models will be proposed. Furthermore, this paper also demonstrates that the proposed approach can study and analyze aspects of capacity loss/fade, kinetics, and transport phenomena of the RFB system.« less

  3. Estimation of Transport and Kinetic Parameters of Vanadium Redox Batteries Using Static Cells

    DOE PAGES

    Lee, Seong Beom; Pratt, III, Harry D.; Anderson, Travis M.; ...

    2018-03-27

    Mathematical models of Redox Flow Batteries (RFBs) can be used to analyze cell performance, optimize battery operation, and control the energy storage system efficiently. Among many other models, physics-based electrochemical models are capable of predicting internal states of the battery, such as temperature, state-of-charge, and state-of-health. In the models, estimating parameters is an important step that can study, analyze, and validate the models using experimental data. A common practice is to determine these parameters either through conducting experiments or based on the information available in the literature. However, it is not easy to investigate all proper parameters for the modelsmore » through this way, and there are occasions when important information, such as diffusion coefficients and rate constants of ions, has not been studied. Also, the parameters needed for modeling charge-discharge are not always available. In this paper, an efficient way to estimate parameters of physics-based redox battery models will be proposed. Furthermore, this paper also demonstrates that the proposed approach can study and analyze aspects of capacity loss/fade, kinetics, and transport phenomena of the RFB system.« less

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

    NASA Astrophysics Data System (ADS)

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

    2017-10-01

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

  5. Extracting surface diffusion coefficients from batch adsorption measurement data: application of the classic Langmuir kinetics model.

    PubMed

    Chu, Khim Hoong

    2017-11-09

    Surface diffusion coefficients may be estimated by fitting solutions of a diffusion model to batch kinetic data. For non-linear systems, a numerical solution of the diffusion model's governing equations is generally required. We report here the application of the classic Langmuir kinetics model to extract surface diffusion coefficients from batch kinetic data. The use of the Langmuir kinetics model in lieu of the conventional surface diffusion model allows derivation of an analytical expression. The parameter estimation procedure requires determining the Langmuir rate coefficient from which the pertinent surface diffusion coefficient is calculated. Surface diffusion coefficients within the 10 -9 to 10 -6  cm 2 /s range obtained by fitting the Langmuir kinetics model to experimental kinetic data taken from the literature are found to be consistent with the corresponding values obtained from the traditional surface diffusion model. The virtue of this simplified parameter estimation method is that it reduces the computational complexity as the analytical expression involves only an algebraic equation in closed form which is easily evaluated by spreadsheet computation.

  6. Improving the quality of parameter estimates obtained from slug tests

    USGS Publications Warehouse

    Butler, J.J.; McElwee, C.D.; Liu, W.

    1996-01-01

    The slug test is one of the most commonly used field methods for obtaining in situ estimates of hydraulic conductivity. Despite its prevalence, this method has received criticism from many quarters in the ground-water community. This criticism emphasizes the poor quality of the estimated parameters, a condition that is primarily a product of the somewhat casual approach that is often employed in slug tests. Recently, the Kansas Geological Survey (KGS) has pursued research directed it improving methods for the performance and analysis of slug tests. Based on extensive theoretical and field research, a series of guidelines have been proposed that should enable the quality of parameter estimates to be improved. The most significant of these guidelines are: (1) three or more slug tests should be performed at each well during a given test period; (2) two or more different initial displacements (Ho) should be used at each well during a test period; (3) the method used to initiate a test should enable the slug to be introduced in a near-instantaneous manner and should allow a good estimate of Ho to be obtained; (4) data-acquisition equipment that enables a large quantity of high quality data to be collected should be employed; (5) if an estimate of the storage parameter is needed, an observation well other than the test well should be employed; (6) the method chosen for analysis of the slug-test data should be appropriate for site conditions; (7) use of pre- and post-analysis plots should be an integral component of the analysis procedure, and (8) appropriate well construction parameters should be employed. Data from slug tests performed at a number of KGS field sites demonstrate the importance of these guidelines.

  7. Obtaining short-fiber orientation model parameters using non-lubricated squeeze flow

    NASA Astrophysics Data System (ADS)

    Lambert, Gregory; Wapperom, Peter; Baird, Donald

    2017-12-01

    Accurate models of fiber orientation dynamics during the processing of polymer-fiber composites are needed for the design work behind important automobile parts. All of the existing models utilize empirical parameters, but a standard method for obtaining them independent of processing does not exist. This study considers non-lubricated squeeze flow through a rectangular channel as a solution. A two-dimensional finite element method simulation of the kinematics and fiber orientation evolution along the centerline of a sample is developed as a first step toward a fully three-dimensional simulation. The model is used to fit to orientation data in a short-fiber-reinforced polymer composite after squeezing. Fiber orientation model parameters obtained in this study do not agree well with those obtained for the same material during startup of simple shear. This is attributed to the vastly different rates at which fibers orient during shearing and extensional flows. A stress model is also used to try to fit to experimental closure force data. Although the model can be tuned to the correct magnitude of the closure force, it does not fully recreate the transient behavior, which is attributed to the lack of any consideration for fiber-fiber interactions.

  8. Evaluation of kinetic constants of biomolecular interaction on optical surface plasmon resonance sensor with Newton Iteration Method

    NASA Astrophysics Data System (ADS)

    Zhao, Yuanyuan; Jiang, Guoliang; Hu, Jiandong; Hu, Fengjiang; Wei, Jianguang; Shi, Liang

    2010-10-01

    In the immunology, there are two important types of biomolecular interaction: antigens-antibodies and receptors-ligands. Monitoring the response rate and affinity of biomolecular interaction can help analyze the protein function, drug discover, genomics and proteomics research. Moreover the association rate constant and dissociation rate constant of receptors-ligands are the important parameters for the study of signal transmission between cells. Recent advances in bioanalyzer instruments have greatly simplified the measurement of the kinetics of molecular interactions. Non-destructive and real-time monitoring the response to evaluate the parameters between antigens and antibodies can be performed by using optical surface plasmon resonance (SPR) biosensor technology. This technology provides a quantitative analysis that is carried out rapidly with label-free high-throughput detection using the binding curves of antigens-antibodies. Consequently, the kinetic parameters of interaction between antigens and antibodies can be obtained. This article presents a low cost integrated SPR-based bioanalyzer (HPSPR-6000) designed by ourselves. This bioanalyzer is mainly composed of a biosensor TSPR1K23, a touch-screen monitor, a microprocessor PIC24F128, a microflow cell with three channels, a clamp and a photoelectric conversion device. To obtain the kinetic parameters, sensorgrams may be modeled using one of several binding models provided with BIAevaluation software 3.0, SensiQ or Autolab. This allows calculation of the association rate constant (ka) and the dissociation rate constant (kd). The ratio of ka to kd can be used to estimate the equilibrium constant. Another kind is the analysis software OriginPro, which can process the obtained data by nonlinear fitting and then get some correlative parameters, but it can't be embedded into the bioanalyzer, so the bioanalyzer don't support the use of OriginPro. This paper proposes a novel method to evaluate the kinetic parameters

  9. Solvolysis kinetics of three components of biomass using polyhydric alcohols as solvents.

    PubMed

    Shi, Yan; Xia, Xueying; Li, Jingdan; Wang, Jing; Zhao, Tiantian; Yang, Hongmin; Jiang, Jianchun; Jiang, Xiaoxiang

    2016-12-01

    The solvolysis behavior and reaction kinetics of the three components of biomass (cellulose, hemicelluloses and lignin) liquefied in polyhydric alcohols (PEG 400 or glycerol) were investigated in this paper. Three stages were observed during the solvolysis process and the main degradation stage could be further divided into two zones. The influences of solvents on the liquefaction process of three main components were compared. Based on Starink and Malek methods, kinetic parameters and mechanism functions were obtained. The derived average activation energy of cellulose, hemicellulose and lignin were 108.73, 95.66 and 94.13kJmol -1 in PEG 400, while the values were 102.16, 77.43 and 89.10kJmol -1 in glycerol, respectively. Higher efficiency was observed when using glycerol as solvent, which could be ascribed to the higher polarity value of glycerol. The conversion curves calculated with obtained mechanism models and kinetic parameters were in good agreement with the experimental data. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Fundamental electrode kinetics

    NASA Technical Reports Server (NTRS)

    Elder, J. P.

    1968-01-01

    Report presents the fundamentals of electrode kinetics and the methods used in evaluating the characteristic parameters of rapid-charge transfer processes at electrode-electrolyte interfaces. The concept of electrode kinetics is outlined, followed by the principles underlying the experimental techniques for the investigation of electrode kinetics.

  11. Non-Isothermal Kinetics.

    ERIC Educational Resources Information Center

    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)

  12. Malonic acid concentration as a control parameter in the kinetic analysis of the Belousov-Zhabotinsky reaction under batch conditions.

    PubMed

    Blagojević, Slavica M; Anić, Slobodan R; Cupić, Zeljko D; Pejić, Natasa D; Kolar-Anić, Ljiljana Z

    2008-11-28

    The influence of the initial malonic acid concentration [MA]0 (8.00 x 10(-3) < or = [MA]0 < or = 4.30 x 10(-2) mol dm(-3)) in the presence of bromate (6.20 x 10(-2) mol dm(-3)), bromide (1.50 x 10(-5) mol dm(-3)), sulfuric acid (1.00 mol dm(-3)) and cerium sulfate (2.50 x 10(-3) mol dm(-3)) on the dynamics and the kinetics of the Belousov-Zhabotinsky (BZ) reactions was examined under batch conditions at 30.0 degrees C. The kinetics of the BZ reaction was analyzed by the earlier proposed method convenient for the examinations of the oscillatory reactions. In the defined region of parameters where oscillograms with only large-amplitude relaxation oscillations appeared, the pseudo-first order of the overall malonic acid decomposition with a corresponding rate constant of 2.14 x 10(-2) min(-1) was established. The numerical results on the dynamics and kinetics of the BZ reaction, carried out by the known skeleton model including the Br2O species, were in good agreement with the experimental ones. The already found saddle node infinite period (SNIPER) bifurcation point in transition from a stable quasi-steady state to periodic orbits and vice versa is confirmed by both experimental and numerical investigations of the system under consideration. Namely, the large-amplitude relaxation oscillations with increasing periods between oscillations in approaching the bifurcation points at the beginning and the end of the oscillatory domain, together with excitability of the stable quasi-steady states in their vicinity are obtained.

  13. Development of an ESI-LC-MS-based assay for kinetic evaluation of Mycobacterium tuberculosis shikimate kinase activity and inhibition.

    PubMed

    Simithy, Johayra; Gill, Gobind; Wang, Yu; Goodwin, Douglas C; Calderón, Angela I

    2015-02-17

    A simple and reliable liquid chromatography-mass spectrometry (LC-MS) assay has been developed and validated for the kinetic characterization and evaluation of inhibitors of shikimate kinase from Mycobacterium tuberculosis (MtSK), a potential target for the development of novel antitubercular drugs. This assay is based on the direct determination of the reaction product shikimate-3-phosphate (S3P) using electrospray ionization (ESI) and a quadrupole time-of-flight (Q-TOF) detector. A comparative analysis of the kinetic parameters of MtSK obtained by the LC-MS assay with those obtained by a conventional UV-assay was performed. Kinetic parameters determined by LC-MS were in excellent agreement with those obtained from the UV assay, demonstrating the accuracy, and reliability of this method. The validated assay was successfully applied to the kinetic characterization of a known inhibitor of shikimate kinase; inhibition constants and mode of inhibition were accurately delineated with LC-MS.

  14. Automated chemical kinetic modeling via hybrid reactive molecular dynamics and quantum chemistry simulations.

    PubMed

    Döntgen, Malte; Schmalz, Felix; Kopp, Wassja A; Kröger, Leif C; Leonhard, Kai

    2018-06-13

    An automated scheme for obtaining chemical kinetic models from scratch using reactive molecular dynamics and quantum chemistry simulations is presented. This methodology combines the phase space sampling of reactive molecular dynamics with the thermochemistry and kinetics prediction capabilities of quantum mechanics. This scheme provides the NASA polynomial and modified Arrhenius equation parameters for all species and reactions that are observed during the simulation and supplies them in the ChemKin format. The ab initio level of theory for predictions is easily exchangeable and the presently used G3MP2 level of theory is found to reliably reproduce hydrogen and methane oxidation thermochemistry and kinetics data. Chemical kinetic models obtained with this approach are ready-to-use for, e.g., ignition delay time simulations, as shown for hydrogen combustion. The presented extension of the ChemTraYzer approach can be used as a basis for methodologically advancing chemical kinetic modeling schemes and as a black-box approach to generate chemical kinetic models.

  15. Fractional superstatistics from a kinetic approach

    NASA Astrophysics Data System (ADS)

    Ourabah, Kamel; Tribeche, Mouloud

    2018-03-01

    Through a kinetic approach, in which temperature fluctuations are taken into account, we obtain generalized fractional statistics interpolating between Fermi-Dirac and Bose-Einstein statistics. The latter correspond to the superstatistical analogues of the Polychronakos and Haldane-Wu statistics. The virial coefficients corresponding to these statistics are worked out and compared to those of an ideal two-dimensional anyon gas. It is shown that the obtained statistics reproduce correctly the second and third virial coefficients of an anyon gas. On this basis, a link is established between the statistical parameter and the strength of fluctuations. A further generalization is suggested by allowing the statistical parameter to fluctuate. As a by-product, superstatistics of ewkons, introduced recently to deal with dark energy [Phys. Rev. E 94, 062115 (2016), 10.1103/PhysRevE.94.062115], are also obtained within the same method.

  16. Mechanistic study of manganese-substituted glycerol dehydrogenase using a kinetic and thermodynamic analysis.

    PubMed

    Fang, Baishan; Niu, Jin; Ren, Hong; Guo, Yingxia; Wang, Shizhen

    2014-01-01

    Mechanistic insights regarding the activity enhancement of dehydrogenase by metal ion substitution were investigated by a simple method using a kinetic and thermodynamic analysis. By profiling the binding energy of both the substrate and product, the metal ion's role in catalysis enhancement was revealed. Glycerol dehydrogenase (GDH) from Klebsiella pneumoniae sp., which demonstrated an improvement in activity by the substitution of a zinc ion with a manganese ion, was used as a model for the mechanistic study of metal ion substitution. A kinetic model based on an ordered Bi-Bi mechanism was proposed considering the noncompetitive product inhibition of dihydroxyacetone (DHA) and the competitive product inhibition of NADH. By obtaining preliminary kinetic parameters of substrate and product inhibition, the number of estimated parameters was reduced from 10 to 4 for a nonlinear regression-based kinetic parameter estimation. The simulated values of time-concentration curves fit the experimental values well, with an average relative error of 11.5% and 12.7% for Mn-GDH and GDH, respectively. A comparison of the binding energy of enzyme ternary complex for Mn-GDH and GDH derived from kinetic parameters indicated that metal ion substitution accelerated the release of dioxyacetone. The metal ion's role in catalysis enhancement was explicated.

  17. An Analytical Approach to Obtaining JWL Parameters from Cylinder Tests

    NASA Astrophysics Data System (ADS)

    Sutton, Ben; Ferguson, James

    2015-06-01

    An analytical method for determining parameters for the JWL equation of state (EoS) from cylinder test data is described. This method is applied to four datasets obtained from two 20.3 mm diameter EDC37 cylinder tests. The calculated parameters and pressure-volume (p-V) curves agree with those produced by hydro-code modelling. The calculated Chapman-Jouguet (CJ) pressure is 38.6 GPa, compared to the model value of 38.3 GPa; the CJ relative volume is 0.729 for both. The analytical pressure-volume curves produced agree with the one used in the model out to the commonly reported expansion of 7 relative volumes, as do the predicted energies generated by integrating under the p-V curve. The calculated and model energies are 8.64 GPa and 8.76 GPa respectively.

  18. 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

    NASA Astrophysics Data System (ADS)

    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

  19. Intrinsic kinetic parameters of Thermococcus onnurineus NA1 strains and prediction of optimum carbon monoxide level for ideal bioreactor operation.

    PubMed

    Jeong, Yeseul; Jang, Nulee; Yasin, Muhammad; Park, Shinyoung; Chang, In Seop

    2016-02-01

    This study determines and compares the intrinsic kinetic parameters (Ks and Ki) of selected Thermococcus onnurineus NA1 strains (wild-type (WT), and mutants MC01, MC02, and WTC156T) using the substrate inhibition model. Ks and Ki values were used to find the optimum dissolved CO (CL) conditions inside the reactor. The results showed that in terms of the maximum specific CO consumption rates (qCO(max)) of WT, MC01, MC02, and WTC156T the optimum activities can be achieved by maintaining the CL levels at 0.56mM, 0.52mM, 0.58mM, and 0.75mM, respectively. The qCO(max) value of WTC156T at 0.75mM was found to be 1.5-fold higher than for the WT strain, confirming its superiority. Kinetic modeling was then used to predict the conditions required to maintain the optimum CL levels and high cell concentrations in the reactor, based on the kinetic parameters of the WTC156T strain. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Kinetic modelling of non-enzymatic browning and changes of physio-chemical parameters of peach juice during storage.

    PubMed

    Lyu, Jian; Liu, Xuan; Bi, Jinfeng; Wu, Xinye; Zhou, Linyan; Ruan, Weihong; Zhou, Mo; Jiao, Yi

    2018-03-01

    Kinetics of non-enzymatic browning and loss of free amino acids during different storage temperature (4, 25, 37 °C) were investigated. Changes of browning degree ( A 420 ), color parameters, Vitamin C ( V c ), free amino acids and 5-hydroxymethylfurfural (5-HMF) were analyzed to evaluate the non-enzymatic browning reactions, which were significantly affected by storage temperature. The lower temperature (4 °C) decreased the loss of V c and the generation of 5-HMF, but induce the highest loss of serine. At the end of storage, loss of serine, alanine and aspartic acid were mainly lost. Results showed that zero-order kinetic model ( R 2  > 0.859), the first-order model ( R 2  > 0.926) and the combined kinetic model ( R 2  > 0.916) were the most appropriate to describe the changes of a * and b * values, the degradation of V c and the changes of A 420 , L * and 5-HMF during different storage temperatures. These kinetic models can be applied for predicting and minimizing the non-enzymatic browning of fresh peach juice during storage.

  1. Impact of process parameters on the breakage kinetics of poorly water-soluble drugs during wet stirred media milling: a microhydrodynamic view.

    PubMed

    Afolabi, Afolawemi; Akinlabi, Olakemi; Bilgili, Ecevit

    2014-01-23

    Wet stirred media milling has proven to be a robust process for producing nanoparticle suspensions of poorly water-soluble drugs. As the process is expensive and energy-intensive, it is important to study the breakage kinetics, which determines the cycle time and production rate for a desired fineness. Although the impact of process parameters on the properties of final product suspensions has been investigated, scant information is available regarding their impact on the breakage kinetics. Here, we elucidate the impact of stirrer speed, bead concentration, and drug loading on the breakage kinetics via a microhydrodynamic model for the bead-bead collisions. Suspensions of griseofulvin, a model poorly water-soluble drug, were prepared in the presence of two stabilizers: hydroxypropyl cellulose and sodium dodecyl sulfate. Laser diffraction, scanning electron microscopy, and rheometry were used to characterize them. Various microhydrodynamic parameters including a newly defined milling intensity factor was calculated. An increase in either the stirrer speed or the bead concentration led to an increase in the specific energy and the milling intensity factor, consequently faster breakage. On the other hand, an increase in the drug loading led to a decrease in these parameters and consequently slower breakage. While all microhydrodynamic parameters provided significant physical insight, only the milling intensity factor was capable of explaining the influence of all parameters directly through its strong correlation with the process time constant. Besides guiding process optimization, the analysis rationalizes the preparation of a single high drug-loaded batch (20% or higher) instead of multiple dilute batches. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Pixel-based approach to assess contrast-enhanced ultrasound kinetics parameters for differential diagnosis of rheumatoid arthritis.

    PubMed

    Rizzo, Gaia; Raffeiner, Bernd; Coran, Alessandro; Ciprian, Luca; Fiocco, Ugo; Botsios, Costantino; Stramare, Roberto; Grisan, Enrico

    2015-07-01

    Inflammatory rheumatic diseases are the leading causes of disability and constitute a frequent medical disorder, leading to inability to work, high comorbidity, and increased mortality. The standard for diagnosing and differentiating arthritis is based on clinical examination, laboratory exams, and imaging findings, such as synovitis, bone edema, or joint erosions. Contrast-enhanced ultrasound (CEUS) examination of the small joints is emerging as a sensitive tool for assessing vascularization and disease activity. Quantitative assessment is mostly performed at the region of interest level, where the mean intensity curve is fitted with an exponential function. We showed that using a more physiologically motivated perfusion curve, and by estimating the kinetic parameters separately pixel by pixel, the quantitative information gathered is able to more effectively characterize the different perfusion patterns. In particular, we demonstrated that a random forest classifier based on pixelwise quantification of the kinetic contrast agent perfusion features can discriminate rheumatoid arthritis from different arthritis forms (psoriatic arthritis, spondyloarthritis, and arthritis in connective tissue disease) with an average accuracy of 97%. On the contrary, clinical evaluation (DAS28), semiquantitative CEUS assessment, serological markers, or region-based parameters do not allow such a high diagnostic accuracy.

  3. Pixel-based approach to assess contrast-enhanced ultrasound kinetics parameters for differential diagnosis of rheumatoid arthritis

    PubMed Central

    Rizzo, Gaia; Raffeiner, Bernd; Coran, Alessandro; Ciprian, Luca; Fiocco, Ugo; Botsios, Costantino; Stramare, Roberto; Grisan, Enrico

    2015-01-01

    Abstract. Inflammatory rheumatic diseases are the leading causes of disability and constitute a frequent medical disorder, leading to inability to work, high comorbidity, and increased mortality. The standard for diagnosing and differentiating arthritis is based on clinical examination, laboratory exams, and imaging findings, such as synovitis, bone edema, or joint erosions. Contrast-enhanced ultrasound (CEUS) examination of the small joints is emerging as a sensitive tool for assessing vascularization and disease activity. Quantitative assessment is mostly performed at the region of interest level, where the mean intensity curve is fitted with an exponential function. We showed that using a more physiologically motivated perfusion curve, and by estimating the kinetic parameters separately pixel by pixel, the quantitative information gathered is able to more effectively characterize the different perfusion patterns. In particular, we demonstrated that a random forest classifier based on pixelwise quantification of the kinetic contrast agent perfusion features can discriminate rheumatoid arthritis from different arthritis forms (psoriatic arthritis, spondyloarthritis, and arthritis in connective tissue disease) with an average accuracy of 97%. On the contrary, clinical evaluation (DAS28), semiquantitative CEUS assessment, serological markers, or region-based parameters do not allow such a high diagnostic accuracy. PMID:27014713

  4. 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.

    PubMed

    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.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Raposo, Maria, E-mail: mfr@fct.unl.pt; Monteiro Timóteo, Ana Rita; Ribeiro, Paulo A.

    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 solutionmore » 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.« less

  6. Water sorption equilibria and kinetics of henna leaves

    NASA Astrophysics Data System (ADS)

    Sghaier, Khamsa; Peczalski, Roman; Bagane, Mohamed

    2018-05-01

    In this work, firstly the sorption isotherms of henna leaves were determined using a dynamic vapor sorption ( DVS) device at 3 temperatures (30, 40, 50 °C). The equilibrium data were well fitted by the GAB model. Secondly, drying kinetics were measured using a pilot convective dryer for 3 air temperatures (same as above), 3 velocities (0.5, 1, 1.42 m/s) and 4 relative humidities (20, 30, 35, 40%). The drying kinetic coefficients were identified by fitting the DVS and pilot dryer data by Lewis semi-empirical model. In order to compare the obtained kinetic parameters with literature, the water diffusivities were also identified by fitting the data by the simplified solution of fickian diffusion equation. The identified kinetic coefficient was mainly dependent on air temperature and velocity what proved that it represented rather the external transfer and not the internal one.

  7. Compost mixture influence of interactive physical parameters on microbial kinetics and substrate fractionation.

    PubMed

    Mohajer, Ardavan; Tremier, Anne; Barrington, Suzelle; Teglia, Cecile

    2010-01-01

    Composting is a feasible biological treatment for the recycling of wastewater sludge as a soil amendment. The process can be optimized by selecting an initial compost recipe with physical properties that enhance microbial activity. The present study measured the microbial O(2) uptake rate (OUR) in 16 sludge and wood residue mixtures to estimate the kinetics parameters of maximum growth rate mu(m) and rate of organic matter hydrolysis K(h), as well as the initial biodegradable organic matter fractions present. The starting mixtures consisted of a wide range of moisture content (MC), waste to bulking agent (BA) ratio (W/BA ratio) and BA particle size, which were placed in a laboratory respirometry apparatus to measure their OUR over 4 weeks. A microbial model based on the activated sludge process was used to calculate the kinetic parameters and was found to adequately reproduced OUR curves over time, except for the lag phase and peak OUR, which was not represented and generally over-estimated, respectively. The maximum growth rate mu(m), was found to have a quadratic relationship with MC and a negative association with BA particle size. As a result, increasing MC up to 50% and using a smaller BA particle size of 8-12 mm was seen to maximize mu(m). The rate of hydrolysis K(h) was found to have a linear association with both MC and BA particle size. The model also estimated the initial readily biodegradable organic matter fraction, MB(0), and the slower biodegradable matter requiring hydrolysis, MH(0). The sum of MB(0) and MH(0) was associated with MC, W/BA ratio and the interaction between these two parameters, suggesting that O(2) availability was a key factor in determining the value of these two fractions. The study reinforced the idea that optimization of the physical characteristics of a compost mixture requires a holistic approach. 2010 Elsevier Ltd. All rights reserved.

  8. Kafirin adsorption on ion-exchange resins: isotherm and kinetic studies.

    PubMed

    Kumar, Prashant; Lau, Pei Wen; Kale, Sandeep; Johnson, Stuart; Pareek, Vishnu; Utikar, Ranjeet; Lali, Arvind

    2014-08-22

    Kafirin is a natural, hydrophobic and celiac safe prolamin protein obtained from sorghum seeds. Today kafirin is found to be useful in designing delayed delivery systems and coatings of pharmaceuticals and nutraceuticals where its purity is important and this can be obtained by adsorptive chromatography. This study is the first scientific insight into the isotherm and kinetic studies of kafirin adsorption on anion- and cation-exchange resins for practical applications in preparative scale chromatography. Adsorption isotherms of kafirin were determined for five anion- and two cation-exchange resins in batch systems. Isotherm parameters such as maximum binding capacity and dissociation constant were determined from Langmuir isotherm, and adsorptive capacity and affinity constant from Freundlich isotherm. Langmuir isotherm was found to fit the adsorption equilibrium data well. Batch uptake kinetics for kafirin adsorption on these resins was also carried out and critical parameters including the diffusion coefficient, film mass transfer coefficient, and Biot number for film-pore diffusion model were calculated. Both the isotherm and the kinetic parameters were considered for selection of appropriate resin for kafirin purification. UNOsphere Q (78.26 mg/ml) and Toyopearl SP-650M (57.4 mg/ml) were found to offer better kafirin binding capacities and interaction strength with excellent uptake kinetics under moderate operating conditions. With these adsorbents, film diffusion resistance was found to be major governing factor for adsorption (Bi<10 and δ<1). Based on designer objective function, UNOsphere Q was found be best adsorbent for binding of kafirin. The data presented is valuable for designing large scale preparative adsorptive chromatographic kafirin purification systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. A three-time-point method for assessing kinetic parameters of 64Cu-labeled Ramucirumab trapping in VEGFR-2 positive lung tumors.

    PubMed

    Laffon, Eric; Marthan, Roger

    2017-11-01

    To describe a three-time-point method for estimating kinetic parameters involved in 64 Cu-labeled Ramucirumab ( 64 Cu-NOTA-RamAb) trapping of VEGFR-2 positive lung tumors. Positron emission tomography (microPET) data of tumor-bearing mice for 64 Cu-NOTA-RamAb trapping in VEGFR-2 positive HCC4006 tumor were used, involving tissue activity measurements acquired at 3, 24 and 48 h post-injection, without and with administration of RamAb blocking dose. A kinetic model provided an analytical formula describing the tissue time-activity-curve, involving 64 Cu-NOTA-RamAb uptake (Ki), release rate constant (k R ) and fraction of free tracer in blood and interstitial volume (F). Fitting analytical formula outcomes on mean microPET data yielded values of the kinetic parameters: Ki = 0.0314/0.0123 gram of blood per hour per gram of tissue, k R  = 0.0387/0.0313 h -1 and F = 0.2075/0.2007 gram of blood per gram of tissue, without/with RamAb blocking dose, respectively (R = 0.99999 for the graph displaying microPET versus theoretical data; P < .01). Three independent kinetic parameters (Ki, k R and F) can be assessed from three data points acquired at early, mid and late imaging, i.e., at 3, 24 and 48 h post-injection, for further characterization of 64 Cu-NOTA-RamAb trapping in VEGFR-2 positive lung tumors. Copyright © 2017 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

  10. Characterization of 12 GnRH peptide agonists - a kinetic perspective.

    PubMed

    Nederpelt, Indira; Georgi, Victoria; Schiele, Felix; Nowak-Reppel, Katrin; Fernández-Montalván, Amaury E; IJzerman, Adriaan P; Heitman, Laura H

    2016-01-01

    Drug-target residence time is an important, yet often overlooked, parameter in drug discovery. Multiple studies have proposed an increased residence time to be beneficial for improved drug efficacy and/or longer duration of action. Currently, there are many drugs on the market targeting the gonadotropin-releasing hormone (GnRH) receptor for the treatment of hormone-dependent diseases. Surprisingly, the kinetic receptor-binding parameters of these analogues have not yet been reported. Therefore, this project focused on determining the receptor-binding kinetics of 12 GnRH peptide agonists, including many marketed drugs. A novel radioligand-binding competition association assay was developed and optimized for the human GnRH receptor with the use of a radiolabelled peptide agonist, [(125) I]-triptorelin. In addition to radioligand-binding studies, a homogeneous time-resolved FRET Tag-lite™ method was developed as an alternative assay for the same purpose. Two novel competition association assays were successfully developed and applied to determine the kinetic receptor-binding characteristics of 12 high-affinity GnRH peptide agonists. Results obtained from both methods were highly correlated. Interestingly, the binding kinetics of the peptide agonists were more divergent than their affinities with residence times ranging from 5.6 min (goserelin) to 125 min (deslorelin). Our research provides new insights by incorporating kinetic, next to equilibrium, binding parameters in current research and development that can potentially improve future drug discovery targeting the GnRH receptor. © 2015 The British Pharmacological Society.

  11. Revisiting gamma-ray burst afterglows with time-dependent parameters

    NASA Astrophysics Data System (ADS)

    Yang, Chao; Zou, Yuan-Chuan; Chen, Wei; Liao, Bin; Lei, Wei-Hua; Liu, Yu

    2018-02-01

    The relativistic external shock model of gamma-ray burst (GRB) afterglows has been established with five free parameters, i.e., the total kinetic energy E, the equipartition parameters for electrons {{ε }}{{e}} and for the magnetic field {{ε }}{{B}}, the number density of the environment n and the index of the power-law distribution of shocked electrons p. A lot of modified models have been constructed to consider the variety of GRB afterglows, such as: the wind medium environment by letting n change with radius, the energy injection model by letting kinetic energy change with time and so on. In this paper, by assuming all four parameters (except p) change with time, we obtain a set of formulas for the dynamics and radiation, which can be used as a reference for modeling GRB afterglows. Some interesting results are obtained. For example, in some spectral segments, the radiated flux density does not depend on the number density or the profile of the environment. As an application, through modeling the afterglow of GRB 060607A, we find that it can be interpreted in the framework of the time dependent parameter model within a reasonable range.

  12. Ultrafast Carbon Dioxide Sorption Kinetics Using Lithium Silicate Nanowires.

    PubMed

    Nambo, Apolo; He, Juan; Nguyen, Tu Quang; Atla, Veerendra; Druffel, Thad; Sunkara, Mahendra

    2017-06-14

    In this paper, the Li 4 SiO 4 nanowires (NWs) were shown to be promising for CO 2 capture with ultrafast kinetics. Specifically, the nanowire powders exhibited an uptake of 0.35 g g -1 of CO 2 at an ultrafast adsorption rate of 0.22 g g -1 min -1 at 650-700 °C. Lithium silicate (Li 4 SiO 4 ) nanowires and nanopowders were synthesized using a "solvo-plasma" technique involving plasma oxidation of silicon precursors mixed with lithium hydroxide. The kinetic parameter values (k) extracted from sorption kinetics obtained using NW powders are 1 order of magnitude higher than those previously reported for the Li 4 SiO 4 -CO 2 reaction system. The time scales for CO 2 sorption using nanowires are approximately 3 min and two orders magnitude faster compared to those obtained using lithium silicate powders with spherical morphologies and aggregates. Furthermore, Li 4 SiO 4 nanowire powders showed reversibility through sorption-desorption cycles indicating their suitability for CO 2 capture applications. All of the morphologies of Li 4 SiO 4 powders exhibited a double exponential behavior in the adsorption kinetics indicating two distinct time constants for kinetic and the mass transfer limited regimes.

  13. Nonisothermal Carbothermal Reduction Kinetics of Titanium-Bearing Blast Furnace Slag

    NASA Astrophysics Data System (ADS)

    Hu, Mengjun; Wei, Ruirui; Hu, Meilong; Wen, Liangying; Ying, Fangqing

    2018-05-01

    The kinetics of carbothermal reduction of titanium-bearing blast furnace (BF) slag has been studied by thermogravimetric analysis and quadrupole mass spectrometry. The kinetic parameters (activation energy, preexponential factor, and reaction model function) were determined using the Flynn-Wall-Ozawa and Šatava-Šesták methods. The results indicated that reduction of titanium-bearing BF slag can be divided into two stages, namely reduction of phases containing iron and gasification of carbon (< 1095°C), followed by reduction of phases containing titanium (> 1095°C). CO2 was the main off-gas in the temperature range of 530-700°C, whereas CO became the main off-gas when the temperature was greater than 900°C. The activation energy calculated using the Flynn-Wall-Ozawa method was 221.2 kJ/mol. D4 is the mechanism function for carbothermal reduction of titanium-bearing BF slag. Meanwhile, a nonisothermal reduction model is proposed based on the obtained kinetic parameters.

  14. Lamtoro charcoal (l. leucocephala) as bioreductor in nickel laterite reduction: performance and kinetics study

    NASA Astrophysics Data System (ADS)

    Petrus, H. T. B. M.; Diga, A.; Rhamdani, A. R.; Warmada, I. W.; Yuliansyah, A. T.; Perdana, I.

    2017-04-01

    The performance and kinetic of nickel laterite reduction were studied. In this work, the reduction of nickel laterite ores by anthracite coal, representing the high-grade carbon content matter, and lamtoro charcoal, representing the bioreductor, were conducted in air and CO2 atmosphere, within the temperature ranged from 800°C and 1000°C. XRD analysis was applied to observe the performance of anthracite and lamtoro as a reductor. Two models were applied, sphere particle geometry model and Ginstling-Brounhstein diffusion model, to study the kinetic parameters. The results indicated that the type of reductant and the reduction atmosphere used greatly influence the kinetic parameters. The obtained values of activation energy vary in the range of 13.42-18.12 kcal/mol.

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

    NASA Astrophysics Data System (ADS)

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

    2018-04-01

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

  16. 40 CFR 60.2945 - Is there a minimum amount of operating parameter monitoring data I must obtain?

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... parameter monitoring data I must obtain? 60.2945 Section 60.2945 Protection of Environment ENVIRONMENTAL... Operator Training and Qualification Monitoring § 60.2945 Is there a minimum amount of operating parameter monitoring data I must obtain? (a) Except for monitor malfunctions, associated repairs, and required quality...

  17. 40 CFR 60.2945 - Is there a minimum amount of operating parameter monitoring data I must obtain?

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... parameter monitoring data I must obtain? 60.2945 Section 60.2945 Protection of Environment ENVIRONMENTAL... Operator Training and Qualification Monitoring § 60.2945 Is there a minimum amount of operating parameter monitoring data I must obtain? (a) Except for monitor malfunctions, associated repairs, and required quality...

  18. 40 CFR 60.2945 - Is there a minimum amount of operating parameter monitoring data I must obtain?

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... parameter monitoring data I must obtain? 60.2945 Section 60.2945 Protection of Environment ENVIRONMENTAL... Operator Training and Qualification Monitoring § 60.2945 Is there a minimum amount of operating parameter monitoring data I must obtain? (a) Except for monitor malfunctions, associated repairs, and required quality...

  19. Gymnasium-based unsupervised exercise maintains benefits in oxygen uptake kinetics obtained following supervised training in type 2 diabetes.

    PubMed

    Macananey, Oscar; O'Shea, Donal; Warmington, Stuart A; Green, Simon; Egaña, Mikel

    2012-08-01

    Supervised exercise (SE) in patients with type 2 diabetes improves oxygen uptake kinetics at the onset of exercise. Maintenance of these improvements, however, has not been examined when supervision is removed. We explored if potential improvements in oxygen uptake kinetics following a 12-week SE that combined aerobic and resistance training were maintained after a subsequent 12-week unsupervised exercise (UE). The involvement of cardiac output (CO) in these improvements was also tested. Nineteen volunteers with type 2 diabetes were recruited. Oxygen uptake kinetics and CO (inert gas rebreathing) responses to constant-load cycling at 50% ventilatory threshold (V(T)), 80% V(T), and mid-point between V(T) and peak workload (50% Δ) were examined at baseline (on 2 occasions) and following each 12-week training period. Participants decided to exercise at a local gymnasium during the UE. Thirteen subjects completed all the interventions. The time constant of phase 2 of oxygen uptake was significantly faster (p < 0.05) post-SE and post-UE compared with baseline at 50% V(T) (17.3 ± 10.7 s and 17.5 ± 5.9 s vs. 29.9 ± 10.7 s), 80% V(T) (18.9 ± 4.7 and 20.9 ± 8.4 vs. 34.3 ± 12.7s), and 50% Δ (20.4 ± 8.2 s and 20.2 ± 6.0 s vs. 27.6 ± 3.7 s). SE also induced faster heart rate kinetics at all 3 intensities and a larger increase in CO at 30 s in relation to 240 s at 80% V(T); and these responses were maintained post-UE. Unsupervised exercise maintained benefits in oxygen uptake kinetics obtained during a supervised exercise in subjects with diabetes, and these benefits were associated with a faster dynamic response of heart rate after training.

  20. A Study of the Optimal Model of the Flotation Kinetics of Copper Slag from Copper Mine BOR

    NASA Astrophysics Data System (ADS)

    Stanojlović, Rodoljub D.; Sokolović, Jovica M.

    2014-10-01

    In this study the effect of mixtures of copper slag and flotation tailings from copper mine Bor, Serbia on the flotation results of copper recovery and flotation kinetics parameters in a batch flotation cell has been investigated. By simultaneous adding old flotation tailings in the ball mill at the rate of 9%, it is possible to increase copper recovery for about 20%. These results are compared with obtained copper recovery of pure copper slag. The results of batch flotation test were fitted by MatLab software for modeling the first-order flotation kinetics in order to determine kinetics parameters and define an optimal model of the flotation kinetics. Six kinetic models are tested on the batch flotation copper recovery against flotation time. All models showed good correlation, however the modified Kelsall model provided the best fit.

  1. Removal of ibuprofen, naproxen and carbamazepine in aqueous solution onto natural clay: equilibrium, kinetics, and thermodynamic study

    NASA Astrophysics Data System (ADS)

    Khazri, Hassen; Ghorbel-Abid, Ibtissem; Kalfat, Rafik; Trabelsi-Ayadi, Malika

    2017-10-01

    This study aimed to describe the adsorption of three pharmaceuticals compounds (ibuprofen, naproxen and carbamazepine) onto natural clay on the basis of equilibrium parameters such as a function of time, effect of pH, varying of the concentration and the temperature. Adsorption kinetic data were modeled using the Lagergren's first-order and the pseudo-second-order kinetic equations. The kinetic results of adsorption are described better using the pseudo-second order model. The isotherm results were tested in the Langmuir, Freundlich and Dubinin-Radushkevich models. The thermodynamic parameters obtained indicate that the adsorption of pharmaceuticals on the clay is a spontaneous and endothermic process.

  2. Esterification of fatty acids using nylon-immobilized lipase in n-hexane: kinetic parameters and chain-length effects.

    PubMed

    Zaidi, A; Gainer, J L; Carta, G; Mrani, A; Kadiri, T; Belarbi, Y; Mir, A

    2002-02-28

    The esterification of long-chain fatty acids in n-hexane catalyzed by nylon-immobilized lipase from Candida rugosa has been investigated. Butyl oleate (22 carbon atoms), oleyl butyrate (22 carbon atoms) and oleyl oleate (36 carbon atoms) were produced at maximum reaction rates of approximately equal to 60 mmol h(-1) g(-1) immobilized enzyme when the substrates were present in equimolar proportions at an initial concentration of 0.6 mol l(-1). The observed kinetic behavior of all the esterification reactions is found to follow a ping-pong bi-bi mechanism with competitive inhibition by both substrates. The effect of the chain-length of the fatty acids and the alcohols could be correlated to some mechanistic models, in accordance with the calculated kinetic parameters.

  3. Microbial community composition of a multi-stage moving bed biofilm reactor and its interaction with kinetic model parameters estimation.

    PubMed

    Wang, Xiaodong; Bi, Xuejun; Hem, Lars John; Ratnaweera, Harsha

    2018-07-15

    Microbial community diversity determines the function of each chamber of multi-stage moving bed biofilm reactor (MBBR) systems. How the microbial community data can be further used to serve wastewater treatment process modelling and optimization has been rarely studied. In this study, a MBBR system was set up to investigate the microbial community diversity of biofilm in each functional chamber. The compositions of microbial community of biofilm from different chambers of MBBR were quantified by high-throughput sequencing. Significantly higher proportion of autotrophs were found in the second aerobic chamber (15.4%), while 4.3% autotrophs were found in the first aerobic chamber. Autotrophs in anoxic chamber were negligible. Moreover, ratios of active heterotrophic biomass and autotrophic biomass (X H /X A ) were obtained by performing respiration tests. By setting heterotroph/autotroph ratios obtained from sequencing analysis equal to X H /X A , a novel approach for kinetic model parameters estimation was developed. This work not only investigated microbial community of MBBR system, but also it provided an approach to make further use of molecular microbiology analysis results. Copyright © 2018 Elsevier Ltd. All rights reserved.

  4. Thermoluminescence glow curve deconvolution and trapping parameters determination of dysprosium doped magnesium borate glass

    NASA Astrophysics Data System (ADS)

    Salama, E.; Soliman, H. A.

    2018-07-01

    In this paper, thermoluminescence glow curves of gamma irradiated magnesium borate glass doped with dysprosium were studied. The number of interfering peaks and in turn the number of electron trap levels are determined using the Repeated Initial Rise (RIR) method. At different heating rates (β), the glow curves were deconvoluted into two interfering peaks based on the results of RIR method. Kinetic parameters such as trap depth, kinetic order (b) and frequency factor (s) for each electron trap level is determined using the Peak Shape (PS) method. The obtained results indicated that, the magnesium borate glass doped with dysprosium has two electron trap levels with the average depth energies of 0.63 and 0.79 eV respectively. These two traps have second order kinetic and are formed at low temperature region. The obtained results due to the glow curve analysis could be used to explain some observed properties such as, high thermal fading and light sensitivity for such thermoluminescence material. In this work, systematic procedures to determine the kinetic parameters of any thermoluminescence material are successfully introduced.

  5. Oxidative desulfurization: kinetic modelling.

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  7. Lunar tidal acceleration obtained from satellite-derived ocean tide parameters

    NASA Technical Reports Server (NTRS)

    Goad, C. C.; Douglas, B. C.

    1978-01-01

    One hundred sets of mean elements of GEOS-3 computed at 2-day intervals yielded observation equations for the M sub 2 ocean tide from the long periodic variations of the inclination and node of the orbit. The 2nd degree Love number was given the value k sub 2 = 0.30 and the solid tide phase angle was taken to be zero. Combining obtained equations with results for the satellite 1967-92A gives the M sub 2 ocean tide parameter values. Under the same assumption of zero solid tide phase lag, the lunar tidal acceleration was found mostly due to the C sub 22 term in the expansion of the M sub 2 tide with additional small contributions from the 0 sub 1 and N sub 2 tides. Using Lambeck's (1975) estimates for the latter, the obtained acceleration in lunar longitudal in excellent agreement with the most recent determinations from ancient and modern astronomical data.

  8. Associations between timing in the baseball pitch and shoulder kinetics, elbow kinetics, and ball speed.

    PubMed

    Urbin, M A; Fleisig, Glenn S; Abebe, Asheber; Andrews, James R

    2013-02-01

    A baseball pitcher's ability to maximize ball speed while avoiding shoulder and elbow injuries is an important determinant of a successful career. Pitching injuries are attributed to microtrauma brought about by the repetitive stress of high-magnitude shoulder and elbow kinetics. Over a number of pitches, variations in timing peak angular velocities of trunk segment rotations will be significantly associated with ball speed and upper extremity kinetic parameters. Descriptive laboratory study. Kinematic and kinetic data were derived from 9 to 15 fastball pitches performed by 16 active, healthy collegiate (n = 8) and professional (n = 8) pitchers via 3-dimensional motion capture (240 Hz). Each pitch was decomposed into 4 phases corresponding to the time between peak angular velocities of sequential body segment rotations. Four mixed models were used to evaluate which phases varied significantly in relation to ball speed, peak shoulder proximal force, peak shoulder internal rotation torque, and peak elbow varus torque. Mixed-model parameter coefficient estimates were used to quantify the influence of these variations in timing on ball speed and upper extremity kinetics. All 4 mixed models were significant (P < .05). The time from stride-foot contact to peak pelvis angular velocity varied significantly in relation to all upper extremity kinetic parameters and ball speed. Increased time in this phase correlated with decreases in all parameters. Decreased ball speed also correlated with increased time between peak upper torso and elbow extension angular velocities. Decreased shoulder proximal force also correlated with increased time between peak pelvis and upper torso angular velocities. There are specific phases that vary in relation to ball speed and upper extremity kinetic parameters, reinforcing the importance of effectively and consistently timing segmental interactions. For the specific interactions that varied significantly, increased phase times were associated

  9. A means to estimate thermal and kinetic parameters of coal dust layer from hot surface ignition tests.

    PubMed

    Park, Haejun; Rangwala, Ali S; Dembsey, Nicholas A

    2009-08-30

    A method to estimate thermal and kinetic parameters of Pittsburgh seam coal subject to thermal runaway is presented using the standard ASTM E 2021 hot surface ignition test apparatus. Parameters include thermal conductivity (k), activation energy (E), coupled term (QA) of heat of reaction (Q) and pre-exponential factor (A) which are required, but rarely known input values to determine the thermal runaway propensity of a dust material. Four different dust layer thicknesses: 6.4, 12.7, 19.1 and 25.4mm, are tested, and among them, a single steady state dust layer temperature profile of 12.7 mm thick dust layer is used to estimate k, E and QA. k is calculated by equating heat flux from the hot surface layer and heat loss rate on the boundary assuming negligible heat generation in the coal dust layer at a low hot surface temperature. E and QA are calculated by optimizing a numerically estimated steady state dust layer temperature distribution to the experimentally obtained temperature profile of a 12.7 mm thick dust layer. Two unknowns, E and QA, are reduced to one from the correlation of E and QA obtained at criticality of thermal runaway. The estimated k is 0.1 W/mK matching the previously reported value. E ranges from 61.7 to 83.1 kJ/mol, and the corresponding QA ranges from 1.7 x 10(9) to 4.8 x 10(11)J/kg s. The mean values of E (72.4 kJ/mol) and QA (2.8 x 10(10)J/kg s) are used to predict the critical hot surface temperatures for other thicknesses, and good agreement is observed between measured and experimental values. Also, the estimated E and QA ranges match the corresponding ranges calculated from the multiple tests method and values reported in previous research.

  10. Kinetic Analysis for Macrocyclizations Involving Anionic Template at the Transition State

    PubMed Central

    Martí-Centelles, Vicente; Burguete, M. Isabel; Luis, Santiago V.

    2012-01-01

    Several kinetic models for the macrocyclization of a C2 pseudopeptide with a dihalide through a SN2 reaction have been developed. These models not only focus on the kinetic analysis of the main macrocyclization reaction, but also consider the competitive oligomerization/polymerization processes yielding undesired oligomeric/polymeric byproducts. The effect of anions has also been included in the kinetic models, as they can act as catalytic templates in the transition state reducing and stabilizing the transition state. The corresponding differential equation systems for each kinetic model can be solved numerically. Through a comprehensive analysis of these results, it is possible to obtain a better understanding of the different parameters that are involved in the macrocyclization reaction mechanism and to develop strategies for the optimization of the desired processes. PMID:22666148

  11. Rotation and kinetic modifications of the tokamak ideal-wall pressure limit.

    PubMed

    Menard, J E; Wang, Z; Liu, Y; Bell, R E; Kaye, S M; Park, J-K; Tritz, K

    2014-12-19

    The impact of toroidal rotation, energetic ions, and drift-kinetic effects on the tokamak ideal wall mode stability limit is considered theoretically and compared to experiment for the first time. It is shown that high toroidal rotation can be an important destabilizing mechanism primarily through the angular velocity shear; non-Maxwellian fast ions can also be destabilizing, and drift-kinetic damping can potentially offset these destabilization mechanisms. These results are obtained using the unique parameter regime accessible in the spherical torus NSTX of high toroidal rotation speed relative to the thermal and Alfvén speeds and high kinetic pressure relative to the magnetic pressure. Inclusion of rotation and kinetic effects significantly improves agreement between measured and predicted ideal stability characteristics and may provide new insight into tearing mode triggering.

  12. Correlation of air void parameters obtained by linear traverse with freeze-thaw durability.

    DOT National Transportation Integrated Search

    1983-01-01

    The correlations obtainable from comparisons of the various air void parameters with the freeze-thaw durability of concretes are listed. It is shown that correlations are no better when only small voids are used than when the total void content is us...

  13. Kinetics of nickel electrodeposition from low electrolyte concentration and at a narrow interelectrode gap

    NASA Astrophysics Data System (ADS)

    Widayatno, Tri

    2015-12-01

    Electrodeposition of nickel onto copper in a system of low Ni2+ concentration and at a narrow interelectrode gap has been carried out. This electrochemical system was required for maskless pattern transfer through electroplating (Enface technique). Kinetics of Electrochemical reaction of Nickel is relatively slow, where such electrochemical system has never been used in this technology. Study on the kinetics of the electrochemical reaction of nickel in such system is essential due to the fact that the quality of an electrodeposited nickel is affected by kinetics. Analytical and graphical methods were utilised to determine kinetic parameters. The kinetic model was approximated by Butler-Volmer and j-η equation. Kinetic parameters such as exchange current density (j0) and charge transfer coefficient (α) were also graphically determined using the plot of η vs. log|j| known as Tafel plot. The polarisation data for an unstirred 0.19 M nickel sulfamate solution at 0.5 mV/s scan rate and RDE system was used. The results indicate that both methods are fairly accurate. For the analytical, the Tafel slope, the exchange current density, and charge transfer coefficient were found to be 149 mV/dec, 1.60 × 10-4 mA/cm2, and 0.39 respectively, whilst for the graphical method were 159 mV/dec, 3.16 × 10-4 mA/cm2, and 0.37. The kinetics parameters in this current study were also compared to those in literature. Significant differences were observed which might be due to the effect of composition and concentration of the electrolytes, operating temperature, and pH leading to the different reaction mechanism. However, the results obtained in this work are in the range of acceptable values. These kinetic parameters will then be used in further study of nickel deposition by modelling and simulation

  14. Pile noise experiment in MINERVE reactor to estimate kinetic parameters using various data processing methods

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Geslot, Benoit; Gruel, Adrien; Pepino, Alexandra

    2015-07-01

    MINERVE is a two-zone pool type zero power reactor operated by CEA (Cadarache, France). Kinetic parameters of the core (prompt neutron decay constant, delayed neutron fraction, generation time) have been recently measured using various pile noise experimental techniques, namely Feynman-α, Rossi-α and Cohn-α. Results are discussed and compared to each other's. The measurement campaign has been conducted in the framework of a tri-partite collaboration between CEA, SCK.CEN and PSI. Results presented in this paper were obtained thanks to a time-stamping acquisition system developed by CEA. PSI performed simultaneous measurements which are presented in a companion paper. Signals come from twomore » high efficiency fission chambers located in the graphite reflector next to the core driver zone. Experiments were conducted at critical state with a reactor power of 0.2 W. The core integral fission rate is obtained from a calibrated miniature fission chamber located at the center of the core. Other results obtained in two sub-critical configurations will be presented elsewhere. Best estimate delayed neutron fraction comes from the Cohn-α method: 747 ± 15 pcm (1σ). In this case, the prompt decay constant is 79 ± 0.5 s{sup -1} and the generation time is 94.5 ± 0.7 μs. Other methods give consistent results within the confidence intervals. Experimental results are compared to calculated values obtained from a full 3D core modeling with the CEA-developed Monte Carlo code TRIPOLI4.9 associated with its continuous energy JEFF3.1.1-based library. A very good agreement is observed for the calculated delayed neutron fraction (748.7 ± 0.4 pcm at 1σ), that is a difference of -0.3% with the experiment. On the contrary, a 10% discrepancy is observed for the calculated generation time (104.4 ± 0.1 μs at 1σ). (authors)« less

  15. iSCHRUNK--In Silico Approach to Characterization and Reduction of Uncertainty in the Kinetic Models of Genome-scale Metabolic Networks.

    PubMed

    Andreozzi, Stefano; Miskovic, Ljubisa; Hatzimanikatis, Vassily

    2016-01-01

    Accurate determination of physiological states of cellular metabolism requires detailed information about metabolic fluxes, metabolite concentrations and distribution of enzyme states. Integration of fluxomics and metabolomics data, and thermodynamics-based metabolic flux analysis contribute to improved understanding of steady-state properties of metabolism. However, knowledge about kinetics and enzyme activities though essential for quantitative understanding of metabolic dynamics remains scarce and involves uncertainty. Here, we present a computational methodology that allow us to determine and quantify the kinetic parameters that correspond to a certain physiology as it is described by a given metabolic flux profile and a given metabolite concentration vector. Though we initially determine kinetic parameters that involve a high degree of uncertainty, through the use of kinetic modeling and machine learning principles we are able to obtain more accurate ranges of kinetic parameters, and hence we are able to reduce the uncertainty in the model analysis. We computed the distribution of kinetic parameters for glucose-fed E. coli producing 1,4-butanediol and we discovered that the observed physiological state corresponds to a narrow range of kinetic parameters of only a few enzymes, whereas the kinetic parameters of other enzymes can vary widely. Furthermore, this analysis suggests which are the enzymes that should be manipulated in order to engineer the reference state of the cell in a desired way. The proposed approach also sets up the foundations of a novel type of approaches for efficient, non-asymptotic, uniform sampling of solution spaces. Copyright © 2015 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

  16. Complete Proteomic-Based Enzyme Reaction and Inhibition Kinetics Reveal How Monolignol Biosynthetic Enzyme Families Affect Metabolic Flux and Lignin in Populus trichocarpa[W

    PubMed Central

    Wang, Jack P.; Naik, Punith P.; Chen, Hsi-Chuan; Shi, Rui; Lin, Chien-Yuan; Liu, Jie; Shuford, Christopher M.; Li, Quanzi; Sun, Ying-Hsuan; Tunlaya-Anukit, Sermsawat; Williams, Cranos M.; Muddiman, David C.; Ducoste, Joel J.; Sederoff, Ronald R.; Chiang, Vincent L.

    2014-01-01

    We established a predictive kinetic metabolic-flux model for the 21 enzymes and 24 metabolites of the monolignol biosynthetic pathway using Populus trichocarpa secondary differentiating xylem. To establish this model, a comprehensive study was performed to obtain the reaction and inhibition kinetic parameters of all 21 enzymes based on functional recombinant proteins. A total of 104 Michaelis-Menten kinetic parameters and 85 inhibition kinetic parameters were derived from these enzymes. Through mass spectrometry, we obtained the absolute quantities of all 21 pathway enzymes in the secondary differentiating xylem. This extensive experimental data set, generated from a single tissue specialized in wood formation, was used to construct the predictive kinetic metabolic-flux model to provide a comprehensive mathematical description of the monolignol biosynthetic pathway. The model was validated using experimental data from transgenic P. trichocarpa plants. The model predicts how pathway enzymes affect lignin content and composition, explains a long-standing paradox regarding the regulation of monolignol subunit ratios in lignin, and reveals novel mechanisms involved in the regulation of lignin biosynthesis. This model provides an explanation of the effects of genetic and transgenic perturbations of the monolignol biosynthetic pathway in flowering plants. PMID:24619611

  17. Combustion and kinetic parameters estimation of torrefied pine, acacia and Miscanthus giganteus using experimental and modelling techniques.

    PubMed

    Wilk, Małgorzata; Magdziarz, Aneta; Gajek, Marcin; Zajemska, Monika; Jayaraman, Kandasamy; Gokalp, Iskender

    2017-11-01

    A novel approach, linking both experiments and modelling, was applied to obtain a better understanding of combustion characteristics of torrefied biomass. Therefore, Pine, Acacia and Miscanthus giganteus have been investigated under 260°C, 1h residence time and argon atmosphere. A higher heating value and carbon content corresponding to a higher fixed carbon, lower volatile matter, moisture content, and ratio O/C were obtained for all torrefied biomass. TGA analysis was used in order to proceed with the kinetics study and Chemkin calculations. The kinetics analysis demonstrated that the torrefaction process led to a decrease in Ea compared to raw biomass. The average Ea of pine using the KAS method changed from 169.42 to 122.88kJ/mol. The changes in gaseous products of combustion were calculated by Chemkin, which corresponded with the TGA results. The general conclusion based on these investigations is that torrefaction improves the physical and chemical properties of biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Quantitative production of compound I from a cytochrome P450 enzyme at low temperatures. Kinetics, activation parameters, and kinetic isotope effects for oxidation of benzyl alcohol.

    PubMed

    Wang, Qin; Sheng, Xin; Horner, John H; Newcomb, Martin

    2009-08-05

    Cytochrome P450 enzymes are commonly thought to oxidize substrates via an iron(IV)-oxo porphyrin radical cation transient termed Compound I, but kinetic studies of P450 Compounds I are essentially nonexistent. We report production of Compound I from cytochrome P450 119 (CYP119) in high conversion from the corresponding Compound II species at low temperatures in buffer mixtures containing 50% glycerol by photolysis with 365 nm light from a pulsed lamp. Compound I was studied as a reagent in oxidations of benzyl alcohol and its benzylic mono- and dideuterio isotopomers. Pseudo-first-order rate constants obtained at -50 degrees C with concentrations of substrates between 1.0 and 6.0 mM displayed saturation kinetics that gave binding constants for the substrate in the Compound I species (K(bind)) and first-order rate constants for the oxidation reactions (k(ox)). Representative results are K(bind) = 214 M(-1) and k(ox) = 0.48 s(-1) for oxidation of benzyl alcohol. For the dideuterated substrate C(6)H(5)CD(2)OH, kinetics were studied between -50 and -25 degrees C, and a van't Hoff plot for complexation and an Arrhenius plot for the oxidation reaction were constructed. The H/D kinetic isotope effects (KIEs) at -50 degrees C were resolved into a large primary KIE (P = 11.9) and a small, inverse secondary KIE (S = 0.96). Comparison of values extrapolated to 22 degrees C of both the rate constant for oxidation of C(6)H(5)CD(2)OH and the KIE for the nondeuterated and dideuterated substrates to values obtained previously in laser flash photolysis experiments suggested that tunneling could be a significant component of the total rate constant at -50 degrees C.

  19. Rock Cutting Depth Model Based on Kinetic Energy of Abrasive Waterjet

    NASA Astrophysics Data System (ADS)

    Oh, Tae-Min; Cho, Gye-Chun

    2016-03-01

    Abrasive waterjets are widely used in the fields of civil and mechanical engineering for cutting a great variety of hard materials including rocks, metals, and other materials. Cutting depth is an important index to estimate operating time and cost, but it is very difficult to predict because there are a number of influential variables (e.g., energy, geometry, material, and nozzle system parameters). In this study, the cutting depth is correlated to the maximum kinetic energy expressed in terms of energy (i.e., water pressure, water flow rate, abrasive feed rate, and traverse speed), geometry (i.e., standoff distance), material (i.e., α and β), and nozzle system parameters (i.e., nozzle size, shape, and jet diffusion level). The maximum kinetic energy cutting depth model is verified with experimental test data that are obtained using one type of hard granite specimen for various parameters. The results show a unique curve for a specific rock type in a power function between cutting depth and maximum kinetic energy. The cutting depth model developed here can be very useful for estimating the process time when cutting rock using an abrasive waterjet.

  20. Relationships between PEMFC Cathode Kinetic Losses and Contaminants’ Dipole Moment and Adsorption Energy on Pt

    DOE PAGES

    St-Pierre, Jean; Zhai, Yunfeng; Ge, Junjie

    2016-01-05

    A database summarizing the effects of 21 contaminants on the performance of proton exchange membrane fuel cells (PEMFCs) was used to examine relationships between cathode kinetic losses and contaminant physicochemical parameters. Impedance spectroscopy data were employed to obtain oxygen reduction kinetic resistances by fitting data in the 10-158 Hz range to a simplified equivalent circuit. The contaminant dipole moment and the adsorption energy of the contaminant on a Pt surface were chosen as parameters. Dipole moments did not correlate with dimensionless cathode kinetic resistances. In contrast, adsorption energies were quantitatively and linearly correlated with minimum dimensionless cathode kinetic resistances. Contaminantsmore » influence the oxygen reduction for contaminant adsorption energies smaller than -24.5 kJ mol -1, a value near the high limit of the adsorption energy of O 2 on Pt. Dimensionless cathode kinetic resistances linearly increase with decreasing O 2 adsorption energies below -24.5 kJ mol -1. Measured total cell voltage losses are mostly larger than the cathode kinetic losses calculated from kinetic resistance changes, which indicates the existence of other sources of performance degradation. Modifications to the experimental procedure are proposed to ensure that data are comparable on a similar basis and improve the correlation between contaminant adsorption energy and kinetic cell voltage losses.« less

  1. Relationships between PEMFC Cathode Kinetic Losses and Contaminants’ Dipole Moment and Adsorption Energy on Pt

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    St-Pierre, Jean; Zhai, Yunfeng; Ge, Junjie

    A database summarizing the effects of 21 contaminants on the performance of proton exchange membrane fuel cells (PEMFCs) was used to examine relationships between cathode kinetic losses and contaminant physicochemical parameters. Impedance spectroscopy data were employed to obtain oxygen reduction kinetic resistances by fitting data in the 10-158 Hz range to a simplified equivalent circuit. The contaminant dipole moment and the adsorption energy of the contaminant on a Pt surface were chosen as parameters. Dipole moments did not correlate with dimensionless cathode kinetic resistances. In contrast, adsorption energies were quantitatively and linearly correlated with minimum dimensionless cathode kinetic resistances. Contaminantsmore » influence the oxygen reduction for contaminant adsorption energies smaller than -24.5 kJ mol -1, a value near the high limit of the adsorption energy of O 2 on Pt. Dimensionless cathode kinetic resistances linearly increase with decreasing O 2 adsorption energies below -24.5 kJ mol -1. Measured total cell voltage losses are mostly larger than the cathode kinetic losses calculated from kinetic resistance changes, which indicates the existence of other sources of performance degradation. Modifications to the experimental procedure are proposed to ensure that data are comparable on a similar basis and improve the correlation between contaminant adsorption energy and kinetic cell voltage losses.« less

  2. Quantitative and predictive model of kinetic regulation by E. coli TPP riboswitches

    PubMed Central

    Guedich, Sondés; Puffer-Enders, Barbara; Baltzinger, Mireille; Hoffmann, Guillaume; Da Veiga, Cyrielle; Jossinet, Fabrice; Thore, Stéphane; Bec, Guillaume; Ennifar, Eric; Burnouf, Dominique; Dumas, Philippe

    2016-01-01

    ABSTRACT Riboswitches are non-coding elements upstream or downstream of mRNAs that, upon binding of a specific ligand, regulate transcription and/or translation initiation in bacteria, or alternative splicing in plants and fungi. We have studied thiamine pyrophosphate (TPP) riboswitches regulating translation of thiM operon and transcription and translation of thiC operon in E. coli, and that of THIC in the plant A. thaliana. For all, we ascertained an induced-fit mechanism involving initial binding of the TPP followed by a conformational change leading to a higher-affinity complex. The experimental values obtained for all kinetic and thermodynamic parameters of TPP binding imply that the regulation by A. thaliana riboswitch is governed by mass-action law, whereas it is of kinetic nature for the two bacterial riboswitches. Kinetic regulation requires that the RNA polymerase pauses after synthesis of each riboswitch aptamer to leave time for TPP binding, but only when its concentration is sufficient. A quantitative model of regulation highlighted how the pausing time has to be linked to the kinetic rates of initial TPP binding to obtain an ON/OFF switch in the correct concentration range of TPP. We verified the existence of these pauses and the model prediction on their duration. Our analysis also led to quantitative estimates of the respective efficiency of kinetic and thermodynamic regulations, which shows that kinetically regulated riboswitches react more sharply to concentration variation of their ligand than thermodynamically regulated riboswitches. This rationalizes the interest of kinetic regulation and confirms empirical observations that were obtained by numerical simulations. PMID:26932506

  3. Quantitative and predictive model of kinetic regulation by E. coli TPP riboswitches.

    PubMed

    Guedich, Sondés; Puffer-Enders, Barbara; Baltzinger, Mireille; Hoffmann, Guillaume; Da Veiga, Cyrielle; Jossinet, Fabrice; Thore, Stéphane; Bec, Guillaume; Ennifar, Eric; Burnouf, Dominique; Dumas, Philippe

    2016-01-01

    Riboswitches are non-coding elements upstream or downstream of mRNAs that, upon binding of a specific ligand, regulate transcription and/or translation initiation in bacteria, or alternative splicing in plants and fungi. We have studied thiamine pyrophosphate (TPP) riboswitches regulating translation of thiM operon and transcription and translation of thiC operon in E. coli, and that of THIC in the plant A. thaliana. For all, we ascertained an induced-fit mechanism involving initial binding of the TPP followed by a conformational change leading to a higher-affinity complex. The experimental values obtained for all kinetic and thermodynamic parameters of TPP binding imply that the regulation by A. thaliana riboswitch is governed by mass-action law, whereas it is of kinetic nature for the two bacterial riboswitches. Kinetic regulation requires that the RNA polymerase pauses after synthesis of each riboswitch aptamer to leave time for TPP binding, but only when its concentration is sufficient. A quantitative model of regulation highlighted how the pausing time has to be linked to the kinetic rates of initial TPP binding to obtain an ON/OFF switch in the correct concentration range of TPP. We verified the existence of these pauses and the model prediction on their duration. Our analysis also led to quantitative estimates of the respective efficiency of kinetic and thermodynamic regulations, which shows that kinetically regulated riboswitches react more sharply to concentration variation of their ligand than thermodynamically regulated riboswitches. This rationalizes the interest of kinetic regulation and confirms empirical observations that were obtained by numerical simulations.

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

    PubMed

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

    2017-08-01

    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 3 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 the 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.

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

    PubMed

    Nagy, Péter

    2013-05-01

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

  6. Hybrid Biodegradable Hydrogels Obtained from Nanoclay and Carboxymethylcellulose Polysaccharide: Hydrophilic, Kinetic, Spectroscopic and Morphological Properties.

    PubMed

    Nascimento, Denis W S; de Moura, Márcia R; Mattoso, Luiz H C; Aouada, Fauze A

    2017-01-01

    In this paper, series of novel nanocomposite hydrogels based on polyacrylamide (PAAm), carboxymethylcellulose (CMC) and nanoclay were synthesized. Hydrophilic, kinetic, spectroscopic and morphological properties were investigated as function of their constituents. Spectroscopic properties confirmed the obtaining of the nanocomposites. It was also observed that the nanocomposites have walls of pores with a more rugged morphology compared with the morphology of the hydrogel without clay, contributing to repel the water molecules. Besides, the results showed that the velocity and quantity of water uptake may be controlled by adjusting of matrix rigidity, i.e., nanoclay content into polymeric matrix. This behavior is required to future application in agriculture fields, specifically as carrier vehicle in controlled release of agrochemicals. Thus, these nanocomposites have technological application.

  7. Characterization of 12 GnRH peptide agonists – a kinetic perspective

    PubMed Central

    Nederpelt, Indira; Georgi, Victoria; Schiele, Felix; Nowak‐Reppel, Katrin; Fernández‐Montalván, Amaury E.; IJzerman, Adriaan P.

    2015-01-01

    Background and Purpose Drug‐target residence time is an important, yet often overlooked, parameter in drug discovery. Multiple studies have proposed an increased residence time to be beneficial for improved drug efficacy and/or longer duration of action. Currently, there are many drugs on the market targeting the gonadotropin‐releasing hormone (GnRH) receptor for the treatment of hormone‐dependent diseases. Surprisingly, the kinetic receptor‐binding parameters of these analogues have not yet been reported. Therefore, this project focused on determining the receptor‐binding kinetics of 12 GnRH peptide agonists, including many marketed drugs. Experimental Approach A novel radioligand‐binding competition association assay was developed and optimized for the human GnRH receptor with the use of a radiolabelled peptide agonist, [125I]‐triptorelin. In addition to radioligand‐binding studies, a homogeneous time‐resolved FRET Tag‐lite™ method was developed as an alternative assay for the same purpose. Key Results Two novel competition association assays were successfully developed and applied to determine the kinetic receptor‐binding characteristics of 12 high‐affinity GnRH peptide agonists. Results obtained from both methods were highly correlated. Interestingly, the binding kinetics of the peptide agonists were more divergent than their affinities with residence times ranging from 5.6 min (goserelin) to 125 min (deslorelin). Conclusions and Implications Our research provides new insights by incorporating kinetic, next to equilibrium, binding parameters in current research and development that can potentially improve future drug discovery targeting the GnRH receptor. PMID:26398856

  8. Kinetic and thermodynamic parameters for thermal denaturation of ovine milk lactoferrin determined by its loss of immunoreactivity.

    PubMed

    Navarro, F; Harouna, S; Calvo, M; Pérez, M D; Sánchez, L

    2015-07-01

    Lactoferrin is a protein with important biological functions that can be obtained from milk and by-products derived from the dairy industry, such as whey. Although bovine lactoferrin has been extensively studied, ovine lactoferrin is not quite as well known. In the present study, the effect of several heat treatments in 3 different media, over a temperature range from 66 to 75°C, has been studied on lactoferrin isolated from sheep milk. Denaturation of lactoferrin was determined by measuring its immunoreactivity with specific polyclonal antibodies. Kinetic and thermodynamic parameters obtained indicate that lactoferrin denatures by heat more rapidly in whey than in phosphate buffer or milk. The value of activation energy found for the denaturation process of lactoferrin when treated in whey is higher (390kJ/mol) than that obtained in milk (194kJ/mol) or phosphate buffer (179kJ/mol). This indicates that a great amount of energy is necessary to start denaturation of ovine lactoferrin, probably due to the interaction of this protein with other whey proteins. The changes in the hydrophobicity of lactoferrin after heat treatments were determined by fluorescence measurement using acrylamide. The decrease in the hydrophobicity constant was very small for the treatments from 66 to 75°C, up to 20min, which indicates that lactoferrin conformation did not experienced a great change. The results obtained in this study permit the prediction of behavior of ovine lactoferrin under several heat treatments and show that high-temperature, short-time pasteurization (72°C, 15 s) does not cause loss of its immunoreactivity and, consequently, would not affect its conformation and biological activity. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  9. Differential effects on enzyme stability and kinetic parameters of mutants related to human triosephosphate isomerase deficiency.

    PubMed

    Cabrera, Nallely; Torres-Larios, Alfredo; García-Torres, Itzhel; Enríquez-Flores, Sergio; Perez-Montfort, Ruy

    2018-06-01

    Human triosephosphate isomerase (TIM) deficiency is a very rare disease, but there are several mutations reported to be causing the illness. In this work, we produced nine recombinant human triosephosphate isomerases which have the mutations reported to produce TIM deficiency. These enzymes were characterized biophysically and biochemically to determine their kinetic and stability parameters, and also to substitute TIM activity in supporting the growth of an Escherichia coli strain lacking the tim gene. Our results allowed us to rate the deleteriousness of the human TIM mutants based on the type and severity of the alterations observed, to classify four "unknown severity mutants" with altered residues in positions 62, 72, 122 and 154 and to explain in structural terms the mutation V231M, the most affected mutant from the kinetic point of view and the only homozygous mutation reported besides E104D. Copyright © 2018 Elsevier B.V. All rights reserved.

  10. Kinetic modeling of kraft delignification of Eucalyptus globulus

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Santos, A.; Rodriguez, F.; Gilarranz, M.A.

    1997-10-01

    A kinetic model for the kraft pulping delignification of Eucalyptus globulus is proposed. This model is discriminated among some kinetic expressions often used in the literature, and the kinetic parameters are determined by fitting of experimental results. A total of 25 isothermal experiments at liquor-to-wood ratios of 50 and 5 L/kg have been carried out. Initial, bulk, and residual delignification stages have been observed during the lignin removal, the transitions being, referring to the lignin initial content, about 82 and 3%. Carbohydrate removal and effective alkali-metal and hydrosulfide consumption have been related with the lignin removal by means of effectivemore » stoichiometric coefficients for each stage, coefficients also being calculated by fitting of the experimental data. The kinetic model chosen has been used to simulate typical kraft pulping experiments carried out at nonisothermal conditions, using a temperature ramp. The model yields simulated values close to those obtained experimentally for the wood studied and also ably reproduces the trends of the literature data.« less

  11. Characterization of metal adsorption kinetic properties in batch and fixed-bed reactors.

    PubMed

    Chen, J Paul; Wang, Lin

    2004-01-01

    Copper adsorption kinetic properties in batch and fixed-bed reactors were studied in this paper. The isothermal adsorption experiments showed that the copper adsorption capacity of a granular activated carbon (Filtrasorb 200) increased when ionic strength was higher. The presence of EDTA diminished the adsorption. An intraparticle diffusion model and a fixed-bed model were successfully used to describe the batch kinetic and fixed-bed operation behaviors. The kinetics became faster when the solution pH was not controlled, implying that the surface precipitation caused some metal uptake. The external mass transfer coefficient, the diffusivity and the dispersion coefficient were obtained from the modeling. It was found that both external mass transfer and dispersion coefficients increased when the flow rate was higher. Finally effects of kinetic parameters on simulation of fixed-bed operation were conducted.

  12. Maximum likelihood estimation of protein kinetic parameters under weak assumptions from unfolding force spectroscopy experiments

    NASA Astrophysics Data System (ADS)

    Aioanei, Daniel; Samorì, Bruno; Brucale, Marco

    2009-12-01

    Single molecule force spectroscopy (SMFS) is extensively used to characterize the mechanical unfolding behavior of individual protein domains under applied force by pulling chimeric polyproteins consisting of identical tandem repeats. Constant velocity unfolding SMFS data can be employed to reconstruct the protein unfolding energy landscape and kinetics. The methods applied so far require the specification of a single stretching force increase function, either theoretically derived or experimentally inferred, which must then be assumed to accurately describe the entirety of the experimental data. The very existence of a suitable optimal force model, even in the context of a single experimental data set, is still questioned. Herein, we propose a maximum likelihood (ML) framework for the estimation of protein kinetic parameters which can accommodate all the established theoretical force increase models. Our framework does not presuppose the existence of a single force characteristic function. Rather, it can be used with a heterogeneous set of functions, each describing the protein behavior in the stretching time range leading to one rupture event. We propose a simple way of constructing such a set of functions via piecewise linear approximation of the SMFS force vs time data and we prove the suitability of the approach both with synthetic data and experimentally. Additionally, when the spontaneous unfolding rate is the only unknown parameter, we find a correction factor that eliminates the bias of the ML estimator while also reducing its variance. Finally, we investigate which of several time-constrained experiment designs leads to better estimators.

  13. Callus Growth Kinetics of Physic Nut (Jatropha curcas L.) and Content of Fatty Acids from Crude Oil Obtained In Vitro.

    PubMed

    da Luz Costa, Jefferson; da Silva, André Luís Lopes; Bier, Mário César Jucoski; Brondani, Gilvano Ebling; Gollo, André Luiz; Letti, Luiz Alberto Junior; Erasmo, Eduardo Andrea Lemus; Soccol, Carlos Ricardo

    2015-06-01

    The callus growth kinetics allows identifying the appropriate moment for callus pealing and monitoring the accumulation of primary and secondary metabolites. The physic nut (Jatropha curcas L.) is a plant species used for biofuel production due to its high oil content; however, this plant presents a great amount of bioactive compounds which can be useful for industry. The aim of this research was to establish a calli growth curve and to evaluate the fatty acid profile of crude oil extracted from callus. The callus growth kinetics presented a sigmoid standard curve with six distinct phases: lag, exponential, linear, deceleration, stationary, and decline. Total soluble sugars were higher at the inoculation day. Reducing sugars were higher at the inoculation day and at the 80th day. The highest percentage of ethereal extract (oil content) was obtained at the 120th day of culture, reaching 18 % of crude oil from the callus. The calli produced medium-chain and long-chain fatty acids (from 10 to 18 carbon atoms). The palmitic acid was the fatty acid with the highest proportion in oil (55.4 %). The lipid profile obtained in callus oil was different from the seed oil profile.

  14. Kinetics of MDR Transport in Tumor-Initiating Cells

    PubMed Central

    Koshkin, Vasilij; Yang, Burton B.; Krylov, Sergey N.

    2013-01-01

    Multidrug resistance (MDR) driven by ABC (ATP binding cassette) membrane transporters is one of the major causes of treatment failure in human malignancy. MDR capacity is thought to be unevenly distributed among tumor cells, with higher capacity residing in tumor-initiating cells (TIC) (though opposite finding are occasionally reported). Functional evidence for enhanced MDR of TICs was previously provided using a “side population” assay. This assay estimates MDR capacity by a single parameter - cell’s ability to retain fluorescent MDR substrate, so that cells with high MDR capacity (“side population”) demonstrate low substrate retention. In the present work MDR in TICs was investigated in greater detail using a kinetic approach, which monitors MDR efflux from single cells. Analysis of kinetic traces obtained allowed for the estimation of both the velocity (V max) and affinity (K M) of MDR transport in single cells. In this way it was shown that activation of MDR in TICs occurs in two ways: through the increase of V max in one fraction of cells, and through decrease of K M in another fraction. In addition, kinetic data showed that heterogeneity of MDR parameters in TICs significantly exceeds that of bulk cells. Potential consequences of these findings for chemotherapy are discussed. PMID:24223908

  15. Kinetic Analysis of Benign and Malignant Breast Lesions With Ultrafast Dynamic Contrast-Enhanced MRI: Comparison With Standard Kinetic Assessment.

    PubMed

    Abe, Hiroyuki; Mori, Naoko; Tsuchiya, Keiko; Schacht, David V; Pineda, Federico D; Jiang, Yulei; Karczmar, Gregory S

    2016-11-01

    The purposes of this study were to evaluate diagnostic parameters measured with ultrafast MRI acquisition and with standard acquisition and to compare diagnostic utility for differentiating benign from malignant lesions. Ultrafast acquisition is a high-temporal-resolution (7 seconds) imaging technique for obtaining 3D whole-breast images. The dynamic contrast-enhanced 3-T MRI protocol consists of an unenhanced standard and an ultrafast acquisition that includes eight contrast-enhanced ultrafast images and four standard images. Retrospective assessment was performed for 60 patients with 33 malignant and 29 benign lesions. A computer-aided detection system was used to obtain initial enhancement rate and signal enhancement ratio (SER) by means of identification of a voxel showing the highest signal intensity in the first phase of standard imaging. From the same voxel, the enhancement rate at each time point of the ultrafast acquisition and the AUC of the kinetic curve from zero to each time point of ultrafast imaging were obtained. There was a statistically significant difference between benign and malignant lesions in enhancement rate and kinetic AUC for ultrafast imaging and also in initial enhancement rate and SER for standard imaging. ROC analysis showed no significant differences between enhancement rate in ultrafast imaging and SER or initial enhancement rate in standard imaging. Ultrafast imaging is useful for discriminating benign from malignant lesions. The differential utility of ultrafast imaging is comparable to that of standard kinetic assessment in a shorter study time.

  16. Microwave Assisted Enzymatic Kinetic Resolution of (±)-1-Phenyl-2-propyn-1-ol in Nonaqueous Media

    PubMed Central

    Devendran, Saravanan; Yadav, Ganapati D.

    2014-01-01

    Kinetic resolution of 1-phenyl-2-propyn-1-ol, an important chiral synthon, was studied through trans-esterification with acyl acetate to investigate synergism between microwave irradiation and enzyme catalysis. Lipases from different microbial origins were employed for the kinetic resolution of (R/S)-1-phenyl-2-propyn-1-ol, among which Candida antarctica lipase B, immobilized on acrylic resin (Novozym 435), was found to be the best catalyst in n-hexane as solvent. Vinyl acetate was the most effective among different acyl esters studied. The effect of various parameters was studied in a systematic manner. Definite synergism between microwave and enzyme was observed. The initial rate was improved around 1.28 times under microwave irradiation than conventional heating. Under optimum conditions, maximum conversion (48.78%) and high enantiomeric excess (93.25%) were obtained in 2 h. From modeling studies, it is concluded that the reaction follows the Ping-Pong bi-bi mechanism with dead end alcohol inhibition. Kinetic parameters were obtained by using nonlinear regression. This process is green, clean, and easily scalable as compared to the chemical process. PMID:24707487

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

    PubMed

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

    2017-02-23

    Changing of CH 4 oxidation potential and biological characteristics with CH 4 concentration was studied in a landfill cover soil reactor (LCSR). The maximum rate of CH 4 oxidation reached 32.40 mol d -1 m -2 by providing sufficient O 2 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 CH 4 and O 2 . The values of [Formula: see text] (0.93-2.29%) and [Formula: see text] (140-524 nmol kg soil-DW -1 ·s -1 ) increased with CH 4 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 CH 4 concentration. These findings provide information for assessing CH 4 oxidation potential and changing of biological characteristics in landfill cover soil.

  18. Numerical methods for solving moment equations in kinetic theory of neuronal network dynamics

    NASA Astrophysics Data System (ADS)

    Rangan, Aaditya V.; Cai, David; Tao, Louis

    2007-02-01

    Recently developed kinetic theory and related closures for neuronal network dynamics have been demonstrated to be a powerful theoretical framework for investigating coarse-grained dynamical properties of neuronal networks. The moment equations arising from the kinetic theory are a system of (1 + 1)-dimensional nonlinear partial differential equations (PDE) on a bounded domain with nonlinear boundary conditions. The PDEs themselves are self-consistently specified by parameters which are functions of the boundary values of the solution. The moment equations can be stiff in space and time. Numerical methods are presented here for efficiently and accurately solving these moment equations. The essential ingredients in our numerical methods include: (i) the system is discretized in time with an implicit Euler method within a spectral deferred correction framework, therefore, the PDEs of the kinetic theory are reduced to a sequence, in time, of boundary value problems (BVPs) with nonlinear boundary conditions; (ii) a set of auxiliary parameters is introduced to recast the original BVP with nonlinear boundary conditions as BVPs with linear boundary conditions - with additional algebraic constraints on the auxiliary parameters; (iii) a careful combination of two Newton's iterates for the nonlinear BVP with linear boundary condition, interlaced with a Newton's iterate for solving the associated algebraic constraints is constructed to achieve quadratic convergence for obtaining the solutions with self-consistent parameters. It is shown that a simple fixed-point iteration can only achieve a linear convergence for the self-consistent parameters. The practicability and efficiency of our numerical methods for solving the moment equations of the kinetic theory are illustrated with numerical examples. It is further demonstrated that the moment equations derived from the kinetic theory of neuronal network dynamics can very well capture the coarse-grained dynamical properties of

  19. Targeted estimation of nuisance parameters to obtain valid statistical inference.

    PubMed

    van der Laan, Mark J

    2014-01-01

    In order to obtain concrete results, we focus on estimation of the treatment specific mean, controlling for all measured baseline covariates, based on observing independent and identically distributed copies of a random variable consisting of baseline covariates, a subsequently assigned binary treatment, and a final outcome. The statistical model only assumes possible restrictions on the conditional distribution of treatment, given the covariates, the so-called propensity score. Estimators of the treatment specific mean involve estimation of the propensity score and/or estimation of the conditional mean of the outcome, given the treatment and covariates. In order to make these estimators asymptotically unbiased at any data distribution in the statistical model, it is essential to use data-adaptive estimators of these nuisance parameters such as ensemble learning, and specifically super-learning. Because such estimators involve optimal trade-off of bias and variance w.r.t. the infinite dimensional nuisance parameter itself, they result in a sub-optimal bias/variance trade-off for the resulting real-valued estimator of the estimand. We demonstrate that additional targeting of the estimators of these nuisance parameters guarantees that this bias for the estimand is second order and thereby allows us to prove theorems that establish asymptotic linearity of the estimator of the treatment specific mean under regularity conditions. These insights result in novel targeted minimum loss-based estimators (TMLEs) that use ensemble learning with additional targeted bias reduction to construct estimators of the nuisance parameters. In particular, we construct collaborative TMLEs (C-TMLEs) with known influence curve allowing for statistical inference, even though these C-TMLEs involve variable selection for the propensity score based on a criterion that measures how effective the resulting fit of the propensity score is in removing bias for the estimand. As a particular special

  20. Identifying mechanical property parameters of planetary soil using in-situ data obtained from exploration rovers

    NASA Astrophysics Data System (ADS)

    Ding, Liang; Gao, Haibo; Liu, Zhen; Deng, Zongquan; Liu, Guangjun

    2015-12-01

    Identifying the mechanical property parameters of planetary soil based on terramechanics models using in-situ data obtained from autonomous planetary exploration rovers is both an important scientific goal and essential for control strategy optimization and high-fidelity simulations of rovers. However, identifying all the terrain parameters is a challenging task because of the nonlinear and coupling nature of the involved functions. Three parameter identification methods are presented in this paper to serve different purposes based on an improved terramechanics model that takes into account the effects of slip, wheel lugs, etc. Parameter sensitivity and coupling of the equations are analyzed, and the parameters are grouped according to their sensitivity to the normal force, resistance moment and drawbar pull. An iterative identification method using the original integral model is developed first. In order to realize real-time identification, the model is then simplified by linearizing the normal and shearing stresses to derive decoupled closed-form analytical equations. Each equation contains one or two groups of soil parameters, making step-by-step identification of all the unknowns feasible. Experiments were performed using six different types of single-wheels as well as a four-wheeled rover moving on planetary soil simulant. All the unknown model parameters were identified using the measured data and compared with the values obtained by conventional experiments. It is verified that the proposed iterative identification method provides improved accuracy, making it suitable for scientific studies of soil properties, whereas the step-by-step identification methods based on simplified models require less calculation time, making them more suitable for real-time applications. The models have less than 10% margin of error comparing with the measured results when predicting the interaction forces and moments using the corresponding identified parameters.

  1. [Upper extremity kinetics and energy expenditure during walker-assisted gait in children with cerebral palsy].

    PubMed

    Konop, Katherine A; Strifling, Kelly M B; Wang, Mei; Cao, Kevin; Eastwood, Daniel; Jackson, Scott; Ackman, Jeffrey; Altiok, Haluk; Schwab, Jeffrey; Harris, Gerald F

    2009-01-01

    We evaluated the relationships between upper extremity (UE) kinetics and the energy expenditure index during anterior and posterior walker-assisted gait in children with spastic diplegic cerebral palsy (CP). Ten children (3 boys, 7 girls; mean age 12.1 years; range 8 to 18 years) with spastic diplegic CP, who ambulated with a walker underwent gait analyses that included UE kinematics and kinetics. Upper extremity kinetics were obtained using instrumented walker handles. Energy expenditure index was obtained using the heart rate method (EEIHR) by subtracting resting heart rate from walking heart rate, and dividing by the walking speed. Correlations were sought between the kinetic variables and the EEIHR and temporal and stride parameters. In general, anterior walker use was associated with a higher EEIHR. Several kinetic variables correlated well with temporal and stride parameters, as well as the EEIHR. All of the significant correlations (r>0.80; p<0.005) occurred during anterior walker use and involved joint reaction forces (JRF) rather than moments. Some variables showed multiple strong correlations during anterior walker use, including the medial JRF in the wrist, the posterior JRF in the elbow, and the inferior and superior JRFs in the shoulder. The observed correlations may indicate a relationship between the force used to advance the body forward within the walker frame and an increased EEIHR. More work is needed to refine the correlations, and to explore relationships with other variables, including the joint kinematics.

  2. Comparison of petroleum generation kinetics by isothermal hydrous and nonisothermal open-system pyrolysis

    USGS Publications Warehouse

    Lewan, M.D.; Ruble, T.E.

    2002-01-01

    This study compares kinetic parameters determined by open-system pyrolysis and hydrous pyrolysis using aliquots of source rocks containing different kerogen types. Kinetic parameters derived from these two pyrolysis methods not only differ in the conditions employed and products generated, but also in the derivation of the kinetic parameters (i.e., isothermal linear regression and non-isothermal nonlinear regression). Results of this comparative study show that there is no correlation between kinetic parameters derived from hydrous pyrolysis and open-system pyrolysis. Hydrous-pyrolysis kinetic parameters determine narrow oil windows that occur over a wide range of temperatures and depths depending in part on the organic-sulfur content of the original kerogen. Conversely, open-system kinetic parameters determine broad oil windows that show no significant differences with kerogen types or their organic-sulfur contents. Comparisons of the kinetic parameters in a hypothetical thermal-burial history (2.5 ??C/my) show open-system kinetic parameters significantly underestimate the extent and timing of oil generation for Type-US kerogen and significantly overestimate the extent and timing of petroleum formation for Type-I kerogen compared to hydrous pyrolysis kinetic parameters. These hypothetical differences determined by the kinetic parameters are supported by natural thermal-burial histories for the Naokelekan source rock (Type-IIS kerogen) in the Zagros basin of Iraq and for the Green River Formation (Type-I kerogen) in the Uinta basin of Utah. Differences in extent and timing of oil generation determined by open-system pyrolysis and hydrous pyrolysis can be attributed to the former not adequately simulating natural oil generation conditions, products, and mechanisms.

  3. Characterization of the cytochrome P450 enzymes and enzyme kinetic parameters for metabolism of BVT.2938 using different in vitro systems.

    PubMed

    Baranczewski, Pawel; Edlund, Per Olof; Postlind, Hans

    2006-03-18

    An important step in the drug development process is identification of enzymes responsible for metabolism of drug candidates and determination of enzyme kinetic parameters. These data are used to increase understanding of the pharmacokinetics and possible metabolic-based drug interactions of drug candidates. The aim of the present study was to characterize the cytochrome P450 enzymes and enzyme kinetic parameters for metabolism of BVT.2938 [1-(3-{2-[(2-ethoxy-3-pyridinyl)oxy]ethoxy}-2-pyrazinyl)-2(R)-methylpiperazine], a potent and selective 5HT2c-receptor agonist. The enzyme kinetic parameters were determined for formation of three main metabolites of BVT.2938 using human liver microsomes and expressed cytochrome P450 (CYP) isoforms. The major metabolite was formed by hydroxylation of the pyridine ring (CL(int)=27 microl/mgmin), and was catalysed by both CYP2D6*1 and CYP1A1, with K(m) values corresponding to 1.4 and 2.7 microM, respectively. The results from enzyme kinetic studies were confirmed by incubation of BVT.2938 in the presence of the chemical inhibitor of CYP2D6*1, quinidine. Quinidine inhibited the formation of the major metabolite by approximately 90%. Additionally, studies with recombinant expressed CYP isoforms from rat indicated that formation of the major metabolite of BVT.2938 was catalysed by CYP2D2. This result was further confirmed by experiments with liver slices from different rat strains, where the formation of the metabolite correlated with phenotype of CYP2D2 isoform (Sprague-Dawley male, extensive; Dark Agouti male, intermediate; Dark Agouti female, poor metabolizer). The present study showed that the major metabolite of BVT.2938 is formed by hydroxylation of the pyridine ring and catalysed by CYP2D6*1. CYP1A1 is also involved in this reaction and its role in extra-hepatic metabolism of BVT.2938 might be significant.

  4. On the Convenience of Using a Computer Simulation to Teach Enzyme Kinetics to Undergraduate Students with Biological Chemistry-Related Curricula

    ERIC Educational Resources Information Center

    Gonzalez-Cruz, Javier; Rodriguez-Sotres, Rogelio; Rodriguez-Penagos, Mireya

    2003-01-01

    Enzyme kinetics is a difficult subject for students to learn and for tutors to teach. During the practicals included in the biochemical courses at the Faculty of Chemistry of Universidad Nacional Autonoma de Mexico, we found that the students acquire good training in the calculations to obtain kinetic parameters such as K[subscript m], V[subscript…

  5. Kinetics of heterotrophic biomass and storage mechanism in wetland cores measured by respirometry.

    PubMed

    Ortigara, A R C; Foladori, P; Andreottola, G

    2011-01-01

    Although oxygen uptake rate has been widely used in activated sludge for measuring kinetic and stoichiometric parameters or for wastewater characterization, its application in constructed wetlands (CWs) cores has been recently proposed. The aim of this research is to estimate the kinetic and stoichiometric parameters of the heterotrophic biomass in CW cores. Respirometric tests were carried out with pure carbonaceous substrate and real wastewater. Endogenous respiration was about 2 gO2 m(-3) h(-1) (per unit of bed volume), while the kinetic parameters obtained for COD oxidation were very high (maximum rate per unit of bed volume of 10.7-26.8 gCOD m(-3) h(-1)) which indicates high biodegradation potential in fully aerobic environment. Regarding to stoichiometric parameter, the maximum growth yield, Y(H), was 0.56-0.59 mgCOD/mgCOD, while the storage yield, Y(STO), was 0.75-0.77 mgCOD/mgCOD. The storage mechanism was observed in CW cores during COD oxidation, which leads to the transformation of the external soluble substrate in internal storage products, probably as response to intermittent loads applied in CW systems, transient concentrations of readily biodegradable substrate and alternance of feast/famine periods.

  6. A Kinetic Model for Calcium Dynamics in RAW 264.7 Cells: 1. Mechanisms, Parameters, and Subpopulational Variability

    PubMed Central

    Maurya, Mano Ram; Subramaniam, Shankar

    2007-01-01

    Calcium (Ca2+) is an important second messenger and has been the subject of numerous experimental measurements and mechanistic studies in intracellular signaling. Calcium profile can also serve as a useful cellular phenotype. Kinetic models of calcium dynamics provide quantitative insights into the calcium signaling networks. We report here the development of a complex kinetic model for calcium dynamics in RAW 264.7 cells stimulated by the C5a ligand. The model is developed using the vast number of measurements of in vivo calcium dynamics carried out in the Alliance for Cellular Signaling (AfCS) Laboratories. Ligand binding, phospholipase C-β (PLC-β) activation, inositol 1,4,5-trisphosphate (IP3) receptor (IP3R) dynamics, and calcium exchange with mitochondria and extracellular matrix have all been incorporated into the model. The experimental data include data from both native and knockdown cell lines. Subpopulational variability in measurements is addressed by allowing nonkinetic parameters to vary across datasets. The model predicts temporal response of Ca2+ concentration for various doses of C5a under different initial conditions. The optimized parameters for IP3R dynamics are in agreement with the legacy data. Further, the half-maximal effect concentration of C5a and the predicted dose response are comparable to those seen in AfCS measurements. Sensitivity analysis shows that the model is robust to parametric perturbations. PMID:17483174

  7. Probabilistic parameter estimation in a 2-step chemical kinetics model for n-dodecane jet autoignition

    NASA Astrophysics Data System (ADS)

    Hakim, Layal; Lacaze, Guilhem; Khalil, Mohammad; Sargsyan, Khachik; Najm, Habib; Oefelein, Joseph

    2018-05-01

    This paper demonstrates the development of a simple chemical kinetics model designed for autoignition of n-dodecane in air using Bayesian inference with a model-error representation. The model error, i.e. intrinsic discrepancy from a high-fidelity benchmark model, is represented by allowing additional variability in selected parameters. Subsequently, we quantify predictive uncertainties in the results of autoignition simulations of homogeneous reactors at realistic diesel engine conditions. We demonstrate that these predictive error bars capture model error as well. The uncertainty propagation is performed using non-intrusive spectral projection that can also be used in principle with larger scale computations, such as large eddy simulation. While the present calibration is performed to match a skeletal mechanism, it can be done with equal success using experimental data only (e.g. shock-tube measurements). Since our method captures the error associated with structural model simplifications, we believe that the optimised model could then lead to better qualified predictions of autoignition delay time in high-fidelity large eddy simulations than the existing detailed mechanisms. This methodology provides a way to reduce the cost of reaction kinetics in simulations systematically, while quantifying the accuracy of predictions of important target quantities.

  8. Preparation, non-isothermal decomposition kinetics, heat capacity and adiabatic time-to-explosion of NTOxDNAZ.

    PubMed

    Ma, Haixia; Yan, Biao; Li, Zhaona; Guan, Yulei; Song, Jirong; Xu, Kangzhen; Hu, Rongzu

    2009-09-30

    NTOxDNAZ was prepared by mixing 3,3-dinitroazetidine (DNAZ) and 3-nitro-1,2,4-triazol-5-one (NTO) in ethanol solution. The thermal behavior of the title compound was studied under a non-isothermal condition by DSC and TG/DTG methods. The kinetic parameters were obtained from analysis of the DSC and TG/DTG curves by Kissinger method, Ozawa method, the differential method and the integral method. The main exothermic decomposition reaction mechanism of NTOxDNAZ is classified as chemical reaction, and the kinetic parameters of the reaction are E(a)=149.68 kJ mol(-1) and A=10(15.81)s(-1). The specific heat capacity of the title compound was determined with continuous C(p) mode of microcalorimeter. The standard mole specific heat capacity of NTOxDNAZ was 352.56 J mol(-1)K(-1) in 298.15K. Using the relationship between C(p) and T and the thermal decomposition parameters, the time of the thermal decomposition from initialization to thermal explosion (adiabatic time-to-explosion) was obtained.

  9. Investigation of thermoluminescence and kinetic parameters of CaMgB{sub 2}O{sub 5}: Dy{sup 3+} nanophosphor

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Manhas, M.; Kumar, Vinay, E-mail: vinaykumar@smvdu.ac.in; Department of Physics, University of the Free State, P.O. Box 339, Bloemfontein ZA9300

    2016-05-06

    In this paper, thermoluminescence (TL) properties of Dy{sup 3+} (1.5 mol %) doped CaMgB{sub 2}O{sub 5} nanophosphor after being exposed to ultraviolet (UV) radiations (λ=254nm) were investigated. In UV exposed samples, the thermoluminescence glow curve consists of a broad glow peak located at 380 K with a small shoulder at 507 K. A shift in glow peak temperature from 367 K to 380 K after the UV exposure for 80 min was observed, which clearly shows that glow peaks follow the second order kinetics. The TL intensity of the peaks increases with an increase in the exposure time of UV rays (10-180 min). The TL Anal programmore » was used to analyze the glow curve. The kinetic parameters such as activation energy (E), the frequency factor (s) and the order of kinetics (b) were calculated for CaMgB{sub 2}O{sub 5}: Dy{sup 3+} nanophosphors.« less

  10. Measurements of Euglena motion parameters by laser light scattering.

    PubMed Central

    Ascoli, C; Barbi, M; Frediani, C; Murè, A

    1978-01-01

    Measurements of Euglena gracilis motion parameters have been performed by the spectral analysis of the scattered laser light. Samples were oriented by a radiofrequency field to obtain easily interpretable spectra. Cell rotation frequency and flagellar beating frequency distributions were obtained from the homodyne spectra, whereas the Doppler lines obtained at small observation angles by heterodyne detection yielded the swimming speed distributions. We discuss the broadening of the heterodyne spectra at large angles of observation. An application of this method to the study of the photo-kinetic effect is also described. Images FIGURE 3 PMID:104747

  11. On the equilibrium between proton kappa distribution and compressible kinetic Alfvenic fluctuations

    NASA Astrophysics Data System (ADS)

    Yoon, P. H.

    2017-12-01

    Protons with a quasi inverse power law energetic population featuring the property f v-α, with α close to 5, are pervasively observed in the heliosphere. While many theoretical attempts have been made in order to describe such a feature, the so-called pump acceleration mechanism put forth by Fisk & Gloeckler is one of the most prominent theories. Their mechanism involves the low-frequency compressional fluctuations accelerating the protons. This presentation aims to reformulate the problem from the perspective of the steady state solution of the self-consistent plasma kinetic theory involving compressible kinetic Alfvenic fluctuations. By considering the steady state proton particle kinetic equation and quasi-linear wave kinetic for the kinetic Alfvenic turbulence we seek to obtain concomitant solutions for both proton velocity distribution function and the spectral intensity for kinetic Alfvenic fluctuation. It is found that the kappa distribution for the protons is a legitimate, if not unique, solution. The steady state spectrum of kinetic Alfvenic fluctuation is also obtained. The present investigation demonstrates that the kappa distribution for the protons featuring energetic tail population characterized by f v-2κ-2, where κ is the parameter for kappa distribution, may represent the background population of the protons in the heliosphere. However, it is speculated that in order to uniquely determine the value of κ, which must be close to 1.5 for asymptotic behavior of f v-5, one must have an additional constraint that involves the balance of nonlinear mode coupling terms in the wave kinetic equation.

  12. Kinetic modeling of the photocatalytic degradation of clofibric acid in a slurry reactor.

    PubMed

    Manassero, Agustina; Satuf, María Lucila; Alfano, Orlando Mario

    2015-01-01

    A kinetic study of the photocatalytic degradation of the pharmaceutical clofibric acid is presented. Experiments were carried out under UV radiation employing titanium dioxide in water suspension. The main reaction intermediates were identified and quantified. Intrinsic expressions to represent the kinetics of clofibric acid and the main intermediates were derived. The modeling of the radiation field in the reactor was carried out by Monte Carlo simulation. Experimental runs were performed by varying the catalyst concentration and the incident radiation. Kinetic parameters were estimated from the experiments by applying a non-linear regression procedure. Good agreement was obtained between model predictions and experimental data, with an error of 5.9 % in the estimations of the primary pollutant concentration.

  13. The nonlocal electron kinetics for a low-pressure glow discharge dusty plasma

    NASA Astrophysics Data System (ADS)

    Liang, Yonggan; Wang, Ying; Li, Hui; Tian, Ruihuan; Yuan, Chengxun; Kudryavtsev, A. A.; Rabadanov, K. M.; Wu, Jian; Zhou, Zhongxiang; Tian, Hao

    2018-05-01

    The nonlocal electron kinetic model based on the Boltzmann equation is developed in low-pressure argon glow discharge dusty plasmas. The additional electron-dust elastic and inelastic collision processes are considered when solving the kinetic equation numerically. The orbital motion limited theory and collision enhanced collection approximation are employed to calculate the dust surface potential. The electron energy distribution function (EEDF), effective electron temperature Teff, and dust surface potential are investigated under different plasma and dust conditions by solving the Boltzmann and the dust charging current balance equations self-consistently. A comparison of the calculation results obtained from nonlocal and local kinetic models is made. It is shown that the appearance of dust particles leads to a deviation of the EEDF from its original profile for both nonlocal and local kinetic models. With the increase in dust density and size, the effective electron temperature and dust surface potential decrease due to the high-energy electron loss on the dust surface. Meanwhile, the nonlocal and local results differ much from each other under the same calculation condition. It is concluded that, for low-pressure (PR ≤ 1 cm*Torr) glow discharge dusty plasmas, the existence of dust particles will amplify the difference of local and nonlocal EEDFs, which makes the local kinetic model more improper to determine the main parameters of the positive column. The nonlocal kinetic model should be used for the calculation of the EEDFs and dusty plasma parameters.

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

    PubMed

    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.

  15. Kinetic study on anaerobic oxidation of methane coupled to denitrification.

    PubMed

    Yu, Hou; Kashima, Hiroyuki; Regan, John M; Hussain, Abid; Elbeshbishy, Elsayed; Lee, Hyung-Sool

    2017-09-01

    Monod kinetic parameters provide information required for kinetic analysis of anaerobic oxidation of methane coupled to denitrification (AOM-D). This information is critical for engineering AOM-D processes in wastewater treatment facilities. We first experimentally determined Monod kinetic parameters for an AOM-D enriched culture and obtained the following values: maximum specific growth rate (μ max ) 0.121/d, maximum substrate-utilization rate (q max ) 28.8mmol CH 4 /g cells-d, half maximum-rate substrate concentration (K s ) 83μΜ CH 4 , growth yield (Y) 4.76gcells/mol CH 4 , decay coefficient (b) 0.031/d, and threshold substrate concentration (S min ) 28.8μM CH 4 . Clone library analysis of 16S rRNA and mcrA gene fragments suggested that AOM-D reactions might have occurred via the syntrophic interaction between denitrifying bacteria (e.g., Ignavibacterium, Acidovorax, and Pseudomonas spp.) and hydrogenotrophic methanogens (Methanobacterium spp.), supporting reverse methanogenesis-dependent AOM-D in our culture. High μ max and q max , and low K s for the AOM-D enrichment imply that AOM-D could play a significant role in mitigating atmospheric methane efflux. In addition, these high kinetic features suggest that engineered AOM-D systems may provide a sustainable alternative to nitrogen removal in wastewater treatment. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Kinetic and temporospatial parameters in male and female cats walking over a pressure sensing walkway.

    PubMed

    Verdugo, Mirela R; Rahal, Sheila C; Agostinho, Felipe S; Govoni, Verônica M; Mamprim, Maria J; Monteiro, Frederico O B

    2013-06-27

    Several factors may influence kinetic data measurements, including body conformation and body mass. In addition, gender differences in gait pattern have been observed in healthy humans. Therefore, the aim of this study was to compare the kinetic and temporospatial parameters in clinically healthy male and female cats using a pressure-sensitive walkway. Eighteen crossbreed adult cats were divided into two groups: G1 had ten male cats (nine neutered) aged from 1 to 4 years and body mass 3.1-6.8 kg; G2 had eight spayed female cats, aged from 1 to 6 years and body mass 3.3-4.75 kg. The data from the first five valid trials were collected for each cat. A trial was considered valid if the cat maintained a velocity between 0.54-0.74 m/s and acceleration from -0.20 to 0.20 m/s2. The peak vertical force (PVF), vertical impulse (VI), gait cycle time, stance time, swing time, stride length, and percentage body weight distribution among the four limbs were determined. In addition, the lengths of each forelimb and each hind limb were measured using a tape with the animal standing. No significant differences were observed in each group in either the forelimbs or the hind limbs or between the left and right sides for any of the variables. For both groups, the PVF (%BW), the VI, and the percentage body weight distribution were higher at the forelimbs than the hind limbs. The stride length was larger for males; however, the other kinetic and temporospatial variables did not show any statistically significant differences between the groups. The lengths of the forelimbs and hind limbs were larger in the male cats. There was a significant moderate positive correlation between the stride length and the length of the limbs. In conclusion, the only difference observed between male and female cats was the stride length, and this was due to the greater body size of male cats. This difference did not affect other temporospatial or kinetics variables.

  17. Kinetic temperature of massive star forming molecular clumps measured with formaldehyde

    NASA Astrophysics Data System (ADS)

    Tang, X. D.; Henkel, C.; Menten, K. M.; Zheng, X. W.; Esimbek, J.; Zhou, J. J.; Yeh, C. C.; König, C.; Yuan, Y.; He, Y. X.; Li, D. L.

    2017-02-01

    Context. For a general understanding of the physics involved in the star formation process, measurements of physical parameters such as temperature and density are indispensable. The chemical and physical properties of dense clumps of molecular clouds are strongly affected by the kinetic temperature. Therefore, this parameter is essential for a better understanding of the interstellar medium. Formaldehyde, a molecule which traces the entire dense molecular gas, appears to be the most reliable tracer to directly measure the gas kinetic temperature. Aims: We aim to determine the kinetic temperature with spectral lines from formaldehyde and to compare the results with those obtained from ammonia lines for a large number of massive clumps. Methods: Three 218 GHz transitions (JKAKC = 303-202, 322-221, and 321-220) of para-H2CO were observed with the 15 m James Clerk Maxwell Telescope (JCMT) toward 30 massive clumps of the Galactic disk at various stages of high-mass star formation. Using the RADEX non-LTE model, we derive the gas kinetic temperature modeling the measured para-H2CO 322-221/303-202 and 321-220/303-202 ratios. Results: The gas kinetic temperatures derived from the para-H2CO (321-220/303-202) line ratios range from 30 to 61 K with an average of 46 ± 9 K. A comparison of kinetic temperature derived from para-H2CO, NH3, and the dust emission indicates that in many cases para-H2CO traces a similar kinetic temperature to the NH3 (2, 2)/(1, 1) transitions and the dust associated with the HII regions. Distinctly higher temperatures are probed by para-H2CO in the clumps associated with outflows/shocks. Kinetic temperatures obtained from para-H2CO trace turbulence to a higher degree than NH3 (2, 2)/(1, 1) in the massive clumps. The non-thermal velocity dispersions of para-H2CO lines are positively correlated with the gas kinetic temperature. The massive clumps are significantly influenced by supersonic non-thermal motions. The reduced spectra (FITS files) are only

  18. An analytical approach to obtaining JWL parameters from cylinder tests

    NASA Astrophysics Data System (ADS)

    Sutton, B. D.; Ferguson, J. W.; Hodgson, A. N.

    2017-01-01

    An analytical method for determining parameters for the JWL Equation of State from cylinder test data is described. This method is applied to four datasets obtained from two 20.3 mm diameter EDC37 cylinder tests. The calculated pressure-relative volume (p-Vr) curves agree with those produced by hydro-code modelling. The average calculated Chapman-Jouguet (CJ) pressure is 38.6 GPa, compared to the model value of 38.3 GPa; the CJ relative volume is 0.729 for both. The analytical pressure-relative volume curves produced agree with the one used in the model out to the commonly reported expansion of 7 relative volumes, as do the predicted energies generated by integrating under the p-Vr curve. The calculated energy is within 1.6% of that predicted by the model.

  19. Desorption kinetics of organic chemicals from albumin.

    PubMed

    Krause, Sophia; Ulrich, Nadin; Goss, Kai-Uwe

    2018-03-01

    When present in blood, most chemicals tend to bind to the plasma protein albumin. For distribution into surrounding tissues, desorption from albumin is necessary, because only the unbound form of a chemical is assumed to be able to cross cell membranes. For metabolism of chemicals, the liver is a particularly important organ. One potentially limiting step for hepatic uptake of the chemicals is desorption from albumin, because blood passes the human liver within seconds. Desorption kinetics from albumin can thus be an important parameter for our pharmacokinetic and toxicokinetic understanding of chemicals. This work presents a dataset of measured desorption rate constants and reveals a possibility for their prediction. Additionally, the obtained extraction profiles directly indicate physiological relevance of desorption kinetics, because desorption of the test chemicals is still incomplete after time frames comparable to the residence time of blood in the liver.

  20. Modelling of slaughterhouse solid waste anaerobic digestion: determination of parameters and continuous reactor simulation.

    PubMed

    López, Iván; Borzacconi, Liliana

    2010-10-01

    A model based on the work of Angelidaki et al. (1993) was applied to simulate the anaerobic biodegradation of ruminal contents. In this study, two fractions of solids with different biodegradation rates were considered. A first-order kinetic was used for the easily biodegradable fraction and a kinetic expression that is function of the extracellular enzyme concentration was used for the slowly biodegradable fraction. Batch experiments were performed to obtain an accumulated methane curve that was then used to obtain the model parameters. For this determination, a methodology derived from the "multiple-shooting" method was successfully used. Monte Carlo simulations allowed a confidence range to be obtained for each parameter. Simulations of a continuous reactor were performed using the optimal set of model parameters. The final steady-states were determined as functions of the operational conditions (solids load and residence time). The simulations showed that methane flow peaked at a flow rate of 0.5-0.8 Nm(3)/d/m(reactor)(3) at a residence time of 10-20 days. Simulations allow the adequate selection of operating conditions of a continuous reactor. (c) 2010 Elsevier Ltd. All rights reserved.

  1. Optimal experimental design for assessment of enzyme kinetics in a drug discovery screening environment.

    PubMed

    Sjögren, Erik; Nyberg, Joakim; Magnusson, Mats O; Lennernäs, Hans; Hooker, Andrew; Bredberg, Ulf

    2011-05-01

    A penalized expectation of determinant (ED)-optimal design with a discrete parameter distribution was used to find an optimal experimental design for assessment of enzyme kinetics in a screening environment. A data set for enzyme kinetic data (V(max) and K(m)) was collected from previously reported studies, and every V(max)/K(m) pair (n = 76) was taken to represent a unique drug compound. The design was restricted to 15 samples, an incubation time of up to 40 min, and starting concentrations (C(0)) for the incubation between 0.01 and 100 μM. The optimization was performed by finding the sample times and C(0) returning the lowest uncertainty (S.E.) of the model parameter estimates. Individual optimal designs, one general optimal design and one, for laboratory practice suitable, pragmatic optimal design (OD) were obtained. In addition, a standard design (STD-D), representing a commonly applied approach for metabolic stability investigations, was constructed. Simulations were performed for OD and STD-D by using the Michaelis-Menten (MM) equation, and enzyme kinetic parameters were estimated with both MM and a monoexponential decay. OD generated a better result (relative standard error) for 99% of the compounds and an equal or better result [(root mean square error (RMSE)] for 78% of the compounds in estimation of metabolic intrinsic clearance. Furthermore, high-quality estimates (RMSE < 30%) of both V(max) and K(m) could be obtained for a considerable number (26%) of the investigated compounds by using the suggested OD. The results presented in this study demonstrate that the output could generally be improved compared with that obtained from the standard approaches used today.

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

    PubMed Central

    2013-01-01

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

  3. Batch Tests To Determine Activity Distribution and Kinetic Parameters for Acetate Utilization in Expanded-Bed Anaerobic Reactors

    PubMed Central

    Fox, Peter; Suidan, Makram T.

    1990-01-01

    Batch tests to measure maximum acetate utilization rates were used to determine the distribution of acetate utilizers in expanded-bed sand and expanded-bed granular activated carbon (GAC) reactors. The reactors were fed a mixture of acetate and 3-ethylphenol, and they contained the same predominant aceticlastic methanogen, Methanothrix sp. Batch tests were performed both on the entire reactor contents and with media removed from the reactors. Results indicated that activity was evenly distributed within the GAC reactors, whereas in the sand reactor a sludge blanket on top of the sand bed contained approximately 50% of the activity. The Monod half-velocity constant (Ks) for the acetate-utilizing methanogens in two expanded-bed GAC reactors was searched for by combining steady-state results with batch test data. All parameters necessary to develop a model with Monod kinetics were experimentally determined except for Ks. However, Ks was a function of the effluent 3-ethylphenol concentration, and batch test results demonstrated that maximum acetate utilization rates were not a function of the effluent 3-ethylphenol concentration. Addition of a competitive inhibition term into the Monod expression predicted the dependence of Ks on the effluent 3-ethylphenol concentration. A two-parameter search determined a Ks of 8.99 mg of acetate per liter and a Ki of 2.41 mg of 3-ethylphenol per liter. Model predictions were in agreement with experimental observations for all effluent 3-ethylphenol concentrations. Batch tests measured the activity for a specific substrate and determined the distribution of activity in the reactor. The use of steady-state data in conjunction with batch test results reduced the number of unknown kinetic parameters and thereby reduced the uncertainty in the results and the assumptions made. PMID:16348175

  4. Batch tests to determine activity distribution and kinetic parameters for acetate utilization in expanded-bed anaerobic reactors.

    PubMed

    Fox, P; Suidan, M T

    1990-04-01

    Batch tests to measure maximum acetate utilization rates were used to determine the distribution of acetate utilizers in expanded-bed sand and expanded-bed granular activated carbon (GAC) reactors. The reactors were fed a mixture of acetate and 3-ethylphenol, and they contained the same predominant aceticlastic methanogen, Methanothrix sp. Batch tests were performed both on the entire reactor contents and with media removed from the reactors. Results indicated that activity was evenly distributed within the GAC reactors, whereas in the sand reactor a sludge blanket on top of the sand bed contained approximately 50% of the activity. The Monod half-velocity constant (K(s)) for the acetate-utilizing methanogens in two expanded-bed GAC reactors was searched for by combining steady-state results with batch test data. All parameters necessary to develop a model with Monod kinetics were experimentally determined except for K(s). However, K(s) was a function of the effluent 3-ethylphenol concentration, and batch test results demonstrated that maximum acetate utilization rates were not a function of the effluent 3-ethylphenol concentration. Addition of a competitive inhibition term into the Monod expression predicted the dependence of K(s) on the effluent 3-ethylphenol concentration. A two-parameter search determined a K(s) of 8.99 mg of acetate per liter and a K(i) of 2.41 mg of 3-ethylphenol per liter. Model predictions were in agreement with experimental observations for all effluent 3-ethylphenol concentrations. Batch tests measured the activity for a specific substrate and determined the distribution of activity in the reactor. The use of steady-state data in conjunction with batch test results reduced the number of unknown kinetic parameters and thereby reduced the uncertainty in the results and the assumptions made.

  5. ITC Recommendations for Transporter Kinetic Parameter Estimation and Translational Modeling of Transport-Mediated PK and DDIs in Humans

    PubMed Central

    Zamek-Gliszczynski, MJ; Lee, CA; Poirier, A; Bentz, J; Chu, X; Ellens, H; Ishikawa, T; Jamei, M; Kalvass, JC; Nagar, S; Pang, KS; Korzekwa, K; Swaan, PW; Taub, ME; Zhao, P; Galetin, A

    2013-01-01

    This white paper provides a critical analysis of methods for estimating transporter kinetics and recommendations on proper parameter calculation in various experimental systems. Rational interpretation of transporter-knockout animal findings and application of static and dynamic physiologically based modeling approaches for prediction of human transporter-mediated pharmacokinetics and drug–drug interactions (DDIs) are presented. The objective is to provide appropriate guidance for the use of in vitro, in vivo, and modeling tools in translational transporter science. PMID:23588311

  6. Thermodynamically consistent model calibration in chemical kinetics

    PubMed Central

    2011-01-01

    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 models. Furthermore, TCMC can

  7. Thermodynamics and kinetics parameters of co-combustion between sewage sludge and water hyacinth in CO2/O2 atmosphere as biomass to solid biofuel.

    PubMed

    Huang, Limao; Liu, Jingyong; He, Yao; Sun, Shuiyu; Chen, Jiacong; Sun, Jian; Chang, KenLin; Kuo, Jiahong; Ning, Xun'an

    2016-10-01

    Thermodynamics and kinetics of sewage sludge (SS) and water hyacinth (WH) co-combustion as a blend fuel (SW) for bioenergy production were studied through thermogravimetric analysis. In CO2/O2 atmosphere, the combustion performance of SS added with 10-40wt.% WH was improved 1-1.97 times as revealed by the comprehensive combustion characteristic index (CCI). The conversion of SW in different atmospheres was identified and their thermodynamic parameters (ΔH,ΔS,ΔG) were obtained. As the oxygen concentration increased from 20% to 70%, the ignition temperature of SW decreased from 243.1°C to 240.3°C, and the maximum weight loss rate and CCI increased from 5.70%·min(-1) to 7.26%·min(-1) and from 4.913%(2)·K(-3)·min(-2) to 6.327%(2)·K(-3)·min(-2), respectively, which corresponded to the variation in ΔS and ΔG. The lowest activation energy (Ea) of SW was obtained in CO2/O2=7/3 atmosphere. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Improving estimation of kinetic parameters in dynamic force spectroscopy using cluster analysis

    NASA Astrophysics Data System (ADS)

    Yen, Chi-Fu; Sivasankar, Sanjeevi

    2018-03-01

    Dynamic Force Spectroscopy (DFS) is a widely used technique to characterize the dissociation kinetics and interaction energy landscape of receptor-ligand complexes with single-molecule resolution. In an Atomic Force Microscope (AFM)-based DFS experiment, receptor-ligand complexes, sandwiched between an AFM tip and substrate, are ruptured at different stress rates by varying the speed at which the AFM-tip and substrate are pulled away from each other. The rupture events are grouped according to their pulling speeds, and the mean force and loading rate of each group are calculated. These data are subsequently fit to established models, and energy landscape parameters such as the intrinsic off-rate (koff) and the width of the potential energy barrier (xβ) are extracted. However, due to large uncertainties in determining mean forces and loading rates of the groups, errors in the estimated koff and xβ can be substantial. Here, we demonstrate that the accuracy of fitted parameters in a DFS experiment can be dramatically improved by sorting rupture events into groups using cluster analysis instead of sorting them according to their pulling speeds. We test different clustering algorithms including Gaussian mixture, logistic regression, and K-means clustering, under conditions that closely mimic DFS experiments. Using Monte Carlo simulations, we benchmark the performance of these clustering algorithms over a wide range of koff and xβ, under different levels of thermal noise, and as a function of both the number of unbinding events and the number of pulling speeds. Our results demonstrate that cluster analysis, particularly K-means clustering, is very effective in improving the accuracy of parameter estimation, particularly when the number of unbinding events are limited and not well separated into distinct groups. Cluster analysis is easy to implement, and our performance benchmarks serve as a guide in choosing an appropriate method for DFS data analysis.

  9. Kinetic Parameters of Efflux of Penicillins by the Multidrug Efflux Transporter AcrAB-TolC of Escherichia coli▿

    PubMed Central

    Lim, Siew Ping; Nikaido, Hiroshi

    2010-01-01

    The multidrug efflux transporter AcrAB-TolC is known to pump out a diverse range of antibiotics, including β-lactams. However, the kinetic constants of the efflux process, needed for the quantitative understanding of resistance, were not available until those accompanying the efflux of some cephalosporins were recently determined by combining efflux with the hydrolysis of drugs by the periplasmic β-lactamase. In the present study we extended this approach to the study of a wide range of penicillins, from ampicillin and penicillin V to ureidopenicillins and isoxazolylpenicillins, by combining efflux with hydrolysis with the OXA-7 penicillinase. We found that the penicillins had a much stronger apparent affinity to AcrB and higher maximum rates of efflux than the cephalosporins. All penicillins showed strong positive cooperativity kinetics for export. The kinetic constants obtained were validated, as the MICs theoretically predicted on the basis of efflux and hydrolysis kinetics were remarkably similar to the observed MICs (except for the isoxazolylpenicillins). Surprisingly, however, the efflux kinetics of cloxacillin, for example, whose MIC decreased 512-fold in Escherichia coli upon the genetic deletion of the acrB gene, were quite similar to those of ampicillin, whose MIC decreased only 2-fold with the same treatment. Analysis of this phenomenon showed that the extensive decrease in the MIC for the acrB mutant is primarily due to the low permeation of the drug and that comparison of the MICs between the parent and the acrB strains is a very poor measure of the ability of AcrB to pump a drug out. PMID:20160052

  10. Bioenergy potential of Wolffia arrhiza appraised through pyrolysis, kinetics, thermodynamics parameters and TG-FTIR-MS study of the evolved gases.

    PubMed

    Ahmad, Muhammad Sajjad; Mehmood, Muhammad Aamer; Liu, Chen-Guang; Tawab, Abdul; Bai, Feng-Wu; Sakdaronnarong, Chularat; Xu, Jianren; Rahimuddin, Sawsan Abdulaziz; Gull, Munazza

    2018-04-01

    This study evaluated the bioenergy potential of Wolffia arrhiza via pyrolysis. The biomass was collected from the pond receiving city wastewater. Oven dried powdered biomass was exposed to thermal degradation at three heating rates (10, 30 and 50° C min -1 ) using Thermogravimetry-Differential Scanning Calorimetry analyzer in an inert environment. Data obtained were subjected to the isoconversional models of Kissenger-Akahira-Sunose (KSA) and Flynn-Wall-Ozawa (FWO) to elucidate the reaction chemistry. Kinetic parameters including, E a (136-172 kJmol -1 ) and Gibb's free energy (171 kJmol -1 ) showed the remarkable bioenergy potential of the biomass. The average enthalpies indicated that the product formation is favored during pyrolysis. Advanced coupled TG-FTIR-MS analyses showed the evolved gases to contain the compounds containing CO functional groups (aldehydes, ketones), aromatic and aliphatic hydrocarbons as major pyrolytic products. This low-cost abundant biomass may be used to produce energy and chemicals in a cost-efficient and environmentally friendly way. Copyright © 2018 Elsevier Ltd. All rights reserved.

  11. Kinetic behaviour of calf intestinal alkaline phosphatase with pNPP.

    PubMed

    Chaudhuri, Gouri; Chatterjee, Saswata; Venu-Babu, P; Ramasamy, K; Thilagaraj, W Richard

    2013-02-01

    The hydrolysis of p-nitrophenyl phosphate (pNPP) by calf intestinal alkaline phosphatase (CIAP) was investigated with respect to kinetic parameters such as V(max), K(m) and K(cat) under varying pH, buffers, substrate concentration, temperature and period of incubation. Highest activity was obtained with Tris-HCl at pH 11, while in the case of glycine-NaOH buffer the peak activity was recorded at pH 9.5. The enzyme showed the following kinetic characteristics with pNPP in 50 mM Tris-HCl at pH 11 and 100 mM glycine-NaOH at pH 9.5 at an incubation temperature of 37 degrees C: V(max), 3.12 and 1.6 micromoles min(-1) unit(-1); K(m), 7.6 x 10(-4) M and 4 x 10(-4) M; and K(cat), 82.98 s(-1) and 42.55 s(-1), respectively. CIAP displayed a high temperature optimum of 45 degrees C at pH 11. The kinetic behaviour of the enzyme under different parameters suggested that the enzyme might undergo subtle conformational changes in response to the buffers displaying unique characteristics. Bioprecipitation of Cu2+ from 50 ppm of CuCl2 solution was studied where 64.3% of precipitation was obtained. P(i) generated from CIAP-mediated hydrolysis of pNPP was found to bind with copper and precipitated as copper-phosphate. Thus, CIAP could be used as a test candidate in bioremediation of heavy metals from industrial wastes through generation of metal-phosphate complexes.

  12. Evaluation of Thermal Evolution Profiles and Estimation of Kinetic Parameters for Pyrolysis of Coal/Corn Stover Blends Using Thermogravimetric Analysis

    DOE PAGES

    Bhagavatula, Abhijit; Huffman, Gerald; Shah, Naresh; ...

    2014-01-01

    The thermal evolution profiles and kinetic parameters for the pyrolysis of two Montana coals (DECS-38 subbituminous coal and DECS-25 lignite coal), one biomass sample (corn stover), and their blends (10%, 20%, and 30% by weight of corn stover) have been investigated at a heating rate of 5°C/min in an inert nitrogen atmosphere, using thermogravimetric analysis. The thermal evolution profiles of subbituminous coal and lignite coal display only one major peak over a wide temperature distribution, ~152–814°C and ~175–818°C, respectively, whereas the thermal decomposition profile for corn stover falls in a much narrower band than that of the coals, ~226–608°C. Themore » nonlinearity in the evolution of volatile matter with increasing percentage of corn stover in the blends verifies the possibility of synergistic behavior in the blends with subbituminous coal where deviations from the predicted yield ranging between 2% and 7% were observed whereas very little deviations (1%–3%) from predicted yield were observed in blends with lignite indicating no significant interactions with corn stover. In addition, a single first-order reaction model using the Coats-Redfern approximation was utilized to predict the kinetic parameters of the pyrolysis reaction. The kinetic analysis indicated that each thermal evolution profile may be represented as a single first-order reaction. Three temperature regimes were identified for each of the coals while corn stover and the blends were analyzed using two and four temperature regimes, respectively.« less

  13. Evaluation of Thermal Evolution Profiles and Estimation of Kinetic Parameters for Pyrolysis of Coal/Corn Stover Blends Using Thermogravimetric Analysis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bhagavatula, Abhijit; Huffman, Gerald; Shah, Naresh

    The thermal evolution profiles and kinetic parameters for the pyrolysis of two Montana coals (DECS-38 subbituminous coal and DECS-25 lignite coal), one biomass sample (corn stover), and their blends (10%, 20%, and 30% by weight of corn stover) have been investigated at a heating rate of 5°C/min in an inert nitrogen atmosphere, using thermogravimetric analysis. The thermal evolution profiles of subbituminous coal and lignite coal display only one major peak over a wide temperature distribution, ~152–814°C and ~175–818°C, respectively, whereas the thermal decomposition profile for corn stover falls in a much narrower band than that of the coals, ~226–608°C. Themore » nonlinearity in the evolution of volatile matter with increasing percentage of corn stover in the blends verifies the possibility of synergistic behavior in the blends with subbituminous coal where deviations from the predicted yield ranging between 2% and 7% were observed whereas very little deviations (1%–3%) from predicted yield were observed in blends with lignite indicating no significant interactions with corn stover. In addition, a single first-order reaction model using the Coats-Redfern approximation was utilized to predict the kinetic parameters of the pyrolysis reaction. The kinetic analysis indicated that each thermal evolution profile may be represented as a single first-order reaction. Three temperature regimes were identified for each of the coals while corn stover and the blends were analyzed using two and four temperature regimes, respectively.« less

  14. Optimization of the parameters for obtaining zirconia-alumina coatings, made by flame spraying from results of numerical simulation

    NASA Astrophysics Data System (ADS)

    Ferrer, M.; Vargas, F.; Peña, G.

    2017-12-01

    The K-Sommerfeld values (K) and the melting percentage (% F) obtained by numerical simulation using the Jets et Poudres software were used to find the projection parameters of zirconia-alumina coatings by thermal spraying flame, in order to obtain coatings with good morphological and structural properties to be used as thermal insulation. The experimental results show the relationship between the Sommerfeld parameter and the porosity of the zirconia-alumina coatings. It is found that the lowest porosity is obtained when the K-Sommerfeld value is close to 45 with an oxidant flame, on the contrary, when superoxidant flames are used K values are close 52, which improve wear resistance.

  15. On-rate based optimization of structure-kinetic relationship--surfing the kinetic map.

    PubMed

    Schoop, Andreas; Dey, Fabian

    2015-10-01

    In the lead discovery process residence time has become an important parameter for the identification and characterization of the most efficacious compounds in vivo. To enable the success of compound optimization by medicinal chemistry toward a desired residence time the understanding of structure-kinetic relationship (SKR) is essential. This article reviews various approaches to monitor SKR and suggests using the on-rate as the key monitoring parameter. The literature is reviewed and examples of compound series with low variability as well as with significant changes in on-rates are highlighted. Furthermore, findings of kinetic on-rate changes are presented and potential underlying rationales are discussed. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Biosensors for monitoring the isothermal breakdown kinetics of peanut oil heated at 180°C. Comparison with results obtained for extra virgin olive oil.

    PubMed

    Tomassetti, M; Vecchio, S; Campanella, L; Dragone, R

    2013-10-15

    The present research was devoted to studying the kinetics of the artificial rancidification of peanut oil (PO) when a sample of this oil was isothermally heated at 180°C in an air stream. The formation of radical species due to heating was evaluated using a radical index whose value was determined using a biosensor method based on a superoxide dismutase (SOD), while the increasing toxicity was monitored using a suitable toxicity measuring probe based on the Clark electrode and immobilized yeast cells. An extra virgin olive oil was isothermally rancidified under the same experimental conditions and the corresponding data were used for the purpose of comparison. Both the so-called "model-fitting" and the classical kinetic methods were applied to the isothermal process biosensor data in order to obtain the kinetic constant rate value at 180°C. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. Impedance Analysis of Ion Transport Through Supported Lipid Membranes Doped with Ionophores: A New Kinetic Approach

    PubMed Central

    Alvarez, P. E.; Vallejo, A. E.

    2008-01-01

    Kinetics of facilitated ion transport through planar bilayer membranes are normally analyzed by electrical conductance methods. The additional use of electrical relaxation techniques, such as voltage jump, is necessary to evaluate individual rate constants. Although electrochemical impedance spectroscopy is recognized as the most powerful of the available electric relaxation techniques, it has rarely been used in connection with these kinetic studies. According to the new approach presented in this work, three steps were followed. First, a kinetic model was proposed that has the distinct quality of being general, i.e., it properly describes both carrier and channel mechanisms of ion transport. Second, the state equations for steady-state and for impedance experiments were derived, exhibiting the input–output representation pertaining to the model’s structure. With the application of a method based on the similarity transformation approach, it was possible to check that the proposed mechanism is distinguishable, i.e., no other model with a different structure exhibits the same input–output behavior for any input as the original. Additionally, the method allowed us to check whether the proposed model is globally identifiable (i.e., whether there is a single set of fit parameters for the model) when analyzed in terms of its impedance response. Thus, our model does not represent a theoretical interpretation of the experimental impedance but rather constitutes the prerequisite to select this type of experiment in order to obtain optimal kinetic identification of the system. Finally, impedance measurements were performed and the results were fitted to the proposed theoretical model in order to obtain the kinetic parameters of the system. The successful application of this approach is exemplified with results obtained for valinomycin–K+ in lipid bilayers supported onto gold substrates, i.e., an arrangement capable of emulating biological membranes. PMID:19669528

  18. Stoichiometry and kinetics of the anaerobic ammonium oxidation (Anammox) with trace hydrazine addition.

    PubMed

    Yao, Zongbao; Lu, Peili; Zhang, Daijun; Wan, Xinyu; Li, Yulian; Peng, Shuchan

    2015-12-01

    Purpose of this study is to investigate the stoichiometry and kinetics of anaerobic ammonium oxidation (Anammox) with trace hydrazine addition. The stoichiometry was established based on the electron balance of Anammox process with trace N2H4 addition. The stoichiometric coefficients were determined by the proton consumption and the changes in substrates and products. It was found that trace N2H4 addition can increase the yield of Anammox bacteria (AnAOB) and reduce NO3(-) yield, which enhances the Anammox. Subsequently, kinetic model of Anammox with trace N2H4 addition was developed, and the parameters of the anaerobic degradation model of N2H4 were obtained for the first time. The maximum specific substrate utilization rate, half-saturation constant and inhibition constant of N2H4 were 25.09mgN/g VSS/d, 10.42mgN/L and 1393.88mgN/L, respectively. These kinetic parameters might provide important information for the engineering applications of Anammox with trace N2H4 addition. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Isotherm, kinetic, and thermodynamic study of ciprofloxacin sorption on sediments.

    PubMed

    Mutavdžić Pavlović, Dragana; Ćurković, Lidija; Grčić, Ivana; Šimić, Iva; Župan, Josip

    2017-04-01

    In this study, equilibrium isotherms, kinetics and thermodynamics of ciprofloxacin on seven sediments in a batch sorption process were examined. The effects of contact time, initial ciprofloxacin concentration, temperature and ionic strength on the sorption process were studied. The K d parameter from linear sorption model was determined by linear regression analysis, while the Freundlich and Dubinin-Radushkevich (D-R) sorption models were applied to describe the equilibrium isotherms by linear and nonlinear methods. The estimated K d values varied from 171 to 37,347 mL/g. The obtained values of E (free energy estimated from D-R isotherm model) were between 3.51 and 8.64 kJ/mol, which indicated a physical nature of ciprofloxacin sorption on studied sediments. According to obtained n values as measure of intensity of sorption estimate from Freundlich isotherm model (from 0.69 to 1.442), ciprofloxacin sorption on sediments can be categorized from poor to moderately difficult sorption characteristics. Kinetics data were best fitted by the pseudo-second-order model (R 2  > 0.999). Thermodynamic parameters including the Gibbs free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) were calculated to estimate the nature of ciprofloxacin sorption. Results suggested that sorption on sediments was a spontaneous exothermic process.

  20. Computational model, method, and system for kinetically-tailoring multi-drug chemotherapy for individuals

    DOEpatents

    Gardner, Shea Nicole

    2007-10-23

    A method and system for tailoring treatment regimens to individual patients with diseased cells exhibiting evolution of resistance to such treatments. A mathematical model is provided which models rates of population change of proliferating and quiescent diseased cells using cell kinetics and evolution of resistance of the diseased cells, and pharmacokinetic and pharmacodynamic models. Cell kinetic parameters are obtained from an individual patient and applied to the mathematical model to solve for a plurality of treatment regimens, each having a quantitative efficacy value associated therewith. A treatment regimen may then be selected from the plurlaity of treatment options based on the efficacy value.

  1. Combined TGA-MS kinetic analysis of multistep processes. Thermal decomposition and ceramification of polysilazane and polysiloxane preceramic polymers.

    PubMed

    García-Garrido, C; Sánchez-Jiménez, P E; Pérez-Maqueda, L A; Perejón, A; Criado, José M

    2016-10-26

    The polymer-to-ceramic transformation kinetics of two widely employed ceramic precursors, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (TTCS) and polyureamethylvinylsilazane (CERASET), have been investigated using coupled thermogravimetry and mass spectrometry (TG-MS), Raman, XRD and FTIR. The thermally induced decomposition of the pre-ceramic polymer is the critical step in the synthesis of polymer derived ceramics (PDCs) and accurate kinetic modeling is key to attaining a complete understanding of the underlying process and to attempt any behavior predictions. However, obtaining a precise kinetic description of processes of such complexity, consisting of several largely overlapping physico-chemical processes comprising the cleavage of the starting polymeric network and the release of organic moieties, is extremely difficult. Here, by using the evolved gases detected by MS as a guide it has been possible to determine the number of steps that compose the overall process, which was subsequently resolved using a semiempirical deconvolution method based on the Frasier-Suzuki function. Such a function is more appropriate that the more usual Gaussian or Lorentzian functions since it takes into account the intrinsic asymmetry of kinetic curves. Then, the kinetic parameters of each constituent step were independently determined using both model-free and model-fitting procedures, and it was found that the processes obey mostly diffusion models which can be attributed to the diffusion of the released gases through the solid matrix. The validity of the obtained kinetic parameters was tested not only by the successful reconstruction of the original experimental curves, but also by predicting the kinetic curves of the overall processes yielded by different thermal schedules and by a mixed TTCS-CERASET precursor.

  2. Experimental and kinetic study for lead removal via photosynthetic consortia using genetic algorithms to parameter estimation.

    PubMed

    Hernández-Melchor, Dulce Jazmín; López-Pérez, Pablo A; Carrillo-Vargas, Sergio; Alberto-Murrieta, Alvaro; González-Gómez, Evanibaldo; Camacho-Pérez, Beni

    2017-09-06

    This work presents an experimental-theoretical strategy for a batch process for lead removal by photosynthetic consortium, conformed by algae and bacteria. Photosynthetic consortium, isolated from a treatment plant wastewater of Tecamac (Mexico), was used as inoculum in bubble column photobioreactors. The consortium was used to evaluate the kinetics of lead removal at different initial concentrations of metal (15, 30, 40, 50, and 60 mgL -1 ), carried out in batch culture with a hydraulic residence time of 14 days using Bold's Basal mineral medium. The photobioreactor was operated under the following conditions: aeration of 0.5 vvm, 80 μmol m -2  s -1 of photon flux density and a photoperiod light/dark 12:12. After determining the best growth kinetics of biomass and metal removal, they were tested under different ratios (30 and 60%) of wastewater-culture medium. Additionally, the biomass growth (X), nitrogen consumption (N), chemical oxygen demand (COD), and metal removal (Pb) were quantified. Achieved lead removal was 97.4% when the initial lead concentration was up to 50 mgL -1 using 60% of wastewater. Additionally, an unstructured-type mathematical model was developed to simulate COD, X, N, and lead removal. Furthermore, a comparison between the Levenberg-Marquardt (L-M) optimization approach and Genetic Algorithms (GA) was carried out for parameter estimation. Also, it was concluded that GA has a slightly better performance and possesses better convergence and computational time than L-M. Hence, the proposed method might be applied for parameter estimation of biological models and be used for the monitoring and control process.

  3. Kinetics of adsorption of dyes from aqueous solution using activated carbon prepared from waste apricot.

    PubMed

    Onal, Yunus

    2006-10-11

    Adsorbent (WA11Zn5) has been prepared from waste apricot by chemical activation with ZnCl(2). Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by N(2) adsorption and DFT plus software. Adsorption of three dyes, namely, Methylene Blue (MB), Malachite Green (MG), Crystal Violet (CV), onto activated carbon in aqueous solution was studied in a batch system with respect to contact time, temperature. The kinetics of adsorption of MB, MG and CV have been discussed using six kinetic models, i.e., the pseudo-first-order model, the pseudo-second-order model, the Elovich equation, the intraparticle diffusion model, the Bangham equation, the modified Freundlich equation. Kinetic parameters and correlation coefficients were determined. It was shown that the second-order kinetic equation could describe the adsorption kinetics for three dyes. The dyes uptake process was found to be controlled by external mass transfer at earlier stages (before 5 min) and by intraparticle diffusion at later stages (after 5 min). Thermodynamic parameters, such as DeltaG, DeltaH and DeltaS, have been calculated by using the thermodynamic equilibrium coefficient obtained at different temperatures and concentrations. The thermodynamics of dyes-WA11Zn5 system indicates endothermic process.

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

    PubMed Central

    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) of liquid-solid ratio, 80°C of extraction temperature, 8.5 of pH, 6.0 mg of enzyme levels, and 130 min of extraction time. Under the optimal conditions, the extraction rate of polyphenols was 3.03%. The kinetic experiments indicated kinetic equation had a good linear relationship with t even under the conditions of different levels of enzyme and temperature, which means fitting curve tallies well with the experimental values. Conclusion: The results of quantification showed that the results provide a reference for enzymatic extracting polyphenols from honeysuckle. SUMMARY Lonicerae flos (Lonicera japonica Thunb.) is a material of traditional Chinese medicine and healthy drinks, of which active compounds mainly is polyphenols. At present, plant polyphenols are the hotspots centents of food, cosmetic and medicine, because it has strong bioactivity. Several traditional methods are available for the extraction of plant polyphenols including impregnation, solvent extraction, ultrasonic extraction, hot-water extraction, alkaline dilute alcohol or alkaline water extraction, microwave extraction and Supercritical CO2 extraction. But now, an increasing number of research on using cellulase to extract active ingredients from plants. Enzymatic method is widely used for enzyme have excellent properties of high reaction efficiency and specificity, moderate reaction conditions, shorter extraction time and easier to control, less damage to the active ingredient. At present, the enzymatic

  5. Does a foot-drop implant improve kinetic and kinematic parameters in the foot and ankle?

    PubMed

    Daniilidis, Kiriakos; Jakubowitz, Eike; Thomann, Anna; Ettinger, Sarah; Stukenborg-Colsman, Christina; Yao, Daiwei

    2017-04-01

    Unlike the drop foot therapy with ortheses, the therapeutic effect of an implantable peroneus nerve stimulator (iPNS) is not well described. IPNS is a dynamic therapy option which is placed directly to the motoric part of the peroneal nerve and evokes a dorsiflexion of the paralysed foot. This retrospective study evaluates the kinematics and kinetics in drop foot patients who were treated with an iPNS. 18 subjects (mean age 51.3 years) with a chronic stroke-related drop foot were treated with an implantable peroneal nerve stimulator. After a mean follow-up from 12.5 months, kinematics and kinetics as well as spatiotemporal parameters were evaluated and compared in activated and deactivated iPNS. Therefore, a gait analysis with motion capture system (Vicon Motion System Ltd®, Oxford, UK) and Plug-in-Gait model was performed. The study showed significantly improved results in ankle dorsiflexion from 6.8° to 1.8° at the initial contact and from -7.3° to 0.9° during swing phase (p ≤ 0.004 and p ≤ 0.005, respectively). Likewise, we could measure improved kinetics, i.a. with a statistically significant improvement in vertical ground reaction force at loading response from 99.76 to 106.71 N/kg (p = 0.043). Enhanced spatiotemporal results in cadence, douple support, stride length, and walking speed could also be achieved, but without statistical significance (p > 0.05). The results show statistically significant improvement in ankle dorsiflexion and vertical ground reaction forces. These facts indicate a more gait stability and gait efficacy. Therefore, the use of an iPNS appears an encouraging therapeutic option for patients with a stroke-related drop foot.

  6. Kinetic Modeling of PET Data Without Blood Sampling

    NASA Astrophysics Data System (ADS)

    Bentourkia, M.

    2005-06-01

    In positron emission tomography (PET) imaging, application of kinetic modeling always requires an input curve (IC) together with the PET data. The IC can be obtained by means of external blood sampling or, in the case of cardiac studies, by means of a region-of-interest (ROI) drawn on the blood pool. It is, however, very unsuitable to withdraw and to analyze blood samples, and in small animals, these operations become difficult, while ICs determined from ROIs are generally contaminated by emissions from neighboring sites, or they are underestimated because of partial volume effect. In this paper, we report a new method to extract kinetic parameters from dynamic PET studies without a priori knowledge of the IC. The method is applied in human brain data measured with fluorodeoxyglucose (FDG) human-brain and in cardiac-rat perfusion studies with /sup 13/N-ammonia and /sup 11/C-acetate. The tissue blood volume (TBV), usually fitted together with the rate constants, is extracted simultaneously with the tissue time activity curves for cardiac studies, while for brain gray matter, TBV is known to be about 4% to 7%. The shape of IC is obtained by means of factor analysis from an ROI drawn around a cardiac tissue or a brain artery. The results show a good correlation (p<0.05) between the cerebral metabolic rate of glucose, myocardial blood flow, and oxygen consumption obtained with the new method in comparison to the usual method. In conclusion, it is possible to apply kinetic modeling without any blood sampling, which significantly simplifies PET acquisition and data analysis.

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

    PubMed

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

    2010-12-14

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

  8. Innovative parameters obtained for digital analysis of microscopic images to evaluate in vitro hemorheological action of anesthetics

    NASA Astrophysics Data System (ADS)

    Alet, Analía. I.; Basso, Sabrina; Delannoy, Marcela; Alet, Nicolás. A.; D'Arrigo, Mabel; Castellini, Horacio V.; Riquelme, Bibiana D.

    2015-06-01

    Drugs used during anesthesia could enhance microvascular flow disturbance, not only for their systemic cardiovascular actions but also by a direct effect on the microcirculation and in particular on hemorheology. This is particularly important in high-risk surgical patients such as those with vascular disease (diabetes, hypertension, etc.). Therefore, in this work we propose a set of innovative parameters obtained by digital analysis of microscopic images to study the in vitro hemorheological effect of propofol and vecuronium on red blood cell from type 2 diabetic patients compared to healthy donors. Obtained innovative parameters allow quantifying alterations in erythrocyte aggregation, which can increase the in vivo risk of microcapillary obstruction.

  9. Structural kinetic modeling of metabolic networks.

    PubMed

    Steuer, Ralf; Gross, Thilo; Selbig, Joachim; Blasius, Bernd

    2006-08-08

    To develop and investigate detailed mathematical models of metabolic processes is one of the primary challenges in systems biology. However, despite considerable advance in the topological analysis of metabolic networks, kinetic modeling is still often severely hampered by inadequate knowledge of the enzyme-kinetic rate laws and their associated parameter values. Here we propose a method that aims to give a quantitative account of the dynamical capabilities of a metabolic system, without requiring any explicit information about the functional form of the rate equations. Our approach is based on constructing a local linear model at each point in parameter space, such that each element of the model is either directly experimentally accessible or amenable to a straightforward biochemical interpretation. This ensemble of local linear models, encompassing all possible explicit kinetic models, then allows for a statistical exploration of the comprehensive parameter space. The method is exemplified on two paradigmatic metabolic systems: the glycolytic pathway of yeast and a realistic-scale representation of the photosynthetic Calvin cycle.

  10. Kinetic and thermodynamic studies on the adsorption of heavy metals from aqueous solution by melanin nanopigment obtained from marine source: Pseudomonas stutzeri.

    PubMed

    Manirethan, Vishnu; Raval, Keyur; Rajan, Reju; Thaira, Harsha; Balakrishnan, Raj Mohan

    2018-05-15

    The difficulty in removal of heavy metals at concentrations below 10 mg/L has led to the exploration of efficient adsorbents for removal of heavy metals. The adsorption capacity of biosynthesized melanin for Mercury (Hg(II)), Chromium (Cr(VI)), Lead (Pb(II)) and Copper (Cu(II)) was investigated at different operating conditions like pH, time, initial concentration and temperature. The heavy metals adsorption process was well illustrated by the Lagergren's pseudo-second-order kinetic model and the equilibrium data fitted excellently to Langmuir isotherm. Maximum adsorption capacity obtained from Langmuir isotherm for Hg(II) was 82.4 mg/g, Cr(VI) was 126.9 mg/g, Pb(II) was 147.5 mg/g and Cu(II) was 167.8 mg/g. The thermodynamic parameters revealed that the adsorption of heavy metals on melanin is favorable, spontaneous and endothermic in nature. Binding of heavy metals on melanin surface was proved by Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). Contemplating the results, biosynthesized melanin can be a potential adsorbent for efficient removal of Hg(II), Cr(VI), Pb(II) and Cu(II) ions from aqueous solution. Copyright © 2018 Elsevier Ltd. All rights reserved.

  11. Preliminary scaling laws for plasma current, ion kinetic temperature, and plasma number density in the NASA Lewis bumpy torus plasma

    NASA Technical Reports Server (NTRS)

    Roth, J. R.

    1976-01-01

    Parametric variation of independent variables which may affect the characteristics of bumpy torus plasma have identified those which have a significant effect on the plasma current, ion kinetic temperature, and plasma number density, and those which do not. Empirical power law correlations of the plasma current, and the ion kinetic temperature and number density were obtained as functions of potential applied to the midplane electrode rings, the background neutral gas pressure, and the magnetic field strength. Additional parameters studied included the type of gas, the polarity of the midplane electrode rings, the mode of plasma operation, and the method of measuring the plasma number density. No significant departures from the scaling laws appear to occur at the highest ion kinetic temperatures or number densities obtained to date.

  12. Kinetic Equations for Describing the Liquid-Glass Transition in Polymers

    NASA Astrophysics Data System (ADS)

    Aksenov, V. L.; Tropin, T. V.; Schmelzer, J. V. P.

    2018-01-01

    We present a theoretical approach based on nonequilibrium thermodynamics and used to describe the kinetics of the transition from the liquid to the glassy state (glass transition). In the framework of this approach, we construct kinetic equations describing the time and temperature evolution of the structural parameter. We discuss modifications of the equations required for taking the nonexponential, nonlinear character of the relaxation in the vitrification region into account. To describe the formation of polymer glasses, we present modified expressions for the system relaxation time. We compare the obtained results with experimental data, measurements of the polystyrene glass transition for different cooling rates using the method of differential scanning calorimetry. We discuss prospects for developing a method for describing the polymer glass transition.

  13. Kinetic Analysis of the Main Temperature Stage of Fast Pyrolysis

    NASA Astrophysics Data System (ADS)

    Yang, Xiaoxiao; Zhao, Yuying; Xu, Lanshu; Li, Rui

    2017-10-01

    Kinetics of the thermal decomposition of eucalyptus chips was evaluated using a high-rate thermogravimetric analyzer (BL-TGA) designed by our research group. The experiments were carried out under non-isothermal condition in order to determine the fast pyrolysis behavior of the main temperature stage (350-540ºC) at heating rates of 60, 120, 180, and 360ºC min-1. The Coats-Redfern integral method and four different reaction mechanism models were adopted to calculate the kinetic parameters including apparent activation energy and pre-exponential factor, and the Flynn-Wall-Ozawa method was employed to testify apparent activation energy. The results showed that estimation value was consistent with the values obtained by linear fitting equations, and the best-fit model for fast pyrolysis was found.

  14. Image analysis and green tea color change kinetics during thin-layer drying.

    PubMed

    Shahabi, Mohammad; Rafiee, Shahin; Mohtasebi, Seyed Saeid; Hosseinpour, Soleiman

    2014-09-01

    This study was conducted to investigate the effect of air temperature and air flow velocity on kinetics of color parameter changes during hot-air drying of green tea, to obtain the best model for hot-air drying of green tea, to apply a computer vision system and to study the color changes during drying. In the proposed computer vision system system, at first RGB values of the images were converted into XYZ values and then to Commission International d'Eclairage L*a*b* color coordinates. The obtained color parameters of L*, a* and b* were calibrated with Hunter-Lab colorimeter. These values were also used for calculation of the color difference, chroma, hue angle and browning index. The values of L* and b* decreased, while the values of a* and color difference (ΔE*ab ) increased during hot-air drying. Drying data were fitted to three kinetic models. Zero, first-order and fractional conversion models were utilized to describe the color changes of green tea. The suitability of fitness was determined using the coefficient of determination (R (2)) and root-mean-square error. Results showed that the fraction conversion model had more acceptable fitness than the other two models in most of color parameters. © The Author(s) 2013 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

  15. Kinetics of substrate utilization and bacterial growth of crude oil degraded by Pseudomonas aeruginosa.

    PubMed

    Talaiekhozani, Amirreza; Jafarzadeh, Nematollah; Fulazzaky, Mohamad Ali; Talaie, Mohammad Reza; Beheshti, Masoud

    2015-01-01

    Pollution associated with crude oil (CO) extraction degrades the quality of waters, threatens drinking water sources and may ham air quality. The systems biology approach aims at learning the kinetics of substrate utilization and bacterial growth for a biological process for which very limited knowledge is available. This study uses the Pseudomonas aeruginosa to degrade CO and determines the kinetic parameters of substrate utilization and bacterial growth modeled from a completely mixed batch reactor. The ability of Pseudomonas aeruginosa can remove 91 % of the total petroleum hydrocarbons and 83 % of the aromatic compounds from oily environment. The value k of 9.31 g of substrate g(-1) of microorganism d(-1) could be far higher than the value k obtained for petrochemical wastewater treatment and that for municipal wastewater treatment. The production of new cells of using CO as the sole carbon and energy source can exceed 2(3) of the existing cells per day. The kinetic parameters are verified to contribute to improving the biological removal of CO from oily environment.

  16. Kinetic modeling of ion conduction in KcsA potassium channel.

    PubMed

    Mafé, Salvador; Pellicer, Julio; Cervera, Javier

    2005-05-22

    KcsA constitutes a potassium channel of known structure that shows both high conduction rates and selectivity among monovalent cations. A kinetic model for ion conduction through this channel that assumes rapid ion transport within the filter has recently been presented by Nelson. In a recent, brief communication, we used the model to provide preliminary explanations to the experimental current-voltage J-V and conductance-concentration g-S curves obtained for a series of monovalent ions (K(+),Tl(+), and Rb(+)). We did not assume rapid ion transport in the calculations, since ion transport within the selectivity filter could be rate limiting for ions other than native K(+). This previous work is now significantly extended to the following experimental problems. First, the outward rectification of the J-V curves in K(+) symmetrical solutions is analyzed using a generalized kinetic model. Second, the J-V and g-S curves for NH(4) (+) are obtained and compared with those of other ions (the NH(4) (+) J-V curve is qualitatively different from those of Rb(+) and Tl(+)). Third, the effects of Na(+) block on K(+) and Rb(+) currents through single KcsA channels are studied and the different blocking behavior is related to the values of the translocation rate constants characteristic of ion transport within the filter. Finally, the significantly decreased K(+) conductance caused by mutation of the wild-type channel is also explained in terms of this rate constant. In order to keep the number of model parameters to a minimum, we do not allow the electrical distance (an empirical parameter of kinetic models that controls the exponential voltage dependence of the dissociation rate) to vary with the ionic species. Without introducing the relatively high number of adjustable parameters of more comprehensive site-based models, we show that ion association to the filter is rate controlling at low concentrations, but ion dissociation from the filter and ion transport within the filter

  17. Higher adsorption capacity of Spirulina platensis alga for Cr(VI) ions removal: parameter optimisation, equilibrium, kinetic and thermodynamic predictions.

    PubMed

    Gunasundari, Elumalai; Senthil Kumar, Ponnusamy

    2017-04-01

    This study discusses about the biosorption of Cr(VI) ion from aqueous solution using ultrasonic assisted Spirulina platensis (UASP). The prepared UASP biosorbent was characterised by Fourier transform infrared spectroscopy, X-ray diffraction, Brunauer-Emmet-Teller, scanning electron spectroscopy and energy dispersive X-ray and thermogravimetric analyses. The optimum condition for the maximum removal of Cr(VI) ions for an initial concentration of 50 mg/l by UASP was measured as: adsorbent dose of 1 g/l, pH of 3.0, contact time of 30 min and temperature of 303 K. Adsorption isotherm, kinetics and thermodynamic parameters were calculated. Freundlich model provided the best results for the removal of Cr(VI) ions by UASP. The adsorption kinetics of Cr(VI) ions onto UASP showed that the pseudo-first-order model was well in line with the experimental data. In the thermodynamic study, the parameters like Gibb's free energy, enthalpy and entropy changes were evaluated. This result explains that the adsorption of Cr(VI) ions onto the UASP was exothermic and spontaneous in nature. Desorption of the biosorbent was done using different desorbing agents in which NaOH gave the best result. The prepared material showed higher affinity for the removal of Cr(VI) ions and this may be an alternative material to the existing commercial adsorbents.

  18. Computation of restoration of ligand response in the random kinetics of a prostate cancer cell signaling pathway.

    PubMed

    Dana, Saswati; Nakakuki, Takashi; Hatakeyama, Mariko; Kimura, Shuhei; Raha, Soumyendu

    2011-01-01

    Mutation and/or dysfunction of signaling proteins in the mitogen activated protein kinase (MAPK) signal transduction pathway are frequently observed in various kinds of human cancer. Consistent with this fact, in the present study, we experimentally observe that the epidermal growth factor (EGF) induced activation profile of MAP kinase signaling is not straightforward dose-dependent in the PC3 prostate cancer cells. To find out what parameters and reactions in the pathway are involved in this departure from the normal dose-dependency, a model-based pathway analysis is performed. The pathway is mathematically modeled with 28 rate equations yielding those many ordinary differential equations (ODE) with kinetic rate constants that have been reported to take random values in the existing literature. This has led to us treating the ODE model of the pathways kinetics as a random differential equations (RDE) system in which the parameters are random variables. We show that our RDE model captures the uncertainty in the kinetic rate constants as seen in the behavior of the experimental data and more importantly, upon simulation, exhibits the abnormal EGF dose-dependency of the activation profile of MAP kinase signaling in PC3 prostate cancer cells. The most likely set of values of the kinetic rate constants obtained from fitting the RDE model into the experimental data is then used in a direct transcription based dynamic optimization method for computing the changes needed in these kinetic rate constant values for the restoration of the normal EGF dose response. The last computation identifies the parameters, i.e., the kinetic rate constants in the RDE model, that are the most sensitive to the change in the EGF dose response behavior in the PC3 prostate cancer cells. The reactions in which these most sensitive parameters participate emerge as candidate drug targets on the signaling pathway. 2011 Elsevier Ireland Ltd. All rights reserved.

  19. Kinetic operational models of agonism for G-protein-coupled receptors.

    PubMed

    Hoare, Samuel R J; Pierre, Nicolas; Moya, Arturo Gonzalez; Larson, Brad

    2018-06-07

    The application of kinetics to research and therapeutic development of G-protein-coupled receptors has become increasingly valuable. Pharmacological models provide the foundation of pharmacology, providing concepts and measurable parameters such as efficacy and potency that have underlain decades of successful drug discovery. Currently there are few pharmacological models that incorporate kinetic activity in such a way as to yield experimentally-accessible drug parameters. In this study, a kinetic model of pharmacological response was developed that provides a kinetic descriptor of efficacy (the transduction rate constant, k τ ) and allows measurement of receptor-ligand binding kinetics from functional data. The model assumes: (1) receptor interacts with a precursor of the response ("Transduction potential") and converts it to the response. (2) The response can decay. Familiar response vs time plots emerge, depending on whether transduction potential is depleted and/or response decays. These are the straight line, the "association" exponential curve, and the rise-and-fall curve. Convenient, familiar methods are described for measuring the model parameters and files are provided for the curve-fitting program Prism (GraphPad Software) that can be used as a guide. The efficacy parameter k τ is straightforward to measure and accounts for receptor reserve; all that is required is measurement of response over time at a maximally-stimulating concentration of agonist. The modular nature of the model framework allows it to be extended. Here this is done to incorporate antagonist-receptor binding kinetics and slow agonist-receptor equilibration. In principle, the modular framework can incorporate other cellular processes, such as receptor desensitization. The kinetic response model described here can be applied to measure kinetic pharmacological parameters than can be used to advance the understanding of GPCR pharmacology and optimize new and improved therapeutics

  20. Kinetic Alfvén solitary and rogue waves in superthermal plasmas

    NASA Astrophysics Data System (ADS)

    Bains, A. S.; Li, Bo; Xia, Li-Dong

    2014-03-01

    We investigate the small but finite amplitude solitary Kinetic Alfvén waves (KAWs) in low β plasmas with superthermal electrons modeled by a kappa-type distribution. A nonlinear Korteweg-de Vries (KdV) equation describing the evolution of KAWs is derived by using the standard reductive perturbation method. Examining the dependence of the nonlinear and dispersion coefficients of the KdV equation on the superthermal parameter κ, plasma β, and obliqueness of propagation, we show that these parameters may change substantially the shape and size of solitary KAW pulses. Only sub-Alfvénic, compressive solitons are supported. We then extend the study to examine kinetic Alfvén rogue waves by deriving a nonlinear Schrödinger equation from the KdV equation. Rational solutions that form rogue wave envelopes are obtained. We examine how the behavior of rogue waves depends on the plasma parameters in question, finding that the rogue envelopes are lowered with increasing electron superthermality whereas the opposite is true when the plasma β increases. The findings of this study may find applications to low β plasmas in astrophysical environments where particles are superthermally distributed.

  1. Excitation of dust kinetic Alfven waves by semi-relativistic ion beams

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Rubab, N.; Jaffer, G.

    2016-05-15

    The growth rates for dust kinetic Alfvén wave (DKAW) based on semi-relativistic Maxwellian distribution function are investigated in a hot and magnetized plasma. The dispersion relation of DKAW is obtained on a dust acoustic velocity branch, and the kinetic instability due to cross-field semi-relativistic ion flow is examined by the effect of dust parameters. Analytical expressions are derived for various modes as a natural consequence of the form of the solution, and is shown through graphical representation that the presence of dust particles and the cross-field semi-relativistic ions sensibly modify the dispersion characteristics of low-frequency DKAW. The results are validmore » for a frequency regime well below the dust cyclotron frequency. We suggest that semi-relativistic particles are an important factor in the growth/damping of DKAWs. It is also found that relativistic effects appear with the dust lower hybrid frequency are more effective for dust kinetic Alfvén waves in the perpendicular component as compared to the parallel one. In particular, the relativistic effects associated with electrons suppress the instability while ions enhance the growth rates. The growth rates are significantly modified with dust parameters and streaming velocity of cross-field ions.« less

  2. Relativistic Kinetic Theory

    NASA Astrophysics Data System (ADS)

    Vereshchagin, Gregory V.; Aksenov, Alexey G.

    2017-02-01

    Preface; Acknowledgements; Acronyms and definitions; Introduction; Part I. Theoretical Foundations: 1. Basic concepts; 2. Kinetic equation; 3. Averaging; 4. Conservation laws and equilibrium; 5. Relativistic BBGKY hierarchy; 6. Basic parameters in gases and plasmas; Part II. Numerical Methods: 7. The basics of computational physics; 8. Direct integration of Boltzmann equations; 9. Multidimensional hydrodynamics; Part III. Applications: 10. Wave dispersion in relativistic plasma; 11. Thermalization in relativistic plasma; 12. Kinetics of particles in strong fields; 13. Compton scattering in astrophysics and cosmology; 14. Self-gravitating systems; 15. Neutrinos, gravitational collapse and supernovae; Appendices; Bibliography; Index.

  3. The moisture outgassing kinetics of a silica reinforced polydimethylsiloxane

    NASA Astrophysics Data System (ADS)

    Sharma, H. N.; McLean, W.; Maxwell, R. S.; Dinh, L. N.

    2016-09-01

    A silica-filled polydimethylsiloxane (PDMS) composite M9787 was investigated for potential outgassing in a vacuum/dry environment with the temperature programmed desorption/reaction method. The outgassing kinetics of 463 K vacuum heat-treated samples, vacuum heat-treated samples which were subsequently re-exposed to moisture, and untreated samples were extracted using the isoconversional and constrained iterative regression methods in a complementary fashion. Density functional theory (DFT) calculations of water interactions with a silica surface were also performed to provide insight into the structural motifs leading to the obtained kinetic parameters. Kinetic analysis/model revealed that no outgassing occurs from the vacuum heat-treated samples in subsequent vacuum/dry environment applications at room temperature (˜300 K). The main effect of re-exposure of the vacuum heat-treated samples to a glove box condition (˜30 ppm by volume of H2O) for even a couple of days was the formation, on the silica surface fillers, of ˜60 ppm by weight of physisorbed and loosely bonded moisture, which subsequently outgasses at room temperature in a vacuum/dry environment in a time span of 10 yr. However, without any vacuum heat treatment and even after 1 h of vacuum pump down, about 300 ppm by weight of H2O would be released from the PDMS in the next few hours. Thereafter the outgassing rate slows down substantially. The presented methodology of using the isoconversional kinetic analysis results and some appropriate nature of the reaction as the constraints for more accurate iterative regression analysis/deconvolution of complex kinetic spectra, and of checking the so-obtained results with first principle calculations such as DFT can serve as a template for treating other complex physical/chemical processes as well.

  4. The moisture outgassing kinetics of a silica reinforced polydimethylsiloxane

    DOE PAGES

    Sharma, H. N.; McLean, W.; Maxwell, R. S.; ...

    2016-09-21

    We investigated a silica-filled polydimethylsiloxane (PDMS) composite M9787 for potential outgassing in a vacuum/dry environment with the temperature programmed desorption/reaction method. The outgassing kinetics of 463 K vacuum heat-treated samples, vacuum heat-treated samples which were subsequently re-exposed to moisture, and untreated samples were extracted using the isoconversional and constrained iterative regression methods in a complementary fashion. Density functional theory (DFT) calculations of water interactions with a silica surface were also performed to provide insight into the structural motifs leading to the obtained kinetic parameters. Kinetic analysis/model revealed that no outgassing occurs from the vacuum heat-treated samples in subsequent vacuum/dry environmentmore » applications at room temperature (~300 K). Moreover, the main effect of re-exposure of the vacuum heat-treated samples to a glove box condition (~30 ppm by volume of H 2O) for even a couple of days was the formation, on the silica surface fillers, of ~60 ppm by weight of physisorbed and loosely bonded moisture, which subsequently outgasses at room temperature in a vacuum/dry environment in a time span of 10 yr. However, without any vacuum heat treatment and even after 1 h of vacuum pump down, about 300 ppm by weight of H 2O would be released from the PDMS in the next few hours. Thereafter the outgassing rate slows down substantially. Our presented methodology of using the isoconversional kinetic analysis results and some appropriate nature of the reaction as the constraints for more accurate iterative regression analysis/deconvolution of complex kinetic spectra, and of checking the so-obtained results with first principle calculations such as DFT can serve as a template for treating other complex physical/chemical processes as well.« less

  5. Kinetics of the Active Medium of a Copper Vapor Brightness Amplifier

    NASA Astrophysics Data System (ADS)

    Kulagin, A. E.; Torgaev, S. N.; Evtushenko, G. S.; Trigub, M. V.

    2018-03-01

    A spatiotemporal kinetics of the active medium of a copper vapor brightness amplifier is described that allows gain characteristics to be investigated during the pump pulse. Model calculations show that changing the discharge parameters allows the radial gain profiles to be improved significantly, as well as the gain and the inversion duration to be increased. The data obtained will be used to choose the operating conditions for the active medium in the brightness amplifier mode.

  6. Simulation of ITG instabilities with fully kinetic ions and drift-kinetic electrons in tokamaks

    NASA Astrophysics Data System (ADS)

    Hu, Youjun; Chen, Yang; Parker, Scott

    2017-10-01

    A turbulence simulation model with fully kinetic ions and drift-kinetic electrons is being developed in the toroidal electromagnetic turbulence code GEM. This is motivated by the observation that gyrokinetic ions are not well justified in simulating turbulence in tokamak edges with steep density profile, where ρi / L is not small enough to be used a small parameter needed by the gyrokinetic ordering (here ρi is the gyro-radius of ions and L is the scale length of density profile). In this case, the fully kinetic ion model may be useful. Our model uses an implicit scheme to suppress high-frequency compressional Alfven waves and waves associated with the gyro-motion of ions. The ion orbits are advanced by using the well-known Boris scheme, which reproduces correct drift-motion even with large time-step comparable to the ion gyro-period. The field equation in this model is Ampere's law with the magnetic field eliminated by using an implicit scheme of Faraday's law. The current contributed by ions are computed by using an implicit δf method. A flux tube approximation is adopted, which makes the field equation much easier to solve. Numerical results of electromagnetic ITG obtained from this model will be presented and compared with the gyrokinetic results. This work is supported by U.S. Department of Energy, Office of Fusion Energy Sciences under Award No. DE-SC0008801.

  7. Improved parameter extraction and classification for dynamic contrast enhanced MRI of prostate

    NASA Astrophysics Data System (ADS)

    Haq, Nandinee Fariah; Kozlowski, Piotr; Jones, Edward C.; Chang, Silvia D.; Goldenberg, S. Larry; Moradi, Mehdi

    2014-03-01

    Magnetic resonance imaging (MRI), particularly dynamic contrast enhanced (DCE) imaging, has shown great potential in prostate cancer diagnosis and prognosis. The time course of the DCE images provides measures of the contrast agent uptake kinetics. Also, using pharmacokinetic modelling, one can extract parameters from the DCE-MR images that characterize the tumor vascularization and can be used to detect cancer. A requirement for calculating the pharmacokinetic DCE parameters is estimating the Arterial Input Function (AIF). One needs an accurate segmentation of the cross section of the external femoral artery to obtain the AIF. In this work we report a semi-automatic method for segmentation of the cross section of the femoral artery, using circular Hough transform, in the sequence of DCE images. We also report a machine-learning framework to combine pharmacokinetic parameters with the model-free contrast agent uptake kinetic parameters extracted from the DCE time course into a nine-dimensional feature vector. This combination of features is used with random forest and with support vector machine classi cation for cancer detection. The MR data is obtained from patients prior to radical prostatectomy. After the surgery, wholemount histopathology analysis is performed and registered to the DCE-MR images as the diagnostic reference. We show that the use of a combination of pharmacokinetic parameters and the model-free empirical parameters extracted from the time course of DCE results in improved cancer detection compared to the use of each group of features separately. We also validate the proposed method for calculation of AIF based on comparison with the manual method.

  8. Detection of kinetic change points in piece-wise linear single molecule motion

    NASA Astrophysics Data System (ADS)

    Hill, Flynn R.; van Oijen, Antoine M.; Duderstadt, Karl E.

    2018-03-01

    Single-molecule approaches present a powerful way to obtain detailed kinetic information at the molecular level. However, the identification of small rate changes is often hindered by the considerable noise present in such single-molecule kinetic data. We present a general method to detect such kinetic change points in trajectories of motion of processive single molecules having Gaussian noise, with a minimum number of parameters and without the need of an assumed kinetic model beyond piece-wise linearity of motion. Kinetic change points are detected using a likelihood ratio test in which the probability of no change is compared to the probability of a change occurring, given the experimental noise. A predetermined confidence interval minimizes the occurrence of false detections. Applying the method recursively to all sub-regions of a single molecule trajectory ensures that all kinetic change points are located. The algorithm presented allows rigorous and quantitative determination of kinetic change points in noisy single molecule observations without the need for filtering or binning, which reduce temporal resolution and obscure dynamics. The statistical framework for the approach and implementation details are discussed. The detection power of the algorithm is assessed using simulations with both single kinetic changes and multiple kinetic changes that typically arise in observations of single-molecule DNA-replication reactions. Implementations of the algorithm are provided in ImageJ plugin format written in Java and in the Julia language for numeric computing, with accompanying Jupyter Notebooks to allow reproduction of the analysis presented here.

  9. Virus Neutralisation: New Insights from Kinetic Neutralisation Curves

    PubMed Central

    Magnus, Carsten

    2013-01-01

    Antibodies binding to the surface of virions can lead to virus neutralisation. Different theories have been proposed to determine the number of antibodies that must bind to a virion for neutralisation. Early models are based on chemical binding kinetics. Applying these models lead to very low estimates of the number of antibodies needed for neutralisation. In contrast, according to the more conceptual approach of stoichiometries in virology a much higher number of antibodies is required for virus neutralisation by antibodies. Here, we combine chemical binding kinetics with (virological) stoichiometries to better explain virus neutralisation by antibody binding. This framework is in agreement with published data on the neutralisation of the human immunodeficiency virus. Knowing antibody reaction constants, our model allows us to estimate stoichiometrical parameters from kinetic neutralisation curves. In addition, we can identify important parameters that will make further analysis of kinetic neutralisation curves more valuable in the context of estimating stoichiometries. Our model gives a more subtle explanation of kinetic neutralisation curves in terms of single-hit and multi-hit kinetics. PMID:23468602

  10. Optimization and kinetic modeling of esterification of the oil obtained from waste plum stones as a pretreatment step in biodiesel production.

    PubMed

    Kostić, Milan D; Veličković, Ana V; Joković, Nataša M; Stamenković, Olivera S; Veljković, Vlada B

    2016-02-01

    This study reports on the use of oil obtained from waste plum stones as a low-cost feedstock for biodiesel production. Because of high free fatty acid (FFA) level (15.8%), the oil was processed through the two-step process including esterification of FFA and methanolysis of the esterified oil catalyzed by H2SO4 and CaO, respectively. Esterification was optimized by response surface methodology combined with a central composite design. The second-order polynomial equation predicted the lowest acid value of 0.53mgKOH/g under the following optimal reaction conditions: the methanol:oil molar ratio of 8.5:1, the catalyst amount of 2% and the reaction temperature of 45°C. The predicted acid value agreed with the experimental acid value (0.47mgKOH/g). The kinetics of FFA esterification was described by the irreversible pseudo first-order reaction rate law. The apparent kinetic constant was correlated with the initial methanol and catalyst concentrations and reaction temperature. The activation energy of the esterification reaction slightly decreased from 13.23 to 11.55kJ/mol with increasing the catalyst concentration from 0.049 to 0.172mol/dm(3). In the second step, the esterified oil reacted with methanol (methanol:oil molar ratio of 9:1) in the presence of CaO (5% to the oil mass) at 60°C. The properties of the obtained biodiesel were within the EN 14214 standard limits. Hence, waste plum stones might be valuable raw material for obtaining fatty oil for the use as alternative feedstock in biodiesel production. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Kinetics study of carbon raiser on the reduction of nickel laterite from Pomalaa, Southeast Sulawesi

    NASA Astrophysics Data System (ADS)

    Petrus, H. T. B. M.; Rhamdani, A. R.; Putera, A. D. P.; Warmada, I. W.; Yuliansyad, A. T.; Perdana, I.

    2016-11-01

    As one of the top ten on nickel laterite ore resources in the world, Indonesia must have been initiating the nickel processing in total amount of about 1.5 million tonnes. In regard to the low nickel laterite processing, one of the possible product is nickel pig iron (NPI) needed for the stainless steel industries. In this study carbon raiser that is waste from oil industries was used to replace metalurgical coke. The kinetic of nickel laterite reduction using carbon raiser was studied and compared with anthrasite coal. In this work, the author conducted the reduction of nickel laterite ores by both carbon raiser and anthrasite coal as reductant, in air and CO2 atmosphere, within the temperature ranged from 800°C and 1000°C. Two models were applied, sphere particle geometry model and Ginstling-Brounhstein diffusion model, to study the kinetic parameters. The results indicated that type of reductants and reduction atmosphere greatly influence the kinetic parameters. The obtained values of activation energy were varied between 17.44-18.12 kcal/mol.

  12. Thermoluminescence kinetic features of Lithium Iodide (LiI) single crystal grown by vertical Bridgman technique

    NASA Astrophysics Data System (ADS)

    Daniel, D. Joseph; Kim, H. J.; Kim, Sunghwan; Khan, Sajid

    2017-08-01

    Single crystal of pure Lithium Iodide (LiI) has been grown from melt by using the vertical Bridgman technique. Thermoluminescence (TL) Measurements were carried out at 1 K/s following X-ray irradiation. The TL glow curve consists of a dominant peak at (peak-maximum Tm) 393 K and one low temperature peak of weaker intensity at 343 K. The order of kinetics (b), activation energy (E), and the frequency factor (S) for a prominent TL glow peak observed around 393 K for LiI crystals are reported for the first time. The peak shape analysis of the glow peak indicates the kinetics to be of the first order. The value of E is calculated using various standard methods such as initial rise (IR), whole glow peak (WGP), peak shape (PS), computerized glow curve deconvolution (CGCD) and Variable Heating rate (VHR) methods. An average value of 1.06 eV is obtained in this case. In order to validate the obtained parameters, numerically integrated TL glow curve has been generated using experimentally determined kinetic parameters. The effective atomic number (Zeff) for this material was determined and found to be 52. X-ray induced emission spectra of pure LiI single crystal are studied at room temperature and it is found that the sample exhibit sharp emission at 457 nm and broad emission at 650 nm.

  13. Probabilistic parameter estimation of activated sludge processes using Markov Chain Monte Carlo.

    PubMed

    Sharifi, Soroosh; Murthy, Sudhir; Takács, Imre; Massoudieh, Arash

    2014-03-01

    One of the most important challenges in making activated sludge models (ASMs) applicable to design problems is identifying the values of its many stoichiometric and kinetic parameters. When wastewater characteristics data from full-scale biological treatment systems are used for parameter estimation, several sources of uncertainty, including uncertainty in measured data, external forcing (e.g. influent characteristics), and model structural errors influence the value of the estimated parameters. This paper presents a Bayesian hierarchical modeling framework for the probabilistic estimation of activated sludge process parameters. The method provides the joint probability density functions (JPDFs) of stoichiometric and kinetic parameters by updating prior information regarding the parameters obtained from expert knowledge and literature. The method also provides the posterior correlations between the parameters, as well as a measure of sensitivity of the different constituents with respect to the parameters. This information can be used to design experiments to provide higher information content regarding certain parameters. The method is illustrated using the ASM1 model to describe synthetically generated data from a hypothetical biological treatment system. The results indicate that data from full-scale systems can narrow down the ranges of some parameters substantially whereas the amount of information they provide regarding other parameters is small, due to either large correlations between some of the parameters or a lack of sensitivity with respect to the parameters. Copyright © 2013 Elsevier Ltd. All rights reserved.

  14. Pre-Steady-State Kinetic Analysis of Single-Nucleotide Incorporation by DNA Polymerases

    PubMed Central

    Su, Yan; Guengerich, F. Peter

    2016-01-01

    Pre-steady-state kinetic analysis is a powerful and widely used method to obtain multiple kinetic parameters. This protocol provides a step-by-step procedure for pre-steady-state kinetic analysis of single-nucleotide incorporation by a DNA polymerase. It describes the experimental details of DNA substrate annealing, reaction mixture preparation, handling of the RQF-3 rapid quench-flow instrument, denaturing polyacrylamide DNA gel preparation, electrophoresis, quantitation, and data analysis. The core and unique part of this protocol is the rationale for preparation of the reaction mixture (the ratio of the polymerase to the DNA substrate) and methods for conducting pre-steady-state assays on an RQF-3 rapid quench-flow instrument, as well as data interpretation after analysis. In addition, the methods for the DNA substrate annealing and DNA polyacrylamide gel preparation, electrophoresis, quantitation and analysis are suitable for use in other studies. PMID:27248785

  15. Kinetic energy offsets for multicharged ions from an electron beam ion source.

    PubMed

    Kulkarni, D D; Ahl, C D; Shore, A M; Miller, A J; Harriss, J E; Sosolik, C E; Marler, J P

    2017-08-01

    Using a retarding field analyzer, we have measured offsets between the nominal and measured kinetic energy of multicharged ions extracted from an electron beam ion source (EBIS). By varying source parameters, a shift in ion kinetic energy was attributed to the trapping potential produced by the space charge of the electron beam within the EBIS. The space charge of the electron beam depends on its charge density, which in turn depends on the amount of negative charge (electron beam current) and its velocity (electron beam energy). The electron beam current and electron beam energy were both varied to obtain electron beams of varying space charge and these were related to the observed kinetic energy offsets for Ar 4+ and Ar 8+ ion beams. Knowledge of these offsets is important for studies that seek to utilize slow, i.e., low kinetic energy, multicharged ions to exploit their high potential energies for processes such as surface modification. In addition, we show that these offsets can be utilized to estimate the effective radius of the electron beam inside the trap.

  16. Influence of new military athletic footwear on the kinetics and kinematics of running in relation to army boots.

    PubMed

    Sinclair, Jonathan; Taylor, Paul J

    2014-10-01

    Musculoskeletal injuries in the lower extremities are common in military recruits. Army boots have frequently been cited as a potential mechanism behind these high injury rates. In response to this, the British Army introduced new footwear models, the PT-03 (cross-trainer) and PT1000 (running shoes), which are issued to each new recruit in an attempt to reduce the incidence of these injuries. The aim of the current investigation was to examine the kinetics and kinematic of the PT-03 and PT1000 footwear in relation to conventional army boots. Thirteen participants ran at 4.0 m·s in each footwear condition. Three-dimensional kinematics from the hip, knee, and ankle were measured using an 8-camera motion analysis system. In addition, simultaneous ground reaction forces were obtained. Kinetic parameters were obtained alongside joint kinematics and compared using repeated-measures analyses of variance. The kinetic analysis revealed that impact parameters were significantly greater when running in the army boot compared with the PT-03 and PT1000. The kinematic analysis indicated that, in comparison with the PT-03 and PT1000, running in army boots was associated with significantly greater eversion and tibial internal rotation. It was also found that when running in the PT-03 footwear, participants exhibited significantly greater hip adduction and knee abduction compared with the army boots and PT1000. The results of this study suggest that the army boots and PT-03 footwear are associated with kinetic and kinematic parameters that have been linked to the etiology of injury; thus, it is recommended that the PT1000 footwear be adopted for running exercises.

  17. Optics-based compressibility parameter for pharmaceutical tablets obtained with the aid of the terahertz refractive index.

    PubMed

    Chakraborty, Mousumi; Ridgway, Cathy; Bawuah, Prince; Markl, Daniel; Gane, Patrick A C; Ketolainen, Jarkko; Zeitler, J Axel; Peiponen, Kai-Erik

    2017-06-15

    The objective of this study is to propose a novel optical compressibility parameter for porous pharmaceutical tablets. This parameter is defined with the aid of the effective refractive index of a tablet that is obtained from non-destructive and contactless terahertz (THz) time-delay transmission measurement. The optical compressibility parameter of two training sets of pharmaceutical tablets with a priori known porosity and mass fraction of a drug was investigated. Both pharmaceutical sets were compressed with one of the most commonly used excipients, namely microcrystalline cellulose (MCC) and drug Indomethacin. The optical compressibility clearly correlates with the skeletal bulk modulus determined by mercury porosimetry and the recently proposed terahertz lumped structural parameter calculated from terahertz measurements. This lumped structural parameter can be used to analyse the pattern of arrangement of excipient and drug particles in porous pharmaceutical tablets. Therefore, we propose that the optical compressibility can serve as a quality parameter of a pharmaceutical tablet corresponding with the skeletal bulk modulus of the porous tablet, which is related to structural arrangement of the powder particles in the tablet. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Obtaining parsimonious hydraulic conductivity fields using head and transport observations: A Bayesian geostatistical parameter estimation approach

    NASA Astrophysics Data System (ADS)

    Fienen, M.; Hunt, R.; Krabbenhoft, D.; Clemo, T.

    2009-08-01

    Flow path delineation is a valuable tool for interpreting the subsurface hydrogeochemical environment. Different types of data, such as groundwater flow and transport, inform different aspects of hydrogeologic parameter values (hydraulic conductivity in this case) which, in turn, determine flow paths. This work combines flow and transport information to estimate a unified set of hydrogeologic parameters using the Bayesian geostatistical inverse approach. Parameter flexibility is allowed by using a highly parameterized approach with the level of complexity informed by the data. Despite the effort to adhere to the ideal of minimal a priori structure imposed on the problem, extreme contrasts in parameters can result in the need to censor correlation across hydrostratigraphic bounding surfaces. These partitions segregate parameters into facies associations. With an iterative approach in which partitions are based on inspection of initial estimates, flow path interpretation is progressively refined through the inclusion of more types of data. Head observations, stable oxygen isotopes (18O/16O ratios), and tritium are all used to progressively refine flow path delineation on an isthmus between two lakes in the Trout Lake watershed, northern Wisconsin, United States. Despite allowing significant parameter freedom by estimating many distributed parameter values, a smooth field is obtained.

  19. Obtaining parsimonious hydraulic conductivity fields using head and transport observations: A Bayesian geostatistical parameter estimation approach

    USGS Publications Warehouse

    Fienen, M.; Hunt, R.; Krabbenhoft, D.; Clemo, T.

    2009-01-01

    Flow path delineation is a valuable tool for interpreting the subsurface hydrogeochemical environment. Different types of data, such as groundwater flow and transport, inform different aspects of hydrogeologic parameter values (hydraulic conductivity in this case) which, in turn, determine flow paths. This work combines flow and transport information to estimate a unified set of hydrogeologic parameters using the Bayesian geostatistical inverse approach. Parameter flexibility is allowed by using a highly parameterized approach with the level of complexity informed by the data. Despite the effort to adhere to the ideal of minimal a priori structure imposed on the problem, extreme contrasts in parameters can result in the need to censor correlation across hydrostratigraphic bounding surfaces. These partitions segregate parameters into facies associations. With an iterative approach in which partitions are based on inspection of initial estimates, flow path interpretation is progressively refined through the inclusion of more types of data. Head observations, stable oxygen isotopes (18O/16O ratios), and tritium are all used to progressively refine flow path delineation on an isthmus between two lakes in the Trout Lake watershed, northern Wisconsin, United States. Despite allowing significant parameter freedom by estimating many distributed parameter values, a smooth field is obtained.

  20. Kinetics of the cellular decomposition of supersaturated solid solutions

    NASA Astrophysics Data System (ADS)

    Ivanov, M. A.; Naumuk, A. Yu.

    2014-09-01

    A consistent description of the kinetics of the cellular decomposition of supersaturated solid solutions with the development of a spatially periodic structure of lamellar (platelike) type, which consists of alternating phases of precipitates on the basis of the impurity component and depleted initial solid solution, is given. One of the equations, which determines the relationship between the parameters that describe the process of decomposition, has been obtained from a comparison of two approaches in order to determine the rate of change in the free energy of the system. The other kinetic parameters can be described with the use of a variational method, namely, by the maximum velocity of motion of the decomposition boundary at a given temperature. It is shown that the mutual directions of growth of the lamellae of different phases are determined by the minimum value of the interphase surface energy. To determine the parameters of the decomposition, a simple thermodynamic model of states with a parabolic dependence of the free energy on the concentrations has been used. As a result, expressions that describe the decomposition rate, interlamellar distance, and the concentration of impurities in the phase that remain after the decomposition have been derived. This concentration proves to be equal to the half-sum of the initial concentration and the equilibrium concentration corresponding to the decomposition temperature.

  1. High resolution approach to the native state ensemble kinetics and thermodynamics.

    PubMed

    Wu, Sangwook; Zhuravlev, Pavel I; Papoian, Garegin A

    2008-12-15

    Many biologically interesting functions such as allosteric switching or protein-ligand binding are determined by the kinetics and mechanisms of transitions between various conformational substates of the native basin of globular proteins. To advance our understanding of these processes, we constructed a two-dimensional free energy surface (FES) of the native basin of a small globular protein, Trp-cage. The corresponding order parameters were defined using two native substructures of Trp-cage. These calculations were based on extensive explicit water all-atom molecular dynamics simulations. Using the obtained two-dimensional FES, we studied the transition kinetics between two Trp-cage conformations, finding that switching process shows a borderline behavior between diffusive and weakly-activated dynamics. The transition is well-characterized kinetically as a biexponential process. We also introduced a new one-dimensional reaction coordinate for the conformational transition, finding reasonable qualitative agreement with the two-dimensional kinetics results. We investigated the distribution of all the 38 native nuclear magnetic resonance structures on the obtained FES, analyzing interactions that stabilize specific low-energy conformations. Finally, we constructed a FES for the same system but with simple dielectric model of water instead of explicit water, finding that the results were surprisingly similar in a small region centered on the native conformations. The dissimilarities between the explicit and implicit model on the larger-scale point to the important role of water in mediating interactions between amino acid residues.

  2. Oxidation Kinetics of Ferritic Alloys in High-Temperature Steam Environments

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Parker, Stephen S.; White, Josh; Hosemann, Peter

    High-temperature isothermal steam oxidation kinetic parameters of several ferritic alloys were determined by thermogravimetric analysis. We measured the oxidation kinetic constant (k) as a function of temperature from 900°C to 1200°C. The results show a marked increase in oxidation resistance compared to reference Zircaloy-2, with kinetic constants 3–5 orders of magnitude lower across the experimental temperature range. Our results of this investigation supplement previous findings on the properties of ferritic alloys for use as candidate cladding materials and extend kinetic parameter measurements to high-temperature steam environments suitable for assessing accident tolerance for light water reactor applications.

  3. Oxidation Kinetics of Ferritic Alloys in High-Temperature Steam Environments

    DOE PAGES

    Parker, Stephen S.; White, Josh; Hosemann, Peter; ...

    2017-11-03

    High-temperature isothermal steam oxidation kinetic parameters of several ferritic alloys were determined by thermogravimetric analysis. We measured the oxidation kinetic constant (k) as a function of temperature from 900°C to 1200°C. The results show a marked increase in oxidation resistance compared to reference Zircaloy-2, with kinetic constants 3–5 orders of magnitude lower across the experimental temperature range. Our results of this investigation supplement previous findings on the properties of ferritic alloys for use as candidate cladding materials and extend kinetic parameter measurements to high-temperature steam environments suitable for assessing accident tolerance for light water reactor applications.

  4. Oxidation Kinetics of Ferritic Alloys in High-Temperature Steam Environments

    NASA Astrophysics Data System (ADS)

    Parker, Stephen S.; White, Josh; Hosemann, Peter; Nelson, Andrew

    2018-02-01

    High-temperature isothermal steam oxidation kinetic parameters of several ferritic alloys were determined by thermogravimetric analysis. The oxidation kinetic constant ( k) was measured as a function of temperature from 900°C to 1200°C. The results show a marked increase in oxidation resistance compared to reference Zircaloy-2, with kinetic constants 3-5 orders of magnitude lower across the experimental temperature range. The results of this investigation supplement previous findings on the properties of ferritic alloys for use as candidate cladding materials and extend kinetic parameter measurements to high-temperature steam environments suitable for assessing accident tolerance for light water reactor applications.

  5. Vector curvaton with varying kinetic function

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dimopoulos, Konstantinos; Karciauskas, Mindaugas; Wagstaff, Jacques M.

    2010-01-15

    A new model realization of the vector curvaton paradigm is presented and analyzed. The model consists of a single massive Abelian vector field, with a Maxwell-type kinetic term. By assuming that the kinetic function and the mass of the vector field are appropriately varying during inflation, it is shown that a scale-invariant spectrum of superhorizon perturbations can be generated. These perturbations can contribute to the curvature perturbation of the Universe. If the vector field remains light at the end of inflation it is found that it can generate substantial statistical anisotropy in the spectrum and bispectrum of the curvature perturbation.more » In this case the non-Gaussianity in the curvature perturbation is predominantly anisotropic, which will be a testable prediction in the near future. If, on the other hand, the vector field is heavy at the end of inflation then it is demonstrated that particle production is approximately isotropic and the vector field alone can give rise to the curvature perturbation, without directly involving any fundamental scalar field. The parameter space for both possibilities is shown to be substantial. Finally, toy models are presented which show that the desired variation of the mass and kinetic function of the vector field can be realistically obtained, without unnatural tunings, in the context of supergravity or superstrings.« less

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

    NASA Astrophysics Data System (ADS)

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

    2018-03-01

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

  7. Kinetic study of Candida antarctica lipase B immobilization using poly(methyl methacrylate) nanoparticles obtained by miniemulsion polymerization as support.

    PubMed

    Valério, Alexsandra; Nicoletti, Gabrieli; Cipolatti, Eliane P; Ninow, Jorge L; Araújo, Pedro H H; Sayer, Cláudia; de Oliveira, Débora

    2015-03-01

    With the objective to obtain immobilized Candida antarctica lipase B (CalB) with good activity and improved utilization rate, this study evaluated the influence of enzyme and crodamol concentrations and initiator type on the CalB enzyme immobilization in nanoparticles consisting of poly(methyl methacrylate) (PMMA) obtained by miniemulsion polymerization. The kinetic study of immobilized CalB enzyme in PMMA nanoparticles was evaluated in terms of monomer conversion, particle size, zeta potential, and relative activity. The optimum immobilization condition for CalB was compared with free enzyme in the p-NPL hydrolysis activity measurement. Results showed a higher CalB enzyme stability after 20 hydrolysis cycles compared with free CalB enzyme; in particular, the relative immobilized enzyme activity was maintained up to 40%. In conclusion, PMMA nanoparticles proved to be a good support for the CalB enzyme immobilization and may be used as a feasible alternative catalyst in industrial processes.

  8. Kinetic study on bonding reaction of gelatin with CdS nanopaticles by UV-visible spectroscopy.

    PubMed

    Tang, Shihua; Wang, Baiyang; Li, Youqun

    2015-04-15

    The chemical kinetics on gelatin-CdS direct conjugates has been systematically investigated as a function of different temperature and reactant concentration (i.e. Cd(2+), S(2-) and gelatin) by UV-visible spectroscopy, for the first time. The nonlinear fitting and the differential method were used to calculate the initial rate based on the absorbance-time data. A double logarithmic linear equation for calculating the rate constant (k) and the reaction order (n) was introduced. The reaction kinetic parameters (n, k, Ea, and Z) and activation thermodynamic parameters (ΔG(≠), ΔH(≠), and ΔS(≠)) were obtained from variable temperature kinetic studies. The overall rate equation allowing evaluation of conditions that provide required reaction rate could be expressed as: r = 1.11 × 10(8) exp(-4971/T)[Cd(2+)][gelatin](0.6)[S(2-)](0.6) (M/S) The calculated values of the reaction rate are well coincide with the experimental results. A suitable kinetic model is also proposed. This work will provide guidance for the rational design of gelatin-directed syntheses of metal sulfide materials, and help to understand the biological effects of nanoparticles at the molecular level. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Modelling the mid-infrared drying of sweet potato: kinetics, mass and heat transfer parameters, and energy consumption

    NASA Astrophysics Data System (ADS)

    Onwude, Daniel I.; Hashim, Norhashila; Abdan, Khalina; Janius, Rimfiel; Chen, Guangnan

    2018-04-01

    This study investigated the drying kinetics, mass and heat transfer characteristics of sweet potato slices (0.4-0.6 cm thickness) during drying based on mid-infrared experimental set-up (intensity of 1100-1400 W/m2). Thin layer drying models were used to evaluate the drying kinetics of sweet potato slices. Two analytical models (Fick's diffusion model, and Dincer and Dost model) were used to study the mass transfer behaviour of sweet potato slices with and without shrinkage during mid-infrared drying. The heat transfer flux between the emitter and sweet potato slices was also investigated. Results demonstrated that an increase in infrared intensity from 1100 W/m2 to 1400 W/m2 resulted in increased in average radiation heat flux by 3.4 times and a 15% reduction in the overall drying time. The two-term exponential model was found to be the best in predicting the drying kinetics of sweet potato slices during mid-infrared drying. The specific heat consumption varied from 0.91-4.82 kWh/kg. The effective moisture diffusivity with and without shrinkage using the Fick's diffusion model varied from 2.632 × 10-9 to 1.596 × 10-8 m2/s, and 1.24 × 10-8 to 2.4 × 10-8 m2/s using Dincer and Dost model, respectively. The obtained values of mass transfer coefficient, Biot number and activation energy varied from 5.99 × 10-6 to 1.17 × 10-5 m/s, 0.53 to 2.62, and 12.83 kJ/mol to 34.64 kJ/mol, respectively. The values obtained for Biot number implied the existence of simultaneous internal and external resistances. The findings further explained that mid-infrared intensity of 1100 W/m2 did not significantly affect the quality of sweet potato during drying, demonstrating a great potential of applying low intensity mid-infrared radiation in the drying of agricultural crops.

  10. Kinetic parameters and nitrate, nitrite changes in bioremediation of Toxic Pentaerythritol Tetranitrate (PETN) contaminated soil

    PubMed Central

    Sadani, Mohsen; Karami, Mohammad Amin; Teimouri, Fahimeh; Amin, Mohammad Mehdi; Moosavi, Seyed Mahdi; Dehdashti, Bahare

    2017-01-01

    Background Cleanup of areas contaminated by explosives is a public health concern. Some explosives can be carcinogenic in humans. Pentaerythritol Tetranitrate (PETN), a powerful explosive with very low water solubility, can be easily transported to ground waters. Objective This study was conducted to determine the removal efficiencies of PETN from soil by bioremediation, and obtain kinetic parameters of biological process. Methods This experimental study was conducted at the Environmental Health Engineering Lab (Isfahan University of Medical Sciences, Isfahan, Iran) in 2015–2016. In the present work, bioremediation of the explosive-polluted soils by PETN in anaerobic-aerobic landfarming method was performed. The influence of seeding and biosurfactant addition on bioremediation was also evaluated. The data were analyzed using Microsoft Excel software. Results The results show that, as the initial concentration of PETN increased, the lag phase was increased and the specific growth rate was increased up to 0.1/day in concentration of 50 mg/kg, and then it was decreased to 0.04/day. Subsequent decreases in specific growth rate can cause substrate inhibition. Seeding causes decrease in lag phase significantly. Biosurfactant addition had little to no impact on the length of lag phase, but biosurfactant plus seeding can increase the growth rate to 0.2/day, however, inhibitory effect of the initial concentration was started in very high concentration of PETN (150 mg/kg). Conclusion Biosurfactant addition and seeding together have an impressive effect on biodegradation of PETN, furthermore seeding can enhance active microbial consortium and biosurfactant can improve the poor aqueous solubility of PETN, therefore making the substrate more accessible. PMID:29238507

  11. A new methodology to determine kinetic parameters for one- and two-step chemical models

    NASA Technical Reports Server (NTRS)

    Mantel, T.; Egolfopoulos, F. N.; Bowman, C. T.

    1996-01-01

    In this paper, a new methodology to determine kinetic parameters for simple chemical models and simple transport properties classically used in DNS of premixed combustion is presented. First, a one-dimensional code is utilized to performed steady unstrained laminar methane-air flame in order to verify intrinsic features of laminar flames such as burning velocity and temperature and concentration profiles. Second, the flame response to steady and unsteady strain in the opposed jet configuration is numerically investigated. It appears that for a well determined set of parameters, one- and two-step mechanisms reproduce the extinction limit of a laminar flame submitted to a steady strain. Computations with the GRI-mech mechanism (177 reactions, 39 species) and multicomponent transport properties are used to validate these simplified models. A sensitivity analysis of the preferential diffusion of heat and reactants when the Lewis number is close to unity indicates that the response of the flame to an oscillating strain is very sensitive to this number. As an application of this methodology, the interaction between a two-dimensional vortex pair and a premixed laminar flame is performed by Direct Numerical Simulation (DNS) using the one- and two-step mechanisms. Comparison with the experimental results of Samaniego et al. (1994) shows a significant improvement in the description of the interaction when the two-step model is used.

  12. An iterative procedure for obtaining maximum-likelihood estimates of the parameters for a mixture of normal distributions, Addendum

    NASA Technical Reports Server (NTRS)

    Peters, B. C., Jr.; Walker, H. F.

    1975-01-01

    New results and insights concerning a previously published iterative procedure for obtaining maximum-likelihood estimates of the parameters for a mixture of normal distributions were discussed. It was shown that the procedure converges locally to the consistent maximum likelihood estimate as long as a specified parameter is bounded between two limits. Bound values were given to yield optimal local convergence.

  13. Generic analysis of kinetically driven inflation

    NASA Astrophysics Data System (ADS)

    Saitou, Rio

    2018-04-01

    We perform a model-independent analysis of kinetically driven inflation (KDI) which (partially) includes generalized G-inflation and ghost inflation. We evaluate the background evolution splitting into the inflationary attractor and the perturbation around it. We also consider the quantum fluctuation of the scalar mode with a usual scaling and derive the spectral index, ignoring the contribution from the second-order products of slow-roll parameters. Using these formalisms, we find that within our generic framework the models of KDI which possess the shift symmetry of scalar field cannot create the quantum fluctuation consistent with the observation. Breaking the shift symmetry, we obtain a few essential conditions for viable models of KDI associated with the graceful exit.

  14. Customized Steady-State Constraints for Parameter Estimation in Non-Linear Ordinary Differential Equation Models

    PubMed Central

    Rosenblatt, Marcus; Timmer, Jens; Kaschek, Daniel

    2016-01-01

    Ordinary differential equation models have become a wide-spread approach to analyze dynamical systems and understand underlying mechanisms. Model parameters are often unknown and have to be estimated from experimental data, e.g., by maximum-likelihood estimation. In particular, models of biological systems contain a large number of parameters. To reduce the dimensionality of the parameter space, steady-state information is incorporated in the parameter estimation process. For non-linear models, analytical steady-state calculation typically leads to higher-order polynomial equations for which no closed-form solutions can be obtained. This can be circumvented by solving the steady-state equations for kinetic parameters, which results in a linear equation system with comparatively simple solutions. At the same time multiplicity of steady-state solutions is avoided, which otherwise is problematic for optimization. When solved for kinetic parameters, however, steady-state constraints tend to become negative for particular model specifications, thus, generating new types of optimization problems. Here, we present an algorithm based on graph theory that derives non-negative, analytical steady-state expressions by stepwise removal of cyclic dependencies between dynamical variables. The algorithm avoids multiple steady-state solutions by construction. We show that our method is applicable to most common classes of biochemical reaction networks containing inhibition terms, mass-action and Hill-type kinetic equations. Comparing the performance of parameter estimation for different analytical and numerical methods of incorporating steady-state information, we show that our approach is especially well-tailored to guarantee a high success rate of optimization. PMID:27243005

  15. Customized Steady-State Constraints for Parameter Estimation in Non-Linear Ordinary Differential Equation Models.

    PubMed

    Rosenblatt, Marcus; Timmer, Jens; Kaschek, Daniel

    2016-01-01

    Ordinary differential equation models have become a wide-spread approach to analyze dynamical systems and understand underlying mechanisms. Model parameters are often unknown and have to be estimated from experimental data, e.g., by maximum-likelihood estimation. In particular, models of biological systems contain a large number of parameters. To reduce the dimensionality of the parameter space, steady-state information is incorporated in the parameter estimation process. For non-linear models, analytical steady-state calculation typically leads to higher-order polynomial equations for which no closed-form solutions can be obtained. This can be circumvented by solving the steady-state equations for kinetic parameters, which results in a linear equation system with comparatively simple solutions. At the same time multiplicity of steady-state solutions is avoided, which otherwise is problematic for optimization. When solved for kinetic parameters, however, steady-state constraints tend to become negative for particular model specifications, thus, generating new types of optimization problems. Here, we present an algorithm based on graph theory that derives non-negative, analytical steady-state expressions by stepwise removal of cyclic dependencies between dynamical variables. The algorithm avoids multiple steady-state solutions by construction. We show that our method is applicable to most common classes of biochemical reaction networks containing inhibition terms, mass-action and Hill-type kinetic equations. Comparing the performance of parameter estimation for different analytical and numerical methods of incorporating steady-state information, we show that our approach is especially well-tailored to guarantee a high success rate of optimization.

  16. Sorption isotherm and kinetic modeling of aniline on Cr-bentonite.

    PubMed

    Zheng, Hong; Liu, Donghong; Zheng, Yan; Liang, Shuping; Liu, Zhe

    2009-08-15

    In this paper, the sorption characteristics of aniline on Cr-bentonite prepared using synthetic wastewater containing chromium was investigated in a batch system at 30 degrees C. The effects of relevant parameters, such as pH value of solution, adsorbent dosage and initial aniline concentration were examined. The experimental data were analyzed by the Langmuir and Freundlich, and Temkin models of sorption. The sorption isotherm data were fitted well to Langmuir isotherm and the monolayer sorption capacity was found to be 21.60 mg/g at 30 degrees C. Dubinin-Redushkevich (D-R) isotherm was applied to describe the nature of aniline uptake and it was found that it occurred chemically. The kinetic data obtained at different concentrations were analyzed using a pseudo first-order, pseudo second-order kinetic equation and intraparticle diffusion model. The experimental data fitted very well the pseudo second-order kinetic model. Intraparticle diffusion affects aniline uptake. The results indicate that there is significant potential for Cr-bentonite as an adsorbent material for aniline removal from aqueous solutions.

  17. Preliminary scaling laws for plasma current, ion kinetic temperature, and plasma number density in the NASA Lewis Bumpy Torus plasma

    NASA Technical Reports Server (NTRS)

    Roth, J. R.

    1976-01-01

    Parametric variation of independent variables which may affect the characteristics of the NASA Lewis Bumpy Torus plasma have identified those which have a significant effect on the plasma current, ion kinetic temperature, and plasma number density, and those which do not. Empirical power-law correlations of the plasma current, and the ion kinetic temperature and number density were obtained as functions of the potential applied to the midplane electrode rings, the background neutral gas pressure, and the magnetic field strength. Additional parameters studied include the type of gas, the polarity of the midplane electrode rings (and hence the direction of the radial electric field), the mode of plasma operation, and the method of measuring the plasma number density. No significant departures from the scaling laws appear to occur at the highest ion kinetic temperatures or number densities obtained to date.

  18. Multisubstrate biodegradation kinetics of naphthalene, phenanthrene, and pyrene mixtures

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Guha, S.; Peters, C.A.; Jaffe, P.R.

    Biodegradation kinetics of naphthalene, phenanthrene and pyrene were studied in sole-substrate systems, and in binary and ternary mixtures to examine substrate interactions. The experiments were conducted in aerobic batch aqueous systems inoculated with a mixed culture that had been isolated from soils contaminated with polycyclic aromatic hydrocarbons (PAHs). Monod kinetic parameters and yield coefficients for the individual parameters and yield coefficients for the individual compounds were estimated from substrate depletion and CO{sub 2} evolution rate data in sole-substrate experiments. In all three binary mixture experiments, biodegradation kinetics were comparable to the sole-substrate kinetics. In the ternary mixture, biodegradation of naphthalenemore » was inhibited and the biodegradation rates of phenanthrene and pyrene were enhanced. A multisubstrate form of the Monod kinetic model was found to adequately predict substrate interactions in the binary and ternary mixtures using only the parameters derived from sole-substrate experiments. Numerical simulations of biomass growth kinetics explain the observed range of behaviors in PAH mixtures. In general, the biodegradation rates of the more degradable and abundant compounds are reduced due to competitive inhibition, but enhanced biodegradation of the more recalcitrant PAHs occurs due to simultaneous biomass growth on multiple substrates. In PAH-contaminated environments, substrate interactions may be very large due to additive effects from the large number of compounds present.« less

  19. TNT Prout-Tompkins Kinetics Calibration with PSUADE

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wemhoff, A P; Hsieh, H

    2007-04-11

    We used the code PSUADE to calibrate Prout-Tompkins kinetic parameters for pure recrystallized TNT. The calibration was based on ALE3D simulations of a series of One Dimensional Time to Explosion (ODTX) experiments. The resultant kinetic parameters differed from TNT data points with an average error of 28%, which is slightly higher than the value of 23% previously calculated using a two-point optimization. The methodology described here provides a basis for future calibration studies using PSUADE. The files used in the procedure are listed in the Appendix.

  20. Fluctuating bottleneck model studies on kinetics of DNA escape from α-hemolysin nanopores

    NASA Astrophysics Data System (ADS)

    Bian, Yukun; Wang, Zilin; Chen, Anpu; Zhao, Nanrong

    2015-11-01

    We have proposed a fluctuation bottleneck (FB) model to investigate the non-exponential kinetics of DNA escape from nanometer-scale pores. The basic idea is that the escape rate is proportional to the fluctuating cross-sectional area of DNA escape channel, the radius r of which undergoes a subdiffusion dynamics subjected to fractional Gaussian noise with power-law memory kernel. Such a FB model facilitates us to obtain the analytical result of the averaged survival probability as a function of time, which can be directly compared to experimental results. Particularly, we have applied our theory to address the escape kinetics of DNA through α-hemolysin nanopores. We find that our theoretical framework can reproduce the experimental results very well in the whole time range with quite reasonable estimation for the intrinsic parameters of the kinetics processes. We believe that FB model has caught some key features regarding the long time kinetics of DNA escape through a nanopore and it might provide a sound starting point to study much wider problems involving anomalous dynamics in confined fluctuating channels.

  1. Kinetics study of palm oil hydrolysis using immobilized lipase Candida rugosa in packed bed reactor.

    PubMed

    Min, C S; Bhatia, S; Kamaruddin, A H

    1999-01-01

    Continuous hydrolysis of palm oil triglyceride in organic solvent using immobilized Candida rugosa on the Amberlite MB-1 as a source of immobilized lipase was studied in packed bed reactor. The enzymatic kinetics of hydrolysis reaction was studied by changing the substrate concentration, reaction temperature and residence time(tau) in the reactor. At 55 degrees C, the optimum water concentration was found to be 15 % weight per volume of solution (%w/v). The Michaelis-Menten kinetic model was used to obtain the reaction parameters, Km(app) and V max(app). The activation energies were found to be quite low indicating that the lipase-catalyzed process is controlled by diffusion of substrates. The Michaelis-Menten kinetic model was found to be suitable at low water concentration 10-15 %w/v of solution. At higher water concentration, substrate inhibition model was used for data analysis. Reactor operation was found to play an important role in the palm oil hydrolysis kinetic.

  2. Design Principles of DNA Enzyme-Based Walkers: Translocation Kinetics and Photoregulation.

    PubMed

    Cha, Tae-Gon; Pan, Jing; Chen, Haorong; Robinson, Heather N; Li, Xiang; Mao, Chengde; Choi, Jong Hyun

    2015-07-29

    Dynamic DNA enzyme-based walkers complete their stepwise movements along the prescribed track through a series of reactions, including hybridization, enzymatic cleavage, and strand displacement; however, their overall translocation kinetics is not well understood. Here, we perform mechanistic studies to elucidate several key parameters that govern the kinetics and processivity of DNA enzyme-based walkers. These parameters include DNA enzyme core type and structure, upper and lower recognition arm lengths, and divalent metal cation species and concentration. A theoretical model is developed within the framework of single-molecule kinetics to describe overall translocation kinetics as well as each reaction step. A better understanding of kinetics and design parameters enables us to demonstrate a walker movement near 5 μm at an average speed of ∼1 nm s(-1). We also show that the translocation kinetics of DNA walkers can be effectively controlled by external light stimuli using photoisomerizable azobenzene moieties. A 2-fold increase in the cleavage reaction is observed when the hairpin stems of enzyme catalytic cores are open under UV irradiation. This study provides general design guidelines to construct highly processive, autonomous DNA walker systems and to regulate their translocation kinetics, which would facilitate the development of functional DNA walkers.

  3. Visual evaluation of kinetic characteristics of PET probe for neuroreceptors using a two-phase graphic plot analysis.

    PubMed

    Ito, Hiroshi; Ikoma, Yoko; Seki, Chie; Kimura, Yasuyuki; Kawaguchi, Hiroshi; Takuwa, Hiroyuki; Ichise, Masanori; Suhara, Tetsuya; Kanno, Iwao

    2017-05-01

    Objectives In PET studies for neuroreceptors, tracer kinetics are described by the two-tissue compartment model (2-TCM), and binding parameters, including the total distribution volume (V T ), non-displaceable distribution volume (V ND ), and binding potential (BP ND ), can be determined from model parameters estimated by kinetic analysis. The stability of binding parameter estimates depends on the kinetic characteristics of radioligands. To describe these kinetic characteristics, we previously developed a two-phase graphic plot analysis in which V ND and V T can be estimated from the x-intercept of regression lines for early and delayed phases, respectively. In this study, we applied this graphic plot analysis to visual evaluation of the kinetic characteristics of radioligands for neuroreceptors, and investigated a relationship between the shape of these graphic plots and the stability of binding parameters estimated by the kinetic analysis with 2-TCM in simulated brain tissue time-activity curves (TACs) with various binding parameters. Methods 90-min TACs were generated with the arterial input function and assumed kinetic parameters according to 2-TCM. Graphic plot analysis was applied to these simulated TACs, and the curvature of the plot for each TAC was evaluated visually. TACs with several noise levels were also generated with various kinetic parameters, and the bias and variation of binding parameters estimated by kinetic analysis were calculated in each TAC. These bias and variation were compared with the shape of graphic plots. Results The graphic plots showed larger curvature for TACs with higher specific binding and slower dissociation of specific binding. The quartile deviations of V ND and BP ND determined by kinetic analysis were smaller for radioligands with slow dissociation. Conclusions The larger curvature of graphic plots for radioligands with slow dissociation might indicate a stable determination of V ND and BP ND by kinetic analysis. For

  4. Solar Fenton and solar TiO2 catalytic treatment of ofloxacin in secondary treated effluents: evaluation of operational and kinetic parameters.

    PubMed

    Michael, I; Hapeshi, E; Michael, C; Fatta-Kassinos, D

    2010-10-01

    Two different technical approaches based on advanced oxidation processes (AOPs), solar Fenton homogeneous photocatalysis (hv/Fe(2+)/H(2)O(2)) and heterogeneous photocatalysis with titanium dioxide (TiO(2)) suspensions were studied for the chemical degradation of the fluoroquinolone ofloxacin in secondary treated effluents. A bench-scale solar simulator in combination with an appropriate photochemical batch reactor was used to evaluate and select the optimal oxidation conditions of ofloxacin spiked in secondary treated domestic effluents. The concentration profile of the examined substrate during degradation was determined by UV/Vis spectrophotometry. Mineralization was monitored by measuring the dissolved organic carbon (DOC). The concentrations of Fe(2+) and H(2)O(2) were the key factors for the solar Fenton process, while the most important parameter of the heterogeneous photocatalysis was proved to be the catalyst loading. Kinetic analyses indicated that the photodegradation of ofloxacin can be described by a pseudo-first-order reaction. The rate constant (k) for the solar Fenton process was determined at different Fe(2+) and H(2)O(2) concentrations whereas the Langmuir-Hinshelwood (LH) kinetic expression was used to assess the kinetics of the heterogeneous photocatalytic process. The conversion of ofloxacin depends on several parameters based on the various experimental conditions, which were investigated. A Daphnia magna bioassay was used to evaluate the potential toxicity of the parent compound and its photo-oxidation by-products in different stages of oxidation. In the present study solar Fenton has been demonstrated to be more effective than the solar TiO(2) process, yielding complete degradation of the examined substrate and DOC reduction of about 50% in 30 min of the photocatalytic treatment. Copyright © 2010 Elsevier Ltd. All rights reserved.

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

    NASA Technical Reports Server (NTRS)

    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.

  6. Effect of temperature on kinetics of biogas production from macroalgae.

    PubMed

    Membere, Edward; Sallis, Paul

    2018-05-08

    An assessment was carried out on the effect of temperature on the anaerobic digestion of Laminaria digitata biomass, in batch reactors (25, 35, 45 and 55 °C) with a hydraulic retention time of 40 days. The first order, modified Gompertz and logistics models were used to obtain the kinetic parameters of the biogas production process. Results indicate the chemical composition of the algae substrate could be written as C 316 H 613 O 289 N 13 S 1 , with a theoretical methane yield of 336 ± 0.86 L CH 4  kg VS -1 . Experimental methane yield obtained from the reactors for 25, 35, 45, and 55 °C were 318 ± 1.58, 293 ± 1.11, 271 ± 0.98 and 352 ± 0.63 mL CH 4 /gVS respectively. Their R 2  > 0.90 indicate both models fits well for predicating kinetics of methane production. The lowest k h (0.31), high biodegradability index (0.96) and lag time (9.3-11.7 days) were obtained for 55 °C. Copyright © 2018 Elsevier Ltd. All rights reserved.

  7. Crystallization kinetics of the Cu{sub 50}Zr{sub 50} metallic glass under isothermal conditions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gao, Qian; Jian, Zengyun, E-mail: jianzengyun@xatu.edu.cn; Xu, Junfeng

    2016-12-15

    Amorphous structure of the melt-spun Cu{sub 50}Zr{sub 50} amorphous alloy ribbons were confirmed by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM). Isothermal crystallization kinetics of these alloy ribbons were investigated using differential scanning calorimetry (DSC). Besides, Arrhenius and Johnson-Mehl-Avrami (JMA) equations were utilized to obtain the isothermal crystallization kinetic parameters. As shown in the results, the local activation energy E{sub α} decreases by a large margin at the crystallized volume fraction α<0.1, which proves that crystallization process is increasingly easy. In addition, the local activation energy E{sub α} is basically constant at 0.1

  8. Assessment and kinetics of soil phosphatase in Brazilian Savanna systems.

    PubMed

    Ferreira, Adão S; Espíndola, Suéllen P; Campos, Maria Rita C

    2016-05-31

    The activity and kinetics of soil phosphatases are important indicators to evaluate soil quality in specific sites such as the Cerrado (Brazilian Savanna). This study aimed to determine the activity and kinetic parameters of soil phosphatase in Cerrado systems. Soil phosphatase activity was assessed in samples of native Cerrado (NC), no-tillage (NT), conventional tillage (CT) and pasture with Brachiaria brizantha (PBb) and evaluated with acetate buffer (AB), tris-HCl buffer (TB), modified universal buffer (MUB) and low MUB. The Michaelis-Menten equation and Eadie-Hofstee model were applied to obtain the kinetic parameters of soil phosphatase using different concentrations of p-nitrophenol phosphate (p-NPP). MUB showed the lowest soil phosphatase activity in all soils whereas AB in NC and NT presented the highest. Low MUB decreased interferences in the assessment of soil phosphatase activity when compared to MUB, suggesting that organic acids interfere on the soil phosphatase activity. In NC and NT, soil phosphatase activity performed with TB was similar to AB and low MUB. Km values from the Michaels-Menten equation were higher in NC than in NT, which indicate a lower affinity of phosphatase activity for the substrate in NC. Vmax values were also higher in NC than in NT. The Eadie-Hofstee model suggests that NC had more phosphatase isoforms than NT. The study showed that buffer type is of fundamental importance when assessing soil phosphatase activity in Cerrado soils.

  9. Surface Dilution Kinetics Using Substrate Analog-Enantiomers as Diluents: Enzymatic Lipolysis by Bee-Venom Phospholipase A2

    PubMed Central

    Singh, Jasmeet; Ranganathan, Radha; Hajdu, Joseph

    2010-01-01

    A novel assay employing D-enantiomers of phospholipids as diluents for characterizing surface kinetics of lipid hydrolysis by phospholipases is introduced. The rationale of the method are: (i) D-enantiomers resist hydrolysis because of the stereoselectivity of the enzymes toward L-enantiomers and (ii) mixtures of L+D-lipids at various L:D ratios but constant L+D-lipid concentrations yield a surface dilution series of variable L-lipid concentration with constant medium properties. Kinetic characterization of bee-venom phospholipase A2 activity at bile salt + phospholipid aggregate-water interfaces was performed using the mixed L+D-lipid surface dilution assay and interface kinetic parameters were obtained. The assay applies to bio-membrane models as well. Activity was measured by pH-Stat methods. Aggregation numbers and interface hydration/microviscosity measured by time resolved fluorescence quenching and electron spin resonance respectively confirmed that interface properties were indeed invariant in a surface dilution series, supporting rationale (ii) and were used to calculate substrate concentrations. Activity data show excellent agreement with a kinetic model derived with D-enantiomers as diluents and also that D-phospholipids bind to the enzyme but resist hydrolysis; underscoring rationale (i). The assay is significant to enabling determination of interface specific kinetic parameters for the first time and thereby characterization of interface specificity of lipolytic enzymes. PMID:20727845

  10. Parameter identification of thermophilic anaerobic degradation of valerate.

    PubMed

    Flotats, Xavier; Ahring, Birgitte K; 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 simultaneous batch experiments with different initial conditions for estimating these parameters. Four simultaneous batch experiments were conducted at 55 degrees C, characterized by four different initial acetate concentrations. Product inhibition of valerate degradation by acetate was considered. Practical identification was done optimizing the sum of the multiple determination coefficients for all measured state variables and for all experiments simultaneously. The estimated values of kinetic parameters and stoichiometric coefficients were characterized by the parameter correlation matrix, the confidence interval, and the student's t-test at 5% significance level with positive results except for the saturation constant, for which more experiments for improving its identifiability should be conducted. In this article, we discuss kinetic parameter estimation methods.

  11. Photoluminescence and thermoluminescence of K2 Mg(SO4 )2 :Eu and evaluation of its kinetic parameters.

    PubMed

    Deshpande, Archana; Dhoble, N S; Gedam, S C; Dhoble, S J

    2017-08-01

    The K 2 Mg(SO 4 ) 2 :Eu phosphor, synthesized by a solid-state diffusion method, was studied for its photoluminescence (PL) and thermoluminescence (TL) characteristics. The X-ray diffraction (XRD) pattern of the material was matched with the standard JCPDF No. 36-1499. For PL characteristics, K 2 Mg(SO 4 ) 2 :Eu 2 + showed an emission peak at 474 nm when excited at 340 nm, while it showed Eu 3 + emission at 580 nm, and 594 nm splitting at 613 nm and 618 nm for an excitation of 396 nm wavelength due to radiative transitions from 5 D 0 to 7 F j (j = 0, 1, 2, 3). The Commission International de I' Eclairage (CIE) chromaticity coordinates were also calculated for the K 2 Mg(SO 4 ) 2 :Eu phosphor, and were close to the NTSC standard values. For the TL study, the prepared sample was irradiated using a 60 Co source of γ-irradiation at the dose rate of 0.322 kGy/h for 2 min. The formation of traps in K 2 Mg (SO 4 ) 2 :Eu and the effects of γ-radiation dose on the glow curve are discussed. Well defined broad glow peaks were obtained at 186°C. With increasing γ-ray dose, the sample showed linearity in intensity. The presence of a single glow peak indicated that there was only one set of traps being activated within the particular temperature range. The presented phosphors were also studied for their fading, reusability and trapping parameters. There was just 2% fading during a period of 30 days, indicating no serious fading problem. Kinetic parameters were calculated using the initial rise method and Chen's half-width method. Activation energy and frequency factor were found to be 0.77 eV and 1.41 × 10 6  sec -1 . Copyright © 2016 John Wiley & Sons, Ltd.

  12. Determination of biodegradability kinetics of RCRA compounds using respirometry for structure-activity relationships

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tabak, H.H.; Desai, S.; Govind, R.

    1990-01-01

    Electrolytic respirometry is attaining prominence in biodegradation studies and is becoming one of the more suitable experimental methods for measuring the biodegradability and the kinetics of biodegradation of toxic organic compounds by the sewage, sludge, and soil microbiota and for determining substrate inhibitory effects to microorganisms in wastewater treatment systems. The purpose of the study was to obtain information on biological treatability of the benzene, phenol, phthalate, ketone organics and of the Superfund CERCLA organics bearing wastes in wastewater treatment systems which will support the development of an EPA technical guidance document on the discharge of the above organics tomore » POTWs. The paper discusses the experimental design and procedural steps for the respirometric biodegradation and toxicity testing approach for individual organics or specific industrial wastes at different concentration levels in a mineral salts medium. A developed multi-level protocol is presented for determination of the biodegradability, microbial acclimation to toxic substrates and first order kinetic parameters of biodegradation for estimation of the Monod kinetic parameter of toxic organic compounds, in order to correlate the extent and rate of biodegradation with a predictive model based on chemical properties and molecular structure of these compounds. Respirometric biodegradation/inhibition and biokinetic data are provided for representative RCRA alkyl benzene and ketone organics.« less

  13. The Kinetics of Dissolution Revisited

    NASA Astrophysics Data System (ADS)

    Antonel, Paula S.; Hoijemberg, Pablo A.; Maiante, Leandro M.; Lagorio, M. Gabriela

    2003-09-01

    An experiment analyzing the kinetics of dissolution of a solid with cylindrical geometry in water is presented. The dissolution process is followed by measuring the solid mass and its size parameters (thickness and diameter) as a function of time. It is verified that the dissolution rate follows the Nernst model. Data treatment is compared with the dissolution of a spherical solid previously described. Kinetics, diffusion concepts, and polynomial fitting of experimental data are combined in this simple experiment.

  14. Kinetic model for microbial growth and desulphurisation with Enterobacter sp.

    PubMed

    Liu, Long; Guo, Zhiguo; Lu, Jianjiang; Xu, Xiaolin

    2015-02-01

    Biodesulphurisation was investigated by using Enterobacter sp. D4, which can selectively desulphurise and convert dibenzothiophene into 2-hydroxybiphenyl (2-HBP). The experimental values of growth, substrate consumption and product generation were obtained at 95 % confidence level of the fitted values using three models: Hinshelwood equation, Luedeking-Piret and Luedeking-Piret-like equations. The average error values between experimental values and fitted values were less than 10 %. These kinetic models describe all the experimental data with good statistical parameters. The production of 2-HBP in Enterobacter sp. was by "coupled growth".

  15. Comment on ‘Information hidden in the velocity distribution of ions and the exact kinetic Bohm criterion’

    NASA Astrophysics Data System (ADS)

    Mustafaev, A. S.; Sukhomlinov, V. S.; Timofeev, N. A.

    2018-03-01

    This Comment is devoted to some mathematical inaccuracies made by the authors of the paper ‘Information hidden in the velocity distribution of ions and the exact kinetic Bohm criterion’ (Plasma Sources Science and Technology 26 055003). In the Comment, we show that the diapason of plasma parameters for the validity of the theoretical results obtained by the authors was defined incorrectly; we made a more accurate definition of this diapason. As a result, we show that it is impossible to confirm or refute the feasibility of the Bohm kinetic criterion on the basis of the data of the cited paper.

  16. Compartmental analysis of [11C]flumazenil kinetics for the estimation of ligand transport rate and receptor distribution using positron emission tomography.

    PubMed

    Koeppe, R A; Holthoff, V A; Frey, K A; Kilbourn, M R; Kuhl, D E

    1991-09-01

    The in vivo kinetic behavior of [11C]flumazenil ([11C]FMZ), a non-subtype-specific central benzodiazepine antagonist, is characterized using compartmental analysis with the aim of producing an optimized data acquisition protocol and tracer kinetic model configuration for the assessment of [11C]FMZ binding to benzodiazepine receptors (BZRs) in human brain. The approach presented is simple, requiring only a single radioligand injection. Dynamic positron emission tomography data were acquired on 18 normal volunteers using a 60- to 90-min sequence of scans and were analyzed with model configurations that included a three-compartment, four-parameter model, a three-compartment, three-parameter model, with a fixed value for free plus nonspecific binding; and a two-compartment, two-parameter model. Statistical analysis indicated that a four-parameter model did not yield significantly better fits than a three-parameter model. Goodness of fit was improved for three- versus two-parameter configurations in regions with low receptor density, but not in regions with moderate to high receptor density. Thus, a two-compartment, two-parameter configuration was found to adequately describe the kinetic behavior of [11C]FMZ in human brain, with stable estimates of the model parameters obtainable from as little as 20-30 min of data. Pixel-by-pixel analysis yields functional images of transport rate (K1) and ligand distribution volume (DV"), and thus provides independent estimates of ligand delivery and BZR binding.

  17. Topological and kinetic determinants of the modal matrices of dynamic models of metabolism

    PubMed Central

    2017-01-01

    Large-scale kinetic models of metabolism are becoming increasingly comprehensive and accurate. A key challenge is to understand the biochemical basis of the dynamic properties of these models. Linear analysis methods are well-established as useful tools for characterizing the dynamic response of metabolic networks. Central to linear analysis methods are two key matrices: the Jacobian matrix (J) and the modal matrix (M-1) arising from its eigendecomposition. The modal matrix M-1 contains dynamically independent motions of the kinetic model near a reference state, and it is sparse in practice for metabolic networks. However, connecting the structure of M-1 to the kinetic properties of the underlying reactions is non-trivial. In this study, we analyze the relationship between J, M-1, and the kinetic properties of the underlying network for kinetic models of metabolism. Specifically, we describe the origin of mode sparsity structure based on features of the network stoichiometric matrix S and the reaction kinetic gradient matrix G. First, we show that due to the scaling of kinetic parameters in real networks, diagonal dominance occurs in a substantial fraction of the rows of J, resulting in simple modal structures with clear biological interpretations. Then, we show that more complicated modes originate from topologically-connected reactions that have similar reaction elasticities in G. These elasticities represent dynamic equilibrium balances within reactions and are key determinants of modal structure. The work presented should prove useful towards obtaining an understanding of the dynamics of kinetic models of metabolism, which are rooted in the network structure and the kinetic properties of reactions. PMID:29267329

  18. Set-base dynamical parameter estimation and model invalidation for biochemical reaction networks.

    PubMed

    Rumschinski, Philipp; Borchers, Steffen; Bosio, Sandro; Weismantel, Robert; Findeisen, Rolf

    2010-05-25

    Mathematical modeling and analysis have become, for the study of biological and cellular processes, an important complement to experimental research. However, the structural and quantitative knowledge available for such processes is frequently limited, and measurements are often subject to inherent and possibly large uncertainties. This results in competing model hypotheses, whose kinetic parameters may not be experimentally determinable. Discriminating among these alternatives and estimating their kinetic parameters is crucial to improve the understanding of the considered process, and to benefit from the analytical tools at hand. In this work we present a set-based framework that allows to discriminate between competing model hypotheses and to provide guaranteed outer estimates on the model parameters that are consistent with the (possibly sparse and uncertain) experimental measurements. This is obtained by means of exact proofs of model invalidity that exploit the polynomial/rational structure of biochemical reaction networks, and by making use of an efficient strategy to balance solution accuracy and computational effort. The practicability of our approach is illustrated with two case studies. The first study shows that our approach allows to conclusively rule out wrong model hypotheses. The second study focuses on parameter estimation, and shows that the proposed method allows to evaluate the global influence of measurement sparsity, uncertainty, and prior knowledge on the parameter estimates. This can help in designing further experiments leading to improved parameter estimates.

  19. Nonextensive kinetic theory and H-theorem in general relativity

    NASA Astrophysics Data System (ADS)

    Santos, A. P.; Silva, R.; Alcaniz, J. S.; Lima, J. A. S.

    2017-11-01

    The nonextensive kinetic theory for degenerate quantum gases is discussed in the general relativistic framework. By incorporating nonadditive modifications in the collisional term of the relativistic Boltzmann equation and entropy current, it is shown that Tsallis entropic framework satisfies a H-theorem in the presence of gravitational fields. Consistency with the 2nd law of thermodynamics is obtained only whether the entropic q-parameter lies in the interval q ∈ [ 0 , 2 ] . As occurs in the absence of gravitational fields, it is also proved that the local collisional equilibrium is described by the extended Bose-Einstein (Fermi-Dirac) q-distributions.

  20. Scrape-off layer modeling with kinetic or diffusion description of charge-exchange atoms

    NASA Astrophysics Data System (ADS)

    Tokar, M. Z.

    2016-12-01

    Hydrogen isotope atoms, generated by charge-exchange (c-x) of neutral particles recycling from the first wall of a fusion reactor, are described either kinetically or in a diffusion approximation. In a one-dimensional (1-D) geometry, kinetic calculations are accelerated enormously by applying an approximate pass method for the assessment of integrals in the velocity space. This permits to perform an exhaustive comparison of calculations done with both approaches. The diffusion approximation is deduced directly from the velocity distribution function of c-x atoms in the limit of charge-exchanges with ions occurring much more frequently than ionization by electrons. The profiles across the flux surfaces of the plasma parameters averaged along the main part of the scrape-off layer (SOL), beyond the X-point and divertor regions, are calculated from the one-dimensional equations where parallel flows of charged particles and energy towards the divertor are taken into account as additional loss terms. It is demonstrated that the heat losses can be firmly estimated from the SOL averaged parameters only; for the particle loss the conditions in the divertor are of importance and the sensitivity of the results to the so-called "divertor impact factor" is investigated. The coupled 1-D models for neutral and charged species, with c-x atoms described either kinetically or in the diffusion approximation, are applied to assess the SOL conditions in a fusion reactor, with the input parameters from the European DEMO project. It is shown that the diffusion approximation provides practically the same profiles across the flux surfaces for the plasma density, electron, and ion temperatures, as those obtained with the kinetic description for c-x atoms. The main difference between the two approaches is observed in the characteristics of these species themselves. In particular, their energy flux onto the wall is underestimated in calculations with the diffusion approximation by 20 % - 30

  1. Comparison of the performance of tracer kinetic model-driven registration for dynamic contrast enhanced MRI using different models of contrast enhancement.

    PubMed

    Buonaccorsi, Giovanni A; Roberts, Caleb; Cheung, Sue; Watson, Yvonne; O'Connor, James P B; Davies, Karen; Jackson, Alan; Jayson, Gordon C; Parker, Geoff J M

    2006-09-01

    The quantitative analysis of dynamic contrast-enhanced (DCE) magnetic resonance imaging (MRI) data is subject to model fitting errors caused by motion during the time-series data acquisition. However, the time-varying features that occur as a result of contrast enhancement can confound motion correction techniques based on conventional registration similarity measures. We have therefore developed a heuristic, locally controlled tracer kinetic model-driven registration procedure, in which the model accounts for contrast enhancement, and applied it to the registration of abdominal DCE-MRI data at high temporal resolution. Using severely motion-corrupted data sets that had been excluded from analysis in a clinical trial of an antiangiogenic agent, we compared the results obtained when using different models to drive the tracer kinetic model-driven registration with those obtained when using a conventional registration against the time series mean image volume. Using tracer kinetic model-driven registration, it was possible to improve model fitting by reducing the sum of squared errors but the improvement was only realized when using a model that adequately described the features of the time series data. The registration against the time series mean significantly distorted the time series data, as did tracer kinetic model-driven registration using a simpler model of contrast enhancement. When an appropriate model is used, tracer kinetic model-driven registration influences motion-corrupted model fit parameter estimates and provides significant improvements in localization in three-dimensional parameter maps. This has positive implications for the use of quantitative DCE-MRI for example in clinical trials of antiangiogenic or antivascular agents.

  2. Kinetic profile of amyloid formation in the presence of an aromatic inhibitor by nuclear magnetic resonance.

    PubMed

    Liu, Gai; Gaines, Jennifer C; Robbins, Kevin J; Lazo, Noel D

    2012-10-11

    The self-assembly of amyloid proteins into β-sheet rich assemblies is associated with human amyloidoses including Alzheimer's disease, Parkinson's disease, and type 2 diabetes. An attractive therapeutic strategy therefore is to develop small molecules that would inhibit protein self-assembly. Natural polyphenols are potential inhibitors of β-sheet formation. How these compounds affect the kinetics of self-assembly studied by thioflavin T (ThT) fluorescence is not understood primarily because their presence interferes with ThT fluorescence. Here, we show that by plotting peak intensities from nuclear magnetic resonance (NMR) against incubation time, kinetic profiles in the presence of the polyphenol can be obtained from which kinetic parameters of self-assembly can be easily determined. In applying this technique to the self-assembly of the islet amyloid polypeptide in the presence of curcumin, a biphenolic compound found in turmeric, we show that the kinetic profile is atypical in that it shows a prenucleation period during which there is no observable decrease in NMR peak intensities.

  3. A kinetics database and scripts for PHREEQC

    NASA Astrophysics Data System (ADS)

    Hu, B.; Zhang, Y.; Teng, Y.; Zhu, C.

    2017-12-01

    Kinetics of geochemical reactions has been increasingly used in numerical models to simulate coupled flow, mass transport, and chemical reactions. However, the kinetic data are scattered in the literature. To assemble a kinetic dataset for a modeling project is an intimidating task for most. In order to facilitate the application of kinetics in geochemical modeling, we assembled kinetics parameters into a database for the geochemical simulation program, PHREEQC (version 3.0). Kinetics data were collected from the literature. Our database includes kinetic data for over 70 minerals. The rate equations are also programmed into scripts with the Basic language. Using the new kinetic database, we simulated reaction path during the albite dissolution process using various rate equations in the literature. The simulation results with three different rate equations gave difference reaction paths at different time scale. Another application involves a coupled reactive transport model simulating the advancement of an acid plume in an acid mine drainage site associated with Bear Creek Uranium tailings pond. Geochemical reactions including calcite, gypsum, and illite were simulated with PHREEQC using the new kinetic database. The simulation results successfully demonstrated the utility of new kinetic database.

  4. Comparison of four kinds of extraction techniques and kinetics of microwave-assisted extraction of vanillin from Vanilla planifolia Andrews.

    PubMed

    Dong, Zhizhe; Gu, Fenglin; Xu, Fei; Wang, Qinghuang

    2014-04-15

    Vanillin yield, microscopic structure, antioxidant activity and overall odour of vanilla extracts obtained by different treatments were investigated. MAE showed the strongest extraction power, shortest time and highest antioxidant activity. Maceration gave higher vanillin yields than UAE and PAE, similar antioxidant activity with UAE, but longer times than UAE and PAE. Overall odour intensity of different vanilla extracts obtained by UAE, PAE and MAE were similar, while higher than maceration extracts. Then, powered vanilla bean with a sample/solvent ratio of 4 g/100 mL was selected as the optimum condition for MAE. Next, compared with other three equations, two-site kinetic equation with lowest RMSD and highest R²(adj) was shown to be more suitable in describing the kinetics of vanillin extraction. By fitting the parameters C(eq), k₁, k₂, and f, a kinetics model was constructed to describe vanillin extraction in terms of irradiation power, ethanol concentration, and extraction time. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Direct estimation of tracer-kinetic parameter maps from highly undersampled brain dynamic contrast enhanced MRI.

    PubMed

    Guo, Yi; Lingala, Sajan Goud; Zhu, Yinghua; Lebel, R Marc; Nayak, Krishna S

    2017-10-01

    The purpose of this work was to develop and evaluate a T 1 -weighted dynamic contrast enhanced (DCE) MRI methodology where tracer-kinetic (TK) parameter maps are directly estimated from undersampled (k,t)-space data. The proposed reconstruction involves solving a nonlinear least squares optimization problem that includes explicit use of a full forward model to convert parameter maps to (k,t)-space, utilizing the Patlak TK model. The proposed scheme is compared against an indirect method that creates intermediate images by parallel imaging and compressed sensing before to TK modeling. Thirteen fully sampled brain tumor DCE-MRI scans with 5-second temporal resolution are retrospectively undersampled at rates R = 20, 40, 60, 80, and 100 for each dynamic frame. TK maps are quantitatively compared based on root mean-squared-error (rMSE) and Bland-Altman analysis. The approach is also applied to four prospectively R = 30 undersampled whole-brain DCE-MRI data sets. In the retrospective study, the proposed method performed statistically better than indirect method at R ≥ 80 for all 13 cases. This approach provided restoration of TK parameter values with less errors in tumor regions of interest, an improvement compared to a state-of-the-art indirect method. Applied prospectively, the proposed method provided whole-brain, high-resolution TK maps with good image quality. Model-based direct estimation of TK maps from k,t-space DCE-MRI data is feasible and is compatible up to 100-fold undersampling. Magn Reson Med 78:1566-1578, 2017. © 2016 International Society for Magnetic Resonance in Medicine. © 2016 International Society for Magnetic Resonance in Medicine.

  6. General solutions for the oxidation kinetics of polymers

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gillen, K.T.; Clough, R.L.; Wise, J.

    1996-08-01

    The simplest general kinetic schemes applicable to the oxidation of polymers are presented, discussed and analyzed in terms of the underlying kinetic assumptions. For the classic basic autoxidation scheme (BAS), which involves three bimolecular termination steps and is applicable mainly to unstabilized polymers, typical assumptions used singly or in groups include (1) long kinetic chain length, (2) a specific ratio of the termination rate constants and (3) insensitivity to the oxygen concentration (e.g., domination by a single termination step). Steady-state solutions for the rate of oxidation are given in terms of one, two, three, or four parameters, corresponding respectively tomore » three, two, one, or zero kinetic assumptions. The recently derived four-parameter solution predicts conditions yielding unusual dependencies of the oxidation rate on oxygen concentration and on initiation rate, as well as conditions leading to some unusual diffusion-limited oxidation profile shapes. For stabilized polymers, unimolecular termination schemes are typically more appropriate than bimolecular. Kinetics incorporating unimolecular termination reactions are shown to result in very simple oxidation expressions which have been experimentally verified for both radiation-initiated oxidation of an EPDM and thermoxidative degradation of nitrile and chloroprene elastomers.« less

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

    NASA Astrophysics Data System (ADS)

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

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

  8. Kinetics of hydrogen peroxide decomposition by catalase: hydroxylic solvent effects.

    PubMed

    Raducan, Adina; Cantemir, Anca Ruxandra; Puiu, Mihaela; Oancea, Dumitru

    2012-11-01

    The effect of water-alcohol (methanol, ethanol, propan-1-ol, propan-2-ol, ethane-1,2-diol and propane-1,2,3-triol) binary mixtures on the kinetics of hydrogen peroxide decomposition in the presence of bovine liver catalase is investigated. In all solvents, the activity of catalase is smaller than in water. The results are discussed on the basis of a simple kinetic model. The kinetic constants for product formation through enzyme-substrate complex decomposition and for inactivation of catalase are estimated. The organic solvents are characterized by several physical properties: dielectric constant (D), hydrophobicity (log P), concentration of hydroxyl groups ([OH]), polarizability (α), Kamlet-Taft parameter (β) and Kosower parameter (Z). The relationships between the initial rate, kinetic constants and medium properties are analyzed by linear and multiple linear regression.

  9. Influence of Prolonged Spaceflight on Heart Rate and Oxygen Uptake Kinetics

    NASA Astrophysics Data System (ADS)

    Hoffmann, U.; Moore, A.; Drescher, U.

    2013-02-01

    During prolonged spaceflight, physical training is used to minimize cardiovascular deconditioning. Measurement of the kinetics of cardiorespiratory parameters, in particular the kinetic analysis of heart rate, respiratory and muscular oxygen uptake, provides useful information with regard to the efficiency and regulation of the cardiorespiratory system. Practically, oxygen uptake kinetics can only be measured at the lung site (V’O2 resp). The dynamics of V’O2 resp, however, is not identical with the dynamics at the site of interest: skeletal muscle. Eight Astronauts were tested pre- and post-flight using pseudo random binary workload changes between 30 and 80 W. Their kinetic responses of heart rate, respiratory as well as muscular V’O2 kinetics were estimated by using time-series analysis. Statistical analysis revealed that the kinetic responses of respiratory as well as muscular V’O2 kinetics are slowed post-flight than pre-flight. Heart rate seems not to be influenced following flight. The influence of other factors (e. g. astronauts’ exercise training) may impact these parameters and is an area for future studies.

  10. Intra-rater repeatability of gait parameters in healthy adults during self-paced treadmill-based virtual reality walking.

    PubMed

    Al-Amri, Mohammad; Al Balushi, Hilal; Mashabi, Abdulrhman

    2017-12-01

    Self-paced treadmill walking is becoming increasingly popular for the gait assessment and re-education, in both research and clinical settings. Its day-to-day repeatability is yet to be established. This study scrutinised the test-retest repeatability of key gait parameters, obtained from the Gait Real-time Analysis Interactive Lab (GRAIL) system. Twenty-three male able-bodied adults (age: 34.56 ± 5.12 years) completed two separate gait assessments on the GRAIL system, separated by 5 ± 3 days. Key gait kinematic, kinetic, and spatial-temporal parameters were analysed. The Intraclass-Correlation Coefficients (ICC), Standard Error Measurement (SEM), Minimum Detectable Change (MDC), and the 95% limits of agreements were calculated to evaluate the repeatability of these gait parameters. Day-to-day agreements were excellent (ICCs > 0.87) for spatial-temporal parameters with low MDC and SEM values, <0.153 and <0.055, respectively. The repeatability was higher for joint kinetic than kinematic parameters, as reflected in small values of SEM (<0.13 Nm/kg and <3.4°) and MDC (<0.335 Nm/kg and <9.44°). The obtained values of all parameters fell within the 95% limits of agreement. Our findings demonstrate the repeatability of the GRAIL system available in our laboratory. The SEM and MDC values can be used to assist researchers and clinicians to distinguish 'real' changes in gait performance over time.

  11. Effect of soil parameters on the kinetics of the displacement of Fe from FeEDDHA chelates by Cu.

    PubMed

    Schenkeveld, Walter D C; Reichwein, Arjen M; Temminghoff, Erwin J M; van Riemsdijk, Willem H

    2012-06-28

    In soil application, o,o-FeEDDHA (iron (3+) ethylene diamine-N,N'-bis(2-hydroxy phenyl acetic acid) complex) is the active ingredient of FeEDDHA chelate-based Fe fertilizers. The effectiveness of o,o-FeEDDHA is potentially compromised by the displacement of Fe from FeEDDHA by Cu. The actual impact of Cu competition is codetermined by the kinetics of the displacement reaction. In this study, the influence of soil parameters on the displacement kinetics has been examined in goethite suspensions. The displacement reaction predominantly takes place on the reactive surface rather than in solution. The rate at which the o,o-FeEDDHA concentration declined depended on the available reactive surface area, the Cu loading, and the FeEDDHA loading. Soil factors reducing FeEDDHA adsorption (high ionic strength, humic acid adsorption onto the goethite surface, and monovalent instead of divalent cations in the electrolyte) decreased the displacement rate. For meso o,o-FeEDDHA, the displacement rate equation was derived, which is first order in FeEDDHA loading and half order in Cu loading. For soil conditions, the equation can be simplified to an exponential decay function in meso o,o-FeEDDHA solution concentration.

  12. Reactivity of organic micropollutants with ozone: A kinetic study

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Brambilla, A.; Bolzacchini, E.; Meinardi, S.

    1995-12-01

    Studies about the chemical reactivity of compounds widely used in the environment are needed. The chemical reactivity of triazines (simazine, atrazine, terbutylazine) and phenylureas (linuron and diuron) was studied. The kinetics of the oxidation of the triazines and phenylureas with ozone at pH 3 and the kinetics of the saturation of the solution with ozone were evaluated. These data may be useful for the prediction of the persistency of these compuonds in the environment and for the treatment of wastewaters contaminated with these compounds. The solution was presaturated with ozone before the addition of the substrate, and the reaction constantsmore » for the pseudo first order kinetics -d[substrate]/dt = k{sub app} [substrate] at 298{degree}K were obtained, assuming a steady state concentration of ozone of 1.91 10{sup -4} mol L{sup -1} for the phenylureas and of 3.03 10{sup -4} and L{sup -1} for the triazines. The data obtained were: atrazine k = 6.86 (L mol{sup -1}s{sup -1}); simazine: 9.26; t-butylazine 7.26; linuron 11.00; diuron 43.90. The activation parameters for the reaction of simazine were {Delta}H{sup =} = 9.35 kcal mol{sup -1} and {Delta}S{sup =} = -22.3 cal mol{sup -1} {degree}K{sup -1} and for the reaction of diuron were {Delta}H{sup =} = 16.83 Kcal mol{sup -1}, {Delta}S{sup =} = 5.696 cal mol{sup -1} {degree}K{sup -1}.« less

  13. Chemometrical assessment of the electrical parameters obtained by long-term operating freshwater sediment microbial fuel cells.

    PubMed

    Mitov, Mario; Bardarov, Ivo; Mandjukov, Petko; Hubenova, Yolina

    2015-12-01

    The electrical parameters of nine freshwater sediment microbial fuel cells (SMFCs) were monitored for a period of over 20 months. The developed SMFCs, divided into three groups, were started up and continuously operated under different constant loads (100, 510 and 1100 Ω) for 2.5 months. At this stage of the experiment, the highest power density values, reaching 1.2 ± 0.2 mW/m(2), were achieved by the SMFCs loaded with 510 Ω. The maximum power obtained at periodical polarization during the rest period, however, ranged between 26.2 ± 2.8 and 35.3 ± 2.8 mW/m(2), strongly depending on the internal cell resistance. The statistical evaluation of data derived from the polarization curves shows that after 300 days of operation all examined SMFCs reached a steady-state and the system might be assumed as homoscedastic. The estimated values of standard and expanded uncertainties of the electric parameters indicate a high repeatability and reproducibility of the SMFCs' performance. Results obtained in subsequent discharge-recovery cycles reveal the opportunity for practical application of studied SMFCs as autonomous power sources.

  14. Kinetic Model of Growth of Arthropoda Populations

    NASA Astrophysics Data System (ADS)

    Ershov, Yu. A.; Kuznetsov, M. A.

    2018-05-01

    Kinetic equations were derived for calculating the growth of crustacean populations ( Crustacea) based on the biological growth model suggested earlier using shrimp ( Caridea) populations as an example. The development cycle of successive stages for populations can be represented in the form of quasi-chemical equations. The kinetic equations that describe the development cycle of crustaceans allow quantitative prediction of the development of populations depending on conditions. In contrast to extrapolation-simulation models, in the developed kinetic model of biological growth the kinetic parameters are the experimental characteristics of population growth. Verification and parametric identification of the developed model on the basis of the experimental data showed agreement with experiment within the error of the measurement technique.

  15. Drug-Target Kinetics in Drug Discovery.

    PubMed

    Tonge, Peter J

    2018-01-17

    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.

  16. Drug–Target Kinetics in Drug Discovery

    PubMed Central

    2017-01-01

    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. PMID:28640596

  17. New model for colour kinetics of plum under infrared vacuum condition and microwave drying.

    PubMed

    Chayjan, Reza Amiri; Alaei, Behnam

    2016-01-01

    Quality of dried foods is affected by the drying method and physiochemical changes in tissue. The drying method affects properties such as colour. The colour of processed food is one of the most important quality indices and plays a determinant role in consumer acceptability of food materials and the processing method. The colour of food materials can be used as an indirect factor to determine changes in quality, since it is simpler and faster than chemical methods. The study focused on the kinetics of colour changes of plum slices, under infrared vacuum and microwave conditions. Drying the samples was implemented at the absolute pressures of 20 and 60 kPa, drying temperatures of 50 and 60°C and microwave power of 90, 270, 450 and 630 W. Colour changes were quantified by the tri-stimulus L* (whiteness/darkness), a* (redness/greenness) and b* (yellowness/blueness) model, which is an international standard for color measurement developed by the Commission Internationale d'Eclairage (CIE). These values were also used to calculate total colour change (∆E), chroma, hue angle, and browning index (BI). A new model was used for mathematical modelling of colour change kinetics. The drying process changed the colour parameters of L*, a*, and b*, causing a colour shift toward the darker region. The values of L* and hue angle decreased, whereas the values of a*, b*, ∆E, chroma and browning index increased during exposure to infrared vacuum conditions and microwave drying. Comparing the results obtained using the new model with two conventional models of zero-order and first-order kinetics indicated that the new model presented more compatibility with the data of colour kinetics for all colour parameters and drying conditions. All kinetic changes in colour parameters can be explained by the new model presented in this study. The hybrid drying system included infrared vacuum conditions and microwave power for initial slow drying of plum slices and provided the desired

  18. Exact solutions for kinetic models of macromolecular dynamics.

    PubMed

    Chemla, Yann R; Moffitt, Jeffrey R; Bustamante, Carlos

    2008-05-15

    Dynamic biological processes such as enzyme catalysis, molecular motor translocation, and protein and nucleic acid conformational dynamics are inherently stochastic processes. However, when such processes are studied on a nonsynchronized ensemble, the inherent fluctuations are lost, and only the average rate of the process can be measured. With the recent development of methods of single-molecule manipulation and detection, it is now possible to follow the progress of an individual molecule, measuring not just the average rate but the fluctuations in this rate as well. These fluctuations can provide a great deal of detail about the underlying kinetic cycle that governs the dynamical behavior of the system. However, extracting this information from experiments requires the ability to calculate the general properties of arbitrarily complex theoretical kinetic schemes. We present here a general technique that determines the exact analytical solution for the mean velocity and for measures of the fluctuations. We adopt a formalism based on the master equation and show how the probability density for the position of a molecular motor at a given time can be solved exactly in Fourier-Laplace space. With this analytic solution, we can then calculate the mean velocity and fluctuation-related parameters, such as the randomness parameter (a dimensionless ratio of the diffusion constant and the velocity) and the dwell time distributions, which fully characterize the fluctuations of the system, both commonly used kinetic parameters in single-molecule measurements. Furthermore, we show that this formalism allows calculation of these parameters for a much wider class of general kinetic models than demonstrated with previous methods.

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

    PubMed Central

    Singh, Arvind K.; Sherry, Angela; Gray, Neil D.; Jones, D. Martin; Bowler, Bernard F. J.; Head, Ian M.

    2014-01-01

    Availability of inorganic nutrients, particularly nitrogen and phosphorous, is often a primary control on crude oil hydrocarbon degradation in marine systems. Many studies have empirically determined optimum levels of inorganic N and P for stimulation of hydrocarbon degradation. 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 and P are not limiting. In the marine sediments studied, crude oil degradation was limited by both N and P availability. In sediments treated with 12.5 mg/g of oil but with no addition of N and P, hydrocarbon degradation rates, assessed on the basis of CO2 production, were 1.10 ± 0.03 μmol CO2/g wet sediment/day which were comparable to rates of CO2 production in sediments to which no oil was added (1.05 ± 0.27 μmol CO2/g wet sediment/day). When inorganic nitrogen was added alone maximum rates of CO2 production measured were 4.25 ± 0.91 μmol CO2/g wet sediment/day. However, when the same levels of inorganic nitrogen 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 increased more than four-fold to 18.40 ± 1.04 μmol CO2/g wet sediment/day. Ks and qmax estimates for inorganic N (in the form of sodium nitrate) when P was not limiting were 1.99 ± 0.86 μmol/g wet sediment and 16.16 ± 1.28 μmol CO2/g wet sediment/day respectively. The corresponding values for P were 63 ± 95 nmol/g wet sediment and 12.05 ± 1.31 μmol CO2/g wet sediment/day. The qmax values with respect to N and P were not significantly different (P < 0.05). When N and P

  20. Kinetic Monte Carlo simulations of water ice porosity: extrapolations of deposition parameters from the laboratory to interstellar space.

    PubMed

    Clements, Aspen R; Berk, Brandon; Cooke, Ilsa R; Garrod, Robin T

    2018-02-21

    Dust grains in cold, dense interstellar clouds build up appreciable ice mantles through the accretion and subsequent surface chemistry of atoms and molecules from the gas. These mantles, of thicknesses on the order of 100 monolayers, are primarily composed of H 2 O, CO, and CO 2 . Laboratory experiments using interstellar ice analogues have shown that porosity could be present and can facilitate diffusion of molecules along the inner pore surfaces. However, the movement of molecules within and upon the ice is poorly described by current chemical kinetics models, making it difficult either to reproduce the formation of experimental porous ice structures or to extrapolate generalized laboratory results to interstellar conditions. Here we use the off-lattice Monte Carlo kinetics model MIMICK to investigate the effects that various deposition parameters have on laboratory ice structures. The model treats molecules as isotropic spheres of a uniform size, using a Lennard-Jones potential. We reproduce experimental trends in the density of amorphous solid water (ASW) for varied deposition angle, rate and surface temperature; ice density decreases when the incident angle or deposition rate is increased, while increasing temperature results in a more-compact water ice. The models indicate that the density behaviour at higher temperatures (≥80 K) is dependent on molecular rearrangement resulting from thermal diffusion. To reproduce trends at lower temperatures, it is necessary to take account of non-thermal diffusion by newly-adsorbed molecules, which bring kinetic energy both from the gas phase and from their acceleration into a surface binding site. Extrapolation of the model to conditions appropriate to protoplanetary disks, in which direct accretion of water from the gas-phase may be the dominant ice formation mechanism, indicate that these ices may be less porous than laboratory ices.

  1. Comparing kinetic curves in liquid chromatography

    NASA Astrophysics Data System (ADS)

    Kurganov, A. A.; Kanat'eva, A. Yu.; Yakubenko, E. E.; Popova, T. P.; Shiryaeva, V. E.

    2017-01-01

    Five equations for kinetic curves which connect the number of theoretical plates N and time of analysis t 0 for five different versions of optimization, depending on the parameters being varied (e.g., mobile phase flow rate, pressure drop, sorbent grain size), are obtained by means of mathematical modeling. It is found that a method based on the optimization of a sorbent grain size at fixed pressure is most suitable for the optimization of rapid separations. It is noted that the advantages of the method are limited by an area of relatively low efficiency, and the advantage of optimization is transferred to a method based on the optimization of both the sorbent grain size and the drop in pressure across a column in the area of high efficiency.

  2. Effect of Slag Composition on the Crystallization Kinetics of Synthetic CaO-SiO2-Al2O3-MgO Slags

    NASA Astrophysics Data System (ADS)

    Esfahani, Shaghayegh; Barati, Mansoor

    2018-04-01

    The crystallization kinetics of CaO-SiO2-Al2O3-MgO (CSAM) slags was studied with the aid of single hot thermocouple technique (SHTT). Kinetic parameters such as the Avrami exponent ( n), rate coefficient ( K), and effective activation energy of crystallization ( E A ) were obtained by kinetic analysis of data obtained from in situ observation of glassy to crystalline transformation and image analysis. Also, the dependence of nucleation and growth rates of crystalline phases were quantified as a function of time, temperature, and slag basicity. Together with the observations of crystallization front, they facilitated establishing the dominant mechanisms of crystallization. In an attempt to predict crystallization rate under non-isothermal conditions, a mathematical model was developed that employs the rate data of isothermal transformation. The model was validated by reproducing an experimental continuous cooling transformation diagram purely from isothermal data.

  3. Evaluation of oxygen reduction activity by the thin-film rotating disk electrode methodology: The effects of potentiodynamic parameters

    DOE PAGES

    Chen, Guangyu; Li, Meng; Kuttiyiel, Kurian A.; ...

    2016-04-11

    Here, an accurate and efficient assessment of activity is critical for the research and development of electrocatalysts for oxygen reduction reaction (ORR). Currently, the methodology combining the thin-film rotating disk electrode (TF-RDE) and potentiodynamic polarization is the most commonly used to pre-evaluate ORR activity, acquire kinetic data (i.e., kinetic current, Tafel slope, etc.), and gain understanding of the ORR mechanism. However, it is often neglected that appropriate potentiodynamic parameters have to be chosen to obtain reliable results. We first evaluate the potentiodynamic and potentiostatic polarization measurements with TF-RDE to examine the ORR activity of Pt nanoelectrocatalyst. Furthermore, our results demonstratemore » that besides depending on the nature of electrocatalyst, the apparent ORR kinetics also strongly depends on the associated potentiodynamic parameters, such as scan rate and scan region, which have a great effect on the coverage of adsorbed OH ad/O ad on Pt surface, thereby affecting the ORR activities of both nanosized and bulk Pt. However, the apparent Tafel slopes remained nearly the same, indicating that the ORR mechanism in all the measurements was not affected by different potentiodynamic parameters.« less

  4. Kinetic Model of Photoautotrophic Growth of Chlorella sp. Microalga, Isolated from the Setúbal Lagoon.

    PubMed

    Heinrich, Josué Miguel; Irazoqui, Horacio Antonio

    2015-01-01

    In this work, a kinetic expression relating light availability in the culture medium with the rate of microalgal growth is obtained. This expression, which is valid for low illumination conditions, was derived from the reactions that take part in the light-dependent stage of photosynthesis. The kinetic expression obtained is a function of the biomass concentration in the culture, as well as of the local volumetric rate of absorption of photons, and only includes two adjustable parameters. To determine the value of these parameters and to test the validity of the hypotheses made, autotrophic cultures of the Chlorella sp. strain were carried out in a modified BBM medium at three CO2 concentrations in the gas stream, namely 0.034%, 0.34% and 3.4%. Moreover, the local volumetric rate of photon absorption was predicted based on a physical model of the interaction of the radiant energy with the suspended biomass, together with a Monte Carlo simulation algorithm. The proposed intrinsic expression of the biomass growth rate, together with the Monte Carlo radiation field simulator, are key to scale up photobioreactors when operating under low irradiation conditions, independently of the configuration of the reactor and of its light source. © 2015 The American Society of Photobiology.

  5. Computer-Aided Construction of Chemical Kinetic Models

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Green, William H.

    2014-12-31

    The combustion chemistry of even simple fuels can be extremely complex, involving hundreds or thousands of kinetically significant species. The most reasonable way to deal with this complexity is to use a computer not only to numerically solve the kinetic model, but also to construct the kinetic model in the first place. Because these large models contain so many numerical parameters (e.g. rate coefficients, thermochemistry) one never has sufficient data to uniquely determine them all experimentally. Instead one must work in “predictive” mode, using theoretical rather than experimental values for many of the numbers in the model, and as appropriatemore » refining the most sensitive numbers through experiments. Predictive chemical kinetics is exactly what is needed for computer-aided design of combustion systems based on proposed alternative fuels, particularly for early assessment of the value and viability of proposed new fuels before those fuels are commercially available. This project was aimed at making accurate predictive chemical kinetics practical; this is a challenging goal which requires a range of science advances. The project spanned a wide range from quantum chemical calculations on individual molecules and elementary-step reactions, through the development of improved rate/thermo calculation procedures, the creation of algorithms and software for constructing and solving kinetic simulations, the invention of methods for model-reduction while maintaining error control, and finally comparisons with experiment. Many of the parameters in the models were derived from quantum chemistry calculations, and the models were compared with experimental data measured in our lab or in collaboration with others.« less

  6. Set-base dynamical parameter estimation and model invalidation for biochemical reaction networks

    PubMed Central

    2010-01-01

    Background Mathematical modeling and analysis have become, for the study of biological and cellular processes, an important complement to experimental research. However, the structural and quantitative knowledge available for such processes is frequently limited, and measurements are often subject to inherent and possibly large uncertainties. This results in competing model hypotheses, whose kinetic parameters may not be experimentally determinable. Discriminating among these alternatives and estimating their kinetic parameters is crucial to improve the understanding of the considered process, and to benefit from the analytical tools at hand. Results In this work we present a set-based framework that allows to discriminate between competing model hypotheses and to provide guaranteed outer estimates on the model parameters that are consistent with the (possibly sparse and uncertain) experimental measurements. This is obtained by means of exact proofs of model invalidity that exploit the polynomial/rational structure of biochemical reaction networks, and by making use of an efficient strategy to balance solution accuracy and computational effort. Conclusions The practicability of our approach is illustrated with two case studies. The first study shows that our approach allows to conclusively rule out wrong model hypotheses. The second study focuses on parameter estimation, and shows that the proposed method allows to evaluate the global influence of measurement sparsity, uncertainty, and prior knowledge on the parameter estimates. This can help in designing further experiments leading to improved parameter estimates. PMID:20500862

  7. Assessment of methane biodegradation kinetics in two-phase partitioning bioreactors by pulse respirometry.

    PubMed

    Ordaz, Alberto; López, Juan C; Figueroa-González, Ivonne; Muñoz, Raúl; Quijano, Guillermo

    2014-12-15

    Biological methane biodegradation is a promising treatment alternative when the methane produced in waste management facilities cannot be used for energy generation. Two-phase partitioning bioreactors (TPPBs), provided with a non-aqueous phase (NAP) with high affinity for the target pollutant, are particularly suitable for the treatment of poorly water-soluble compounds such as methane. Nevertheless, little is known about the influence of the presence of the NAP on the resulting biodegradation kinetics in TPPBs. In this study, an experimental framework based on the in situ pulse respirometry technique was developed to assess the impact of NAP addition on the methane biodegradation kinetics using Methylosinus sporium as a model methane-degrading microorganism. A comprehensive mass transfer characterization was performed in order to avoid mass transfer limiting scenarios and ensure a correct kinetic parameter characterization. The presence of the NAP mediated significant changes in the apparent kinetic parameters of M. sporium during methane biodegradation, with variations of 60, 120, and 150% in the maximum oxygen uptake rate, half-saturation constant and maximum specific growth rate, respectively, compared with the intrinsic kinetic parameters retrieved from a control without NAP. These significant changes in the kinetic parameters mediated by the NAP must be considered for the design, operation and modeling of TPPBs devoted to air pollution control. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. Antioxidant pool in beer and kinetics of EPR spin-trapping.

    PubMed

    Kocherginsky, Nikolai M; Kostetski, Yuri Yu; Smirnov, Alex I

    2005-08-24

    The kinetics of spin-trap adduct formation in beer oxidation exhibits an induction period if the reaction is carried out at elevated temperatures and in the presence of air. This lag period lasts until the endogenous antioxidants are almost completely depleted, and its duration is used as an indicator of the flavor stability and shelf life of beer. This paper demonstrates that the total kinetics of the process can be characterized by three parameters-the lag period, the rate of spin-trap adduct formation, and, finally, the steady-state spin-adduct concentration. A steady-state chain reaction mechanism is described, and quantitative estimates of the main kinetic parameters such as the initiation rate, antioxidant pool, effective content of organic molecules participating in the chain reactions, and the rate constant of the 1-hydroxyethyl radical EtOH(*) spin-adduct disappearance are given. An additional new dimensionless parameter is suggested to characterize the antioxidant pool-the product of the lag time and the rate of spin-trap radical formation immediately after the lag time, normalized by the steady-state concentration of the adducts. The results of spin-tapping EPR experiments are compared with the nitroxide reduction kinetics measured in the same beer samples. It is shown that although the kinetics of nitroxide reduction in beer can be used to evaluate the reducing power of beer, the latter parameter does not correlate with the antioxidant pool. The relationship of free radical processes, antioxidant pool, reducing power, and beer staling is discussed.

  9. Effect of temperature on Brettanomyces bruxellensis: metabolic and kinetic aspects.

    PubMed

    Brandam, Cédric; Castro-Martínez, Claudia; Délia, Marie-Line; Ramón-Portugal, Felipe; Strehaiano, Pierre

    2008-01-01

    The effect of temperatures ranging from 15 to 35 degrees C on a culture of Brettanomyces bruxellensis was investigated in regards to thermodynamics, metabolism, and kinetics. In this temperature range, we observed an increase in growth and production rates. The growth behavior was well represented using the Arrhenius model, and an apparent activation energy of 16.61 kcal/mol was estimated. A stuck fermentation was observed at 35 degrees C as represented by high cell death. The carbon balance established that temperature had no effect on repartition of the glucose consumption between biomass and products. Hence, the same biomass concentration was obtained for all temperatures, except at 35 degrees C. Moreover, using logistic and Luedeking-Piret models, we demonstrated that production rates of ethanol and acetic acid were partially growth associated. Parameters associated with growth (alpha eth and alpha aa) remained constant with changing temperature, whereas, parameters associated with the population (beta eth and beta aa) varied. Optimal values were obtained at 32 degrees C for ethanol and at 25 degrees C for acetic acid.

  10. Gasification Characteristics and Kinetics of Coke with Chlorine Addition

    NASA Astrophysics Data System (ADS)

    Wang, Cui; Zhang, Jianliang; Jiao, Kexin; Liu, Zhengjian; Chou, Kuochih

    2017-10-01

    The gasification process of metallurgical coke with 0, 1.122, 3.190, and 7.132 wt pct chlorine was investigated through thermogravimetric method from ambient temperature to 1593 K (1320 °C) in purified CO2 atmosphere. The variations in the temperature parameters that T i decreases gradually with increasing chlorine, T f and T max first decrease and then increase, but both in a downward trend indicated that the coke gasification process was catalyzed by the chlorine addition. Then the kinetic model of the chlorine-containing coke gasification was obtained through the advanced determination of the average apparent activation energy, the optimal reaction model, and the pre-exponential factor. The average apparent activation energies were 182.962, 118.525, 139.632, and 111.953 kJ/mol, respectively, which were in the same decreasing trend with the temperature parameters analyzed by the thermogravimetric method. It was also demonstrated that the coke gasification process was catalyzed by chlorine. The optimal kinetic model to describe the gasification process of chlorine-containing coke was the Šesták Berggren model using Málek's method, and the pre-exponential factors were 6.688 × 105, 2.786 × 103, 1.782 × 104, and 1.324 × 103 min-1, respectively. The predictions of chlorine-containing coke gasification from the Šesták Berggren model were well fitted with the experimental data.

  11. Kinetic transition in the order-disorder transformation at a solid/liquid interface

    NASA Astrophysics Data System (ADS)

    Galenko, P. K.; Nizovtseva, I. G.; Reuther, K.; Rettenmayr, M.

    2018-01-01

    Phase-field analysis for the kinetic transition in an ordered crystal structure growing from an undercooled liquid is carried out. The results are interpreted on the basis of analytical and numerical solutions of equations describing the dynamics of the phase field, the long-range order parameter as well as the atomic diffusion within the crystal/liquid interface and in the bulk crystal. As an example, the growth of a binary A50B50 crystal is described, and critical undercoolings at characteristic changes of growth velocity and the long-range order parameter are defined. For rapidly growing crystals, analogies and qualitative differences are found in comparison with known non-equilibrium effects, particularly solute trapping and disorder trapping. The results and model predictions are compared qualitatively with results of the theory of kinetic phase transitions (Chernov 1968 Sov. Phys. JETP 26, 1182-1190) and with experimental data obtained for rapid dendritic solidification of congruently melting alloy with order-disorder transition (Hartmann et al. 2009 Europhys. Lett. 87, 40007 (doi:10.1209/0295-5075/87/40007)). This article is part of the theme issue `From atomistic interfaces to dendritic patterns'.

  12. Extracting survival parameters from isothermal, isobaric, and "iso-concentration" inactivation experiments by the "3 end points method".

    PubMed

    Corradini, M G; Normand, M D; Newcomer, C; Schaffner, D W; Peleg, M

    2009-01-01

    Theoretically, if an organism's resistance can be characterized by 3 survival parameters, they can be found by solving 3 simultaneous equations that relate the final survival ratio to the lethal agent's intensity. (For 2 resistance parameters, 2 equations will suffice.) In practice, the inevitable experimental scatter would distort the results of such a calculation or render the method unworkable. Averaging the results obtained with more than 3 final survival ratio triplet combinations, determined in four or more treatments, can remove this impediment. This can be confirmed by the ability of a kinetic inactivation model derived from the averaged parameters to predict survival patterns under conditions not employed in their determination, as demonstrated with published isothermal survival data of Clostridium botulinum spores, isobaric data of Escherichia coli under HPP, and Pseudomonas exposed to hydrogen peroxide. Both the method and the underlying assumption that the inactivation followed a Weibull-Log logistic (WeLL) kinetics were confirmed in this way, indicating that when an appropriate survival model is available, it is possible to predict the entire inactivation curves from several experimental final survival ratios alone. Where applicable, the method could simplify the experimental procedure and lower the cost of microbial resistance determinations. In principle, the methodology can be extended to deteriorative chemical reactions if they too can be characterized by 2 or 3 kinetic parameters.

  13. Estimating Arrhenius parameters using temperature programmed molecular dynamics.

    PubMed

    Imandi, Venkataramana; Chatterjee, Abhijit

    2016-07-21

    Kinetic rates at different temperatures and the associated Arrhenius parameters, whenever Arrhenius law is obeyed, are efficiently estimated by applying maximum likelihood analysis to waiting times collected using the temperature programmed molecular dynamics method. When transitions involving many activated pathways are available in the dataset, their rates may be calculated using the same collection of waiting times. Arrhenius behaviour is ascertained by comparing rates at the sampled temperatures with ones from the Arrhenius expression. Three prototype systems with corrugated energy landscapes, namely, solvated alanine dipeptide, diffusion at the metal-solvent interphase, and lithium diffusion in silicon, are studied to highlight various aspects of the method. The method becomes particularly appealing when the Arrhenius parameters can be used to find rates at low temperatures where transitions are rare. Systematic coarse-graining of states can further extend the time scales accessible to the method. Good estimates for the rate parameters are obtained with 500-1000 waiting times.

  14. Estimating Arrhenius parameters using temperature programmed molecular dynamics

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Imandi, Venkataramana; Chatterjee, Abhijit, E-mail: abhijit@che.iitb.ac.in

    2016-07-21

    Kinetic rates at different temperatures and the associated Arrhenius parameters, whenever Arrhenius law is obeyed, are efficiently estimated by applying maximum likelihood analysis to waiting times collected using the temperature programmed molecular dynamics method. When transitions involving many activated pathways are available in the dataset, their rates may be calculated using the same collection of waiting times. Arrhenius behaviour is ascertained by comparing rates at the sampled temperatures with ones from the Arrhenius expression. Three prototype systems with corrugated energy landscapes, namely, solvated alanine dipeptide, diffusion at the metal-solvent interphase, and lithium diffusion in silicon, are studied to highlight variousmore » aspects of the method. The method becomes particularly appealing when the Arrhenius parameters can be used to find rates at low temperatures where transitions are rare. Systematic coarse-graining of states can further extend the time scales accessible to the method. Good estimates for the rate parameters are obtained with 500-1000 waiting times.« less

  15. Evaluation of the cure kinetics of the wood/pMDI bondline

    Treesearch

    David P. Harper; Michael P. Wolcott; Timothy G. Rials

    2001-01-01

    Micro-dielectric analysis (µDEA) and differentia1 scanning calorimetry (DSC) were used to monitor cure of polymeric diphenyl-methane diisocyanate (pMDI) resin with wood strands in a saturated steam environment. A first-order autocatalyzed kinetic model was employed to determine kinetic parameters. The kinetics were found to follow an Arrhenius relation. A single ramp...

  16. Pseudo second order kinetics and pseudo isotherms for malachite green onto activated carbon: comparison of linear and non-linear regression methods.

    PubMed

    Kumar, K Vasanth; Sivanesan, S

    2006-08-25

    Pseudo second order kinetic expressions of Ho, Sobkowsk and Czerwinski, Blanachard et al. and Ritchie were fitted to the experimental kinetic data of malachite green onto activated carbon by non-linear and linear method. Non-linear method was found to be a better way of obtaining the parameters involved in the second order rate kinetic expressions. Both linear and non-linear regression showed that the Sobkowsk and Czerwinski and Ritchie's pseudo second order model were the same. Non-linear regression analysis showed that both Blanachard et al. and Ho have similar ideas on the pseudo second order model but with different assumptions. The best fit of experimental data in Ho's pseudo second order expression by linear and non-linear regression method showed that Ho pseudo second order model was a better kinetic expression when compared to other pseudo second order kinetic expressions. The amount of dye adsorbed at equilibrium, q(e), was predicted from Ho pseudo second order expression and were fitted to the Langmuir, Freundlich and Redlich Peterson expressions by both linear and non-linear method to obtain the pseudo isotherms. The best fitting pseudo isotherm was found to be the Langmuir and Redlich Peterson isotherm. Redlich Peterson is a special case of Langmuir when the constant g equals unity.

  17. Kinetic rate laws of Cd, Pb, and Zn vaporization during municipal solid waste incineration.

    PubMed

    Falcoz, Quentin; Gauthier, Daniel; Abanades, Stéphane; Flamant, Gilles; Patisson, Fabrice

    2009-03-15

    The kinetic rate laws of heavy metal (HM) vaporization from municipal solid waste during its incineration were studied. Realistic artificial waste (RAW) samples spiked with Pb, Zn, and Cd were injected into a fluidized bed reactor. Metal vaporization wastracked by continuous measure ofthe above metals in exhaust gases. An inverse model of the reactor was used to calculate the metal vaporization rates from the concentration vs time profiles in the outlet gas. For each metal, experiments were carried out at several temperatures in order to determine the kinetic parameters and to obtain specific rate laws as functions of temperature. Temperature has a strong influence on the HM vaporization dynamics, especially on the vaporization kinetics profile. This phenomenon was attributed to internal diffusion control of the HM release. Two types of kinetic rate laws were established based on temperature: a fourth- or fifth-order polynomial rate law (r(x) = k0e(-E(A)/RT)p(x)) for temperatures lower than 740 degrees C and a first-order polynomial (r(x) = k0e(-E(A)/ RT(q-q(f) for temperatures higher than 740 degrees C.

  18. Kinetic modelling of anaerobic hydrolysis of solid wastes, including disintegration processes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    García-Gen, Santiago; Sousbie, Philippe; Rangaraj, Ganesh

    2015-01-15

    Highlights: • Fractionation of solid wastes into readily and slowly biodegradable fractions. • Kinetic coefficients estimation from mono-digestion batch assays. • Validation of kinetic coefficients with a co-digestion continuous experiment. • Simulation of batch and continuous experiments with an ADM1-based model. - Abstract: A methodology to estimate disintegration and hydrolysis kinetic parameters of solid wastes and validate an ADM1-based anaerobic co-digestion model is presented. Kinetic parameters of the model were calibrated from batch reactor experiments treating individually fruit and vegetable wastes (among other residues) following a new protocol for batch tests. In addition, decoupled disintegration kinetics for readily and slowlymore » biodegradable fractions of solid wastes was considered. Calibrated parameters from batch assays of individual substrates were used to validate the model for a semi-continuous co-digestion operation treating simultaneously 5 fruit and vegetable wastes. The semi-continuous experiment was carried out in a lab-scale CSTR reactor for 15 weeks at organic loading rate ranging between 2.0 and 4.7 g VS/L d. The model (built in Matlab/Simulink) fit to a large extent the experimental results in both batch and semi-continuous mode and served as a powerful tool to simulate the digestion or co-digestion of solid wastes.« less

  19. The influence of technological parameters on the dynamic behavior of "liquid wood" samples obtained by injection molding

    NASA Astrophysics Data System (ADS)

    Plavanescu Mazurchevici, Simona; Carausu, Constantin; Comaneci, Radu; Nedelcu, Dumitru

    2017-10-01

    The plastic products contribute to environmental pollution. Replacing the plastic materials with biodegradable materials with superior properties is an absolute necessity and important research direction for the near future. The first steps in this regard were the creation of composite materials containing natural fibers with positive effects on the environment that have penetrated in different fields. The bioplastics and biocomposites made from natural fibers is a topical solution. The next step was made towards obtaining biodegradable and recyclable materials based on cellulose, lignin and no carcinogens. In this category fall the "liquid wood" with a use up to five times without affecting the mechanical properties. "Liquid wood" is a high quality thermoplastic biocomposite. "Liquid wood" is a biopolymer composite divided in three categories, ARBOFORM®, ARBOBLEND® and ARBOFILL®, which have differed composition in terms of lignin percentage, being delivered by Tecnaro, as granules, [1]. The paper's research was focus on Arboform L V3 Nature and Arboform L V3 Nature reinforced with aramid fiber. In the experimental plan were taken into account six parameters (Dinj - direction of injection [°]; Ttop - melting temperature [°C]; Pinj - injection pressure [MPa] Ss - speed [m/min]; tinj - injection time [s] and tc - cooling time [s]) each with two levels, research carried on by Taguchi methodology. Processing Taguchi method allowed both Taguchi setting work parameters influence on storage modulus and damping as the size and influence their ranking. Experimental research concerning the influence technological parameters on storage modulus of samples obtained by injection from Arboform L V3 Nature yielded an average of 6055MPa and descending order as follows: Trac, Ss, Pinj, Dinj and Ttop. The average of model for reinforced material was 6419MPa and descending order of parameters influence such as: Dinj, Trac, Ttop, tinj, Ss and Pinj.

  20. Effect of q-nonextensive parameter and saturation time on electron density steepening in electron-positron-ion plasmas

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hashemzadeh, M., E-mail: hashemzade@gmail.com

    2015-11-15

    The effect of q-nonextensive parameter and saturation time on the electron density steepening in electron-positron-ion plasmas is studied by particle in cell method. Phase space diagrams show that the size of the holes, and consequently, the number of trapped particles strongly depends on the q-parameter and saturation time. Furthermore, the mechanism of the instability and exchange of energy between electron-positron and electric field is explained by the profiles of the energy density. Moreover, it is found that the q-parameter, saturation time, and electron and positron velocities affect the nonlinear evolution of the electron density which leads to the steepening ofmore » its structure. The q-nonextensive parameter or degree of nonextensivity is the relation between temperature gradient and potential energy of the system. Therefore, the deviation of q-parameter from unity indicates the degree of inhomogeneity of temperature or deviation from equilibrium. Finally, using the kinetic theory, a generalized q-dispersion relation is presented for electron-positron-ion plasma systems. It is found that the simulation results in the linear regime are in good agreement with the growth rate results obtained by the kinetic theory.« less

  1. Kinetic sensitivity of a receptor-binding radiopharmaceutical: Technetium-99m galactosyl-neoglycoalbumin

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Vera, D.R.; Woodle, E.S.; Stadalnik, R.C.

    1989-09-01

    Kinetic sensitivity is the ability of a physiochemical parameter to alter the time-activity curve of a radiotracer. The kinetic sensitivity of liver and blood time-activity data resulting from a single bolus injection of ({sup 99m}Tc)galactosyl-neoglycoalbumin (( Tc)NGA) into healthy pigs was examined. Three parameters, hepatic plasma flow scaled as flow per plasma volume, ligand-receptor affinity, and total receptor concentration, were tested using (Tc)NGA injections of various molar doses and affinities. Simultaneous measurements of plasma volume (iodine-125 human serum albumin dilution), and hepatic plasma flow (indocyanine green extraction) were performed during 12 (Tc)NGA studies. Paired data sets demonstrated differences (P(chi v2)more » less than 0.01) in liver and blood time-activity curves in response to changes in each of the tested parameters. We conclude that the (Tc)NGA radiopharmacokinetic system is therefore sensitive to hepatic plasma flow, ligand-receptor affinity, and receptor concentration. In vivo demonstration of kinetic sensitivity permits delineation of the physiologic parameters that determine the biodistribution of a radiopharmaceutical. This delineation is a prerequisite to a valid analytic assessment of receptor biochemistry via kinetic modeling.« less

  2. Kinetic corrections from analytic non-Maxwellian distribution functions in magnetized plasmas

    NASA Astrophysics Data System (ADS)

    Izacard, Olivier

    2016-08-01

    In magnetized plasma physics, almost all developed analytic theories assume a Maxwellian distribution function (MDF) and in some cases small deviations are described using the perturbation theory. The deviations with respect to the Maxwellian equilibrium, called kinetic effects, are required to be taken into account especially for fusion reactor plasmas. Generally, because the perturbation theory is not consistent with observed steady-state non-Maxwellians, these kinetic effects are numerically evaluated by very central processing unit (CPU)-expensive codes, avoiding the analytic complexity of velocity phase space integrals. We develop here a new method based on analytic non-Maxwellian distribution functions constructed from non-orthogonal basis sets in order to (i) use as few parameters as possible, (ii) increase the efficiency to model numerical and experimental non-Maxwellians, (iii) help to understand unsolved problems such as diagnostics discrepancies from the physical interpretation of the parameters, and (iv) obtain analytic corrections due to kinetic effects given by a small number of terms and removing the numerical error of the evaluation of velocity phase space integrals. This work does not attempt to derive new physical effects even if it could be possible to discover one from the better understandings of some unsolved problems, but here we focus on the analytic prediction of kinetic corrections from analytic non-Maxwellians. As applications, examples of analytic kinetic corrections are shown for the secondary electron emission, the Langmuir probe characteristic curve, and the entropy. This is done by using three analytic representations of the distribution function: the Kappa distribution function, the bi-modal or a new interpreted non-Maxwellian distribution function (INMDF). The existence of INMDFs is proved by new understandings of the experimental discrepancy of the measured electron temperature between two diagnostics in JET. As main results, it

  3. Kinetic corrections from analytic non-Maxwellian distribution functions in magnetized plasmas

    DOE PAGES

    Izacard, Olivier

    2016-08-02

    In magnetized plasma physics, almost all developed analytic theories assume a Maxwellian distribution function (MDF) and in some cases small deviations are described using the perturbation theory. The deviations with respect to the Maxwellian equilibrium, called kinetic effects, are required to be taken into account especially for fusion reactor plasmas. Generally, because the perturbation theory is not consistent with observed steady-state non-Maxwellians, these kinetic effects are numerically evaluated by very central processing unit (CPU)-expensive codes, avoiding the analytic complexity of velocity phase space integrals. We develop here a new method based on analytic non-Maxwellian distribution functions constructed from non-orthogonal basismore » sets in order to (i) use as few parameters as possible, (ii) increase the efficiency to model numerical and experimental non-Maxwellians, (iii) help to understand unsolved problems such as diagnostics discrepancies from the physical interpretation of the parameters, and (iv) obtain analytic corrections due to kinetic effects given by a small number of terms and removing the numerical error of the evaluation of velocity phase space integrals. This work does not attempt to derive new physical effects even if it could be possible to discover one from the better understandings of some unsolved problems, but here we focus on the analytic prediction of kinetic corrections from analytic non-Maxwellians. As applications, examples of analytic kinetic corrections are shown for the secondary electron emission, the Langmuir probe characteristic curve, and the entropy. This is done by using three analytic representations of the distribution function: the Kappa distribution function, the bi-modal or a new interpreted non-Maxwellian distribution function (INMDF). The existence of INMDFs is proved by new understandings of the experimental discrepancy of the measured electron temperature between two diagnostics in JET. As main

  4. Kinetic corrections from analytic non-Maxwellian distribution functions in magnetized plasmas

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Izacard, Olivier, E-mail: izacard@llnl.gov

    In magnetized plasma physics, almost all developed analytic theories assume a Maxwellian distribution function (MDF) and in some cases small deviations are described using the perturbation theory. The deviations with respect to the Maxwellian equilibrium, called kinetic effects, are required to be taken into account especially for fusion reactor plasmas. Generally, because the perturbation theory is not consistent with observed steady-state non-Maxwellians, these kinetic effects are numerically evaluated by very central processing unit (CPU)-expensive codes, avoiding the analytic complexity of velocity phase space integrals. We develop here a new method based on analytic non-Maxwellian distribution functions constructed from non-orthogonal basismore » sets in order to (i) use as few parameters as possible, (ii) increase the efficiency to model numerical and experimental non-Maxwellians, (iii) help to understand unsolved problems such as diagnostics discrepancies from the physical interpretation of the parameters, and (iv) obtain analytic corrections due to kinetic effects given by a small number of terms and removing the numerical error of the evaluation of velocity phase space integrals. This work does not attempt to derive new physical effects even if it could be possible to discover one from the better understandings of some unsolved problems, but here we focus on the analytic prediction of kinetic corrections from analytic non-Maxwellians. As applications, examples of analytic kinetic corrections are shown for the secondary electron emission, the Langmuir probe characteristic curve, and the entropy. This is done by using three analytic representations of the distribution function: the Kappa distribution function, the bi-modal or a new interpreted non-Maxwellian distribution function (INMDF). The existence of INMDFs is proved by new understandings of the experimental discrepancy of the measured electron temperature between two diagnostics in JET. As main

  5. Shape-Controlled Synthesis of Colloidal Metal Nanocrystals: Thermodynamic versus Kinetic Products.

    PubMed

    Xia, Younan; Xia, Xiaohu; Peng, Hsin-Chieh

    2015-07-01

    This Perspective provides a contemporary understanding of the shape evolution of colloidal metal nanocrystals under thermodynamically and kinetically controlled conditions. It has been extremely challenging to investigate this subject in the setting of one-pot synthesis because both the type and number of seeds involved would be changed whenever the experimental conditions are altered, making it essentially impossible to draw conclusions when comparing the outcomes of two syntheses conducted under different conditions. Because of the uncertainty about seeds, most of the mechanistic insights reported in literature for one-pot syntheses of metal nanocrystals with different shapes are either incomplete or ambiguous, and some of them might be misleading or even wrong. Recently, with the use of well-defined seeds for such syntheses, it became possible to separate growth from nucleation and therefore investigate the explicit role(s) played by a specific thermodynamic or kinetic parameter in directing the evolution of colloidal metal nanocrystals into a specific shape. Starting from single-crystal seeds enclosed by a mix of {100}, {111}, and {110} facets, for example, one can obtain colloidal nanocrystals with diversified shapes by adjusting various thermodynamic or kinetic parameters. The mechanistic insights learnt from these studies can also be extended to account for the products of conventional one-pot syntheses that involve self-nucleation only. The knowledge can be further applied to many other types of seeds with twin defects or stacking faults, making it an exciting time to design and synthesize colloidal metal nanocrystals with the shapes sought for a variety of fundamental studies and technologically important applications.

  6. Quantitative Correlation between Viscosity of Concentrated MAb Solutions and Particle Size Parameters Obtained from Small-Angle X-ray Scattering.

    PubMed

    Fukuda, Masakazu; Moriyama, Chifumi; Yamazaki, Tadao; Imaeda, Yoshimi; Koga, Akiko

    2015-12-01

    To investigate the relationship between viscosity of concentrated MAb solutions and particle size parameters obtained from small-angle X-ray scattering (SAXS). The viscosity of three MAb solutions (MAb1, MAb2, and MAb3; 40-200 mg/mL) was measured by electromagnetically spinning viscometer. The protein interactions of MAb solutions (at 60 mg/mL) was evaluated by SAXS. The phase behavior of 60 mg/mL MAb solutions in a low-salt buffer was observed after 1 week storage at 25°C. The MAb1 solutions exhibited the highest viscosity among the three MAbs in the buffer containing 50 mM NaCl. Viscosity of MAb1 solutions decreased with increasing temperature, increasing salt concentration, and addition of amino acids. Viscosity of MAb1 solutions was lowest in the buffer containing histidine, arginine, and aspartic acid. Particle size parameters obtained from SAXS measurements correlated very well with the viscosity of MAb solutions at 200 mg/mL. MAb1 exhibited liquid-liquid phase separation at a low salt concentration. Simultaneous addition of basic and acidic amino acids effectively suppressed intermolecular attractive interactions and decreased viscosity of MAb1 solutions. SAXS can be performed using a small volume of samples; therefore, the particle size parameters obtained from SAXS at intermediate protein concentration could be used to screen for low viscosity antibodies in the early development stage.

  7. Impact of angiogenesis-related gene expression on the tracer kinetics of 18F-FDG in colorectal tumors.

    PubMed

    Strauss, Ludwig G; Koczan, Dirk; Klippel, Sven; Pan, Leyun; Cheng, Caixia; Willis, Stefan; Haberkorn, Uwe; Dimitrakopoulou-Strauss, Antonia

    2008-08-01

    18F-FDG kinetics are primarily dependent on the expression of genes associated with glucose transporters and hexokinases but may be modulated by other genes. The dependency of 18F-FDG kinetics on angiogenesis-related gene expression was evaluated in this study. Patients with primary colorectal tumors (n = 25) were examined with PET and 18F-FDG within 2 days before surgery. Tissue specimens were obtained from the tumor and the normal colon during surgery, and gene expression was assessed using gene arrays. Overall, 23 angiogenesis-related genes were identified with a tumor-to-normal ratio exceeding 1.50. Analysis revealed a significant correlation between k1 and vascular endothelial growth factor (VEGF-A, r = 0.51) and between fractal dimension and angiopoietin-2 (r = 0.48). k3 was negatively correlated with VEGF-B (r = -0.46), and a positive correlation was noted for angiopoietin-like 4 gene (r = 0.42). A multiple linear regression analysis was used for the PET parameters to predict the gene expression, and a correlation coefficient of r = 0.75 was obtained for VEGF-A and of r = 0.76 for the angiopoietin-2 expression. Thus, on the basis of these multiple correlation coefficients, angiogenesis-related gene expression contributes to about 50% of the variance of the 18F-FDG kinetic data. The global 18F-FDG uptake, as measured by the standardized uptake value and influx, was not significantly correlated with angiogenesis-associated genes. 18F-FDG kinetics are modulated by angiogenesis-related genes. The transport rate for 18F-FDG (k1) is higher in tumors with a higher expression of VEGF-A and angiopoietin-2. The regression functions for the PET parameters provide the possibility to predict the gene expression of VEGF-A and angiopoietin-2.

  8. A novel approach to the experimental study on methane/steam reforming kinetics using the Orthogonal Least Squares method

    NASA Astrophysics Data System (ADS)

    Sciazko, Anna; Komatsu, Yosuke; Brus, Grzegorz; Kimijima, Shinji; Szmyd, Janusz S.

    2014-09-01

    For a mathematical model based on the result of physical measurements, it becomes possible to determine their influence on the final solution and its accuracy. However, in classical approaches, the influence of different model simplifications on the reliability of the obtained results are usually not comprehensively discussed. This paper presents a novel approach to the study of methane/steam reforming kinetics based on an advanced methodology called the Orthogonal Least Squares method. The kinetics of the reforming process published earlier are divergent among themselves. To obtain the most probable values of kinetic parameters and enable direct and objective model verification, an appropriate calculation procedure needs to be proposed. The applied Generalized Least Squares (GLS) method includes all the experimental results into the mathematical model which becomes internally contradicted, as the number of equations is greater than number of unknown variables. The GLS method is adopted to select the most probable values of results and simultaneously determine the uncertainty coupled with all the variables in the system. In this paper, the evaluation of the reaction rate after the pre-determination of the reaction rate, which was made by preliminary calculation based on the obtained experimental results over a Nickel/Yttria-stabilized Zirconia catalyst, was performed.

  9. Impact of ambiguity resolution and application of transformation parameters obtained by regional GNSS network in Precise Point Positioning

    NASA Astrophysics Data System (ADS)

    Gandolfi, S.; Poluzzi, L.; Tavasci, L.

    2012-12-01

    Precise Point Positioning (PPP) is one of the possible approaches for GNSS data processing. As known this technique is faster and more flexible compared to the others which are based on a differenced approach and constitute a reliable methods for accurate positioning of remote GNSS stations, even in some remote area such as Antarctica. Until few years ago one of the major limits of the method was the impossibility to resolve the ambiguity as integer but nowadays many methods are available to resolve this aspect. The first software package permitting a PPP solution was the GIPSY OASIS realized, developed and maintained by JPL (NASA). JPL produce also orbits and files ready to be used with GIPSY. Recently, using these products came possible to resolve ambiguities improving the stability of solutions. PPP permit to estimate position into the reference frame of the orbits (IGS) and when coordinate in others reference frames, such al ITRF, are needed is necessary to apply a transformation. Within his products JPL offer, for each day, a global 7 parameter transformation that permit to locate the survey into the ITRF RF. In some cases it's also possible to create a costumed process and obtain analogous parameters using local/regional reference network of stations which coordinates are available also in the desired reference frame. In this work some tests on accuracy has been carried out comparing different PPP solutions obtained using the same software packages (GIPSY) but considering the ambiguity resolution, the global and regional transformation parameters. In particular two test area have been considered, first one located in Antarctica and the second one in Italy. Aim of the work is the evaluation of the impact of ambiguity resolution and the use of local/regional transformation parameter in the final solutions. Tests shown how the ambiguity resolution improve the precision, especially in the EAST component with a scattering reduction about 8%. And the use of global

  10. Adsorption of saturated fatty acid in urea complexation: Kinetics and equilibrium studies

    NASA Astrophysics Data System (ADS)

    Setyawardhani, Dwi Ardiana; Sulistyo, Hary; Sediawan, Wahyudi Budi; Fahrurrozi, Mohammad

    2018-02-01

    Urea complexation is fractionation process for concentrating poly-unsaturated fatty acids (PUFAs) from vegetable oil or animal fats. For process design and optimization in commercial industries, it is necessary to provide kinetics and equilibrium data. Urea inclusion compounds (UICs) as the product is a unique complex form which one molecule (guest) is enclosed within another molecule (host). In urea complexation, the guest-host bonding exists between saturated fatty acids (SFAs) and crystalline urea. This research studied the complexation is analogous to an adsorption process. The Batch adsorption process was developed to obtain the experimental data. The ethanolic urea solution was mixed with SFA in certain compositions and adsorption times. The mixture was heated until it formed homogenous and clear solution, then it cooled very slowly until the first numerous crystal appeared. Adsorption times for the kinetic data were determined since the crystal formed. The temperature was maintained constant at room temperature. Experimental sets of data were observed with adsorption kinetics and equilibrium models. High concentration of saturated fatty acid (SFA) was used to represent adsorption kinetics and equilibrium parameters. Kinetic data were examined with pseudo first-order, pseudo second-order and intra particle diffusion models. Linier, Freundlich and Langmuir isotherm were used to study the equilibrium model of this adsorption. The experimental data showed that SFA adsorption in urea crystal followed pseudo second-order model. The compatibility of the data with Langmuir isotherm showed that urea complexation was a monolayer adsorption.

  11. Chemiomics: network reconstruction and kinetics of port wine aging.

    PubMed

    Monforte, Ana Rita; Jacobson, Dan; Silva Ferreira, A C

    2015-03-11

    Network reconstruction (NR) has proven to be useful in the detection and visualization of relationships among the compounds present in a Port wine aging data set. This view of the data provides a considerable amount of information with which to understand the kinetic contexts of the molecules represented by peaks in each chromatogram. The aim of this study was to use NR together with the determination of kinetic parameters to extract more information about the mechanisms involved in Port wine aging. The volatile compounds present in samples of Port wines spanning 128 years in age were measured with the use of GC-MS. After chromatogram alignment, a peak matrix was created, and all peak vectors were compared to one another to determine their Pearson correlations over time. A correlation network was created and filtered on the basis of the resulting correlation values. Some nodes in the network were further studied in experiments on Port wines stored under different conditions of oxygen and temperature in order to determine their kinetic parameters. The resulting network can be divided into three main branches. The first branch is related to compounds that do not directly correlate to age, the second branch contains compounds affected by temperature, and the third branch contains compounds associated with oxygen. Compounds clustered in the same branch of the network have similar expression patterns over time as well as the same kinetic order, thus are likely to be dependent on the same technological parameters. Network construction and visualization provides more information with which to understand the probable kinetic contexts of the molecules represented by peaks in each chromatogram. The approach described here is a powerful tool for the study of mechanisms and kinetics in complex systems and should aid in the understanding and monitoring of wine quality.

  12. Chemiomics: Network Reconstruction and Kinetics of Port Wine Aging

    DOE PAGES

    Monforte, Ana Rita; Jacobson, Dan; Silva Ferreira, A. C.

    2015-02-11

    Network reconstruction (NR) has proven to be useful in the detection and visualization of relationships among the compounds present in a Port wine aging data set. This view of the data provides a considerable amount of information with which to understand the kinetic contexts of the molecules represented by peaks in each chromatogram. The aim of this paper was to use NR together with the determination of kinetic parameters to extract more information about the mechanisms involved in Port wine aging. The volatile compounds present in samples of Port wines spanning 128 years in age were measured with the usemore » of GC-MS. After chromatogram alignment, a peak matrix was created, and all peak vectors were compared to one another to determine their Pearson correlations over time. A correlation network was created and filtered on the basis of the resulting correlation values. Some nodes in the network were further studied in experiments on Port wines stored under different conditions of oxygen and temperature in order to determine their kinetic parameters. The resulting network can be divided into three main branches. The first branch is related to compounds that do not directly correlate to age, the second branch contains compounds affected by temperature, and the third branch contains compounds associated with oxygen. Compounds clustered in the same branch of the network have similar expression patterns over time as well as the same kinetic order, thus are likely to be dependent on the same technological parameters. Network construction and visualization provides more information with which to understand the probable kinetic contexts of the molecules represented by peaks in each chromatogram. Finally, the approach described here is a powerful tool for the study of mechanisms and kinetics in complex systems and should aid in the understanding and monitoring of wine quality.« less

  13. New insights on timing of oil and gas generation in the central Gulf Coast interior zone based on hydrous-pyrolysis kinetic parameters

    USGS Publications Warehouse

    Lewan, Michael D.; Dutton, Shirley P.; Ruppel, Stephen C.; Hentz, Tucker F.

    2002-01-01

    Timing of oil and gas generation from Turonian and Smackover source rocks in the central Gulf CoastInterior Zone was determined in one-dimensional burial-history curves (BHCs) using hydrous-pyrolysis kinetic parameters. The results predict that basal Smackover source-rock intervals with Type-IIS kerogen completed oil generation between 121 and 99 Ma, and Turonian source-rocks with Type-II kerogen remain immature over most of the same area. The only exception to the latter occurs in the northwestern part of the Mississippi salt basin, where initial stages of oil generation have started as a result of higher thermal gradients. This maturity difference between Turonian and Smackover source rocks is predicted with present-day thermal gradients. Predicted oil generation prior to the Sabine and Monroe uplifts suggests that a significant amount of the oil emplaced in Cretaceous reservoirs of these uplifts would have been lost during periods of erosion. Hydrous-pyrolysis kineticparameters predict that cracking of Smackover oil to gas started 52 Ma, which postdates major uplift and erosional events of the Sabine and Monroe uplifts. This generated gas would accumulate and persist in these uplift areas as currently observed. The predicted timing of oil and gas generation with hydrous-pyrolysis kinetic parameters is in accordance with the observed scarcity of oil from Turonian source rocks, predominance of gas accumulations on the Sabine and Monroe uplifts, and predominance of oil accumulations along the northern rim of the Interior Zone.

  14. A Sequential Fluid-mechanic Chemical-kinetic Model of Propane HCCI Combustion

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Aceves, S M; Flowers, D L; Martinez-Frias, J

    2000-11-29

    We have developed a methodology for predicting combustion and emissions in a Homogeneous Charge Compression Ignition (HCCI) Engine. This methodology combines a detailed fluid mechanics code with a detailed chemical kinetics code. Instead of directly linking the two codes, which would require an extremely long computational time, the methodology consists of first running the fluid mechanics code to obtain temperature profiles as a function of time. These temperature profiles are then used as input to a multi-zone chemical kinetics code. The advantage of this procedure is that a small number of zones (10) is enough to obtain accurate results. Thismore » procedure achieves the benefits of linking the fluid mechanics and the chemical kinetics codes with a great reduction in the computational effort, to a level that can be handled with current computers. The success of this procedure is in large part a consequence of the fact that for much of the compression stroke the chemistry is inactive and thus has little influence on fluid mechanics and heat transfer. Then, when chemistry is active, combustion is rather sudden, leaving little time for interaction between chemistry and fluid mixing and heat transfer. This sequential methodology has been capable of explaining the main characteristics of HCCI combustion that have been observed in experiments. In this paper, we use our model to explore an HCCI engine running on propane. The paper compares experimental and numerical pressure traces, heat release rates, and hydrocarbon and carbon monoxide emissions. The results show an excellent agreement, even in parameters that are difficult to predict, such as chemical heat release rates. Carbon monoxide emissions are reasonably well predicted, even though it is intrinsically difficult to make good predictions of CO emissions in HCCI engines. The paper includes a sensitivity study on the effect of the heat transfer correlation on the results of the analysis. Importantly, the paper

  15. Kinetic study of ion acoustic twisted waves with kappa distributed electrons

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Arshad, Kashif, E-mail: kashif.arshad.butt@gmail.com; Aman-ur-Rehman, E-mail: amansadiq@gmail.com; Mahmood, Shahzad, E-mail: shahzadm100@gmail.com

    2016-05-15

    The kinetic theory of Landau damping of ion acoustic twisted modes is developed in the presence of orbital angular momentum of the helical (twisted) electric field in plasmas with kappa distributed electrons and Maxwellian ions. The perturbed distribution function and helical electric field are considered to be decomposed by Laguerre-Gaussian mode function defined in cylindrical geometry. The Vlasov-Poisson equation is obtained and solved analytically to obtain the weak damping rates of the ion acoustic twisted waves in a non-thermal plasma. The strong damping effects of ion acoustic twisted waves at low values of temperature ratio of electrons and ions aremore » also obtained by using exact numerical method and illustrated graphically, where the weak damping wave theory fails to explain the phenomenon properly. The obtained results of Landau damping rates of the twisted ion acoustic wave are discussed at different values of azimuthal wave number and non-thermal parameter kappa for electrons.« less

  16. Revealing the physical insight of a length-scale parameter in metamaterials by exploiting the variational formulation

    NASA Astrophysics Data System (ADS)

    Abali, B. Emek

    2018-04-01

    For micro-architectured materials with a substructure, called metamaterials, we can realize a direct numerical simulation in the microscale by using classical mechanics. This method is accurate, however, computationally costly. Instead, a solution of the same problem in the macroscale is possible by means of the generalized mechanics. In this case, no detailed modeling of the substructure is necessary; however, new parameters emerge. A physical interpretation of these metamaterial parameters is challenging leading to a lack of experimental strategies for their determination. In this work, we exploit the variational formulation based on action principles and obtain a direct relation between a parameter used in the kinetic energy and a metamaterial parameter in the case of a viscoelastic model.

  17. A general moment expansion method for stochastic kinetic models

    NASA Astrophysics Data System (ADS)

    Ale, Angelique; Kirk, Paul; Stumpf, Michael P. H.

    2013-05-01

    Moment approximation methods are gaining increasing attention for their use in the approximation of the stochastic kinetics of chemical reaction systems. In this paper we derive a general moment expansion method for any type of propensities and which allows expansion up to any number of moments. For some chemical reaction systems, more than two moments are necessary to describe the dynamic properties of the system, which the linear noise approximation is unable to provide. Moreover, also for systems for which the mean does not have a strong dependence on higher order moments, moment approximation methods give information about higher order moments of the underlying probability distribution. We demonstrate the method using a dimerisation reaction, Michaelis-Menten kinetics and a model of an oscillating p53 system. We show that for the dimerisation reaction and Michaelis-Menten enzyme kinetics system higher order moments have limited influence on the estimation of the mean, while for the p53 system, the solution for the mean can require several moments to converge to the average obtained from many stochastic simulations. We also find that agreement between lower order moments does not guarantee that higher moments will agree. Compared to stochastic simulations, our approach is numerically highly efficient at capturing the behaviour of stochastic systems in terms of the average and higher moments, and we provide expressions for the computational cost for different system sizes and orders of approximation. We show how the moment expansion method can be employed to efficiently quantify parameter sensitivity. Finally we investigate the effects of using too few moments on parameter estimation, and provide guidance on how to estimate if the distribution can be accurately approximated using only a few moments.

  18. Fission fragment mass and total kinetic energy distributions of spontaneously fissioning plutonium isotopes

    NASA Astrophysics Data System (ADS)

    Pomorski, K.; Nerlo-Pomorska, B.; Bartel, J.; Schmitt, C.

    2018-03-01

    The fission-fragment mass and total kinetic energy (TKE) distributions are evaluated in a quantum mechanical framework using elongation, mass asymmetry, neck degree of freedom as the relevant collective parameters in the Fourier shape parametrization recently developed by us. The potential energy surfaces (PES) are calculated within the macroscopic-microscopic model based on the Lublin-Strasbourg Drop (LSD), the Yukawa-folded (YF) single-particle potential and a monopole pairing force. The PES are presented and analysed in detail for even-even Plutonium isotopes with A = 236-246. They reveal deep asymmetric valleys. The fission-fragment mass and TKE distributions are obtained from the ground state of a collective Hamiltonian computed within the Born-Oppenheimer approximation, in the WKB approach by introducing a neck-dependent fission probability. The calculated mass and total kinetic energy distributions are found in good agreement with the data.

  19. Sorption of albendazole in sediments and soils: Isotherms and kinetics.

    PubMed

    Mutavdžić Pavlović, Dragana; Glavač, Antonija; Gluhak, Mihaela; Runje, Mislav

    2018-02-01

    Albendazole is a broad-spectrum anthelmintic drug effective against gastrointestinal parasites in humans and animals. Despite the fact that it has been detected in environment (water, sediment and soil), there is no information on its fate in the environment. So, in order to understand the sorption process of albendazole in environment, the sorption mechanism and kinetic properties were investigated through sorption equilibrium and sorption rate experiments. For that purpose, batch sorption of albendazole on five sediment samples and five soil samples from Croatia's region with different physico-chemical properties was investigated. Except physico-chemical properties of used environmental solid samples, the effects of various parameters such as contact time, initial concentration, ionic strength and pH on the albendazole sorption were studied. The K d parameter from linear sorption model was determined by linear regression analysis, while the Freundlich and Langmuir sorption models were applied to describe the equilibrium isotherms. The estimated K d values varied from 29.438 to 104.43 mLg -1 at 0.01 M CaCl 2 and for natural pH value of albendazole solution (pH 6.6). Experimental data showed that the best agreement was obtained with the linear model (R 2  > 0.99), while the rate of albendazole sorption is the best described with the kinetic model of pseudo-second-order. Obtained results point to a medium or even strong sorption of albendazole for soil or sediment particles, which is particularly dependent on the proportion of organic matter, pH, copper and zinc in them. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Kinetic Folding Mechanism of Erythropoietin

    PubMed Central

    Banks, Douglas D.; Scavezze, Joanna L.; Siska, Christine C.

    2009-01-01

    This report describes what to our knowledge is the first kinetic folding studies of erythropoietin, a glycosylated four-helical bundle cytokine responsible for the regulation of red blood cell production. Kinetic responses for folding and unfolding reactions initiated by manual mixing were monitored by far-ultraviolet circular dichroism and fluorescence spectroscopy, and folding reactions initiated by stopped-flow mixing were monitored by fluorescence. The urea concentration dependence of the observed kinetics were best described by a three-state model with a transiently populated intermediate species that is on-pathway and obligatory. This folding scheme was further supported by the excellent agreement between the free energy of unfolding and m-value calculated from the microscopic rate constants derived from this model and these parameters determined from separate equilibrium unfolding experiments. Compared to the kinetics of other members of the four-helical bundle cytokine family, erythropoietin folding and unfolding reactions were slower and less susceptible to aggregation. We tentatively attribute these slower rates and protection from association events to the large amount of carbohydrate attached to erythropoietin at four sites. PMID:19450492

  1. Kinetics of trichloroethylene cometabolism and toluene biodegradation: Model application to soil batch experiments

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    El-Farhan, Y.H.; Scow, K.M.; Fan, S.

    Trichloroethylene (TCE) biodegradation in soil under aerobic conditions requires the presence of another compound, such as toluene, to support growth of microbial populations and enzyme induction. The biodegradation kinetics of TCE and toluene were examined by conducting three groups of experiments in soil: toluene only, toluene combined with low TCE concentrations, and toluene with TCE concentrations similar to or higher than toluene. The biodegradation of TCE and toluene and their interrelationships were modeled using a combination of several biodegradation functions. In the model, the pollutants were described as existing in the solid, liquid, and gas phases of soil, with biodegradationmore » occurring only in the liquid phase. The distribution of the chemicals between the solid and liquid phase was described by a linear sorption isotherm, whereas liquid-vapor partitioning was described by Henry's law. Results from 12 experiments with toluene only could be described by a single set of kinetic parameters. The same set of parameters could describe toluene degradation in 10 experiments where low TCE concentrations were present. From these 10 experiments a set of parameters describing TCE cometabolism induced by toluene also was obtained. The complete set of parameters was used to describe the biodegradation of both compounds in 15 additional experiments, where significant TCE toxicity and inhibition effects were expected. Toluene parameters were similar to values reported for pure culture systems. Parameters describing the interaction of TCE with toluene and biomass were different from reported values for pure cultures, suggesting that the presence of soil may have affected the cometabolic ability of the indigenous soil microbial populations.« less

  2. Kinetic energy partition method applied to ground state helium-like atoms.

    PubMed

    Chen, Yu-Hsin; Chao, Sheng D

    2017-03-28

    We have used the recently developed kinetic energy partition (KEP) method to solve the quantum eigenvalue problems for helium-like atoms and obtain precise ground state energies and wave-functions. The key to treating properly the electron-electron (repulsive) Coulomb potential energies for the KEP method to be applied is to introduce a "negative mass" term into the partitioned kinetic energy. A Hartree-like product wave-function from the subsystem wave-functions is used to form the initial trial function, and the variational search for the optimized adiabatic parameters leads to a precise ground state energy. This new approach sheds new light on the all-important problem of solving many-electron Schrödinger equations and hopefully opens a new way to predictive quantum chemistry. The results presented here give very promising evidence that an effective one-electron model can be used to represent a many-electron system, in the spirit of density functional theory.

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

    NASA Astrophysics Data System (ADS)

    Fatmawati, Akbarningrum; Agustriyanto, Rudy

    2015-12-01

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

  4. The platinum microelectrode/Nafion interface - An electrochemical impedance spectroscopic analysis of oxygen reduction kinetics and Nafion characteristics

    NASA Technical Reports Server (NTRS)

    Parthasarathy, Arvind; Dave, Bhasker; Srinivasan, Supramaniam; Appleby, John A.; Martin, Charles R.

    1992-01-01

    The objectives of this study were to use electrochemical impedance spectroscopy (EIS) to study the oxygen-reduction reaction under lower humidification conditions than previously studied. The EIS technique permits the discrimination of electrode kinetics of oxygen reduction, mass transport of O2 in the membrane, and the electrical characteristics of the membrane. Electrode-kinetic parameters for the oxygen-reduction reaction, corrosion current densities for Pt, and double-layer capacitances were calculated. The production of water due to electrochemical reduction of oxygen greatly influenced the EIS response and the electrode kinetics at the Pt/Nafion interface. From the finite-length Warburg behavior, a measure of the diffusion coefficient of oxygen in Nafion and diffusion-layer thickness was obtained. An analysis of the EIS data in the high-frequency domain yielded membrane and interfacial characteristics such as ionic conductivity of the membrane, membrane grain-boundary capacitance and resistance, and uncompensated resistance.

  5. Preparation of steam activated carbon from rubberwood sawdust (Hevea brasiliensis) and its adsorption kinetics.

    PubMed

    Prakash Kumar, B G; Shivakamy, K; Miranda, Lima Rose; Velan, M

    2006-08-25

    Activated carbon was produced from a biowaste product, rubberwood sawdust (RWSD) using steam in a high temperature fluidized bed reactor. Experiments were carried out to investigate the influence of various process parameters such as activation time, activation temperature, particle size and fluidising velocity on the quality of the activated carbon. The activated carbon was characterized based on its iodine number, methylene blue number, Brauner Emmet Teller (BET) surface area and surface area obtained using the ethylene glycol mono ethyl ether (EGME) retention method. The best quality activated carbon was obtained at an activation time and temperature of 1h and 750 degrees C for an average particle size of 0.46 mm. The adsorption kinetics shows that pseudo-second-order rate fitted the adsorption kinetics better than pseudo-first-order rate equation. The adsorption capacity of carbon produced from RWSD was found to be 1250 mg g(-1) for the Bismark Brown dye. The rate constant and diffusion coefficient for intraparticle transport were determined for steam activated carbon. The characteristic of the prepared activated carbon was found comparable to the commercial activated carbon.

  6. Kinetic rate laws as derived from order parameter theory I: Theoretical concepts

    NASA Astrophysics Data System (ADS)

    Salje, Ekhard

    1988-03-01

    A theoretical concept is outlined, which links the kinetics of structural transformations with thermodynamic theories of structural phase transitions. Starting from Landau theory and Markovian processes, the general rate laws for crystals with long correlation lengths are derived. The rate laws in Ginzburg-Landau theory are 269_2004_Article_BF00311038_TeX2GIFE1.gif 1{text{n }}Δ Q - 1{text{n }}fleft( Q right) ∝ - t/tau {text{ for }}T ≪ T_c {text{ and }}T ≫ T_c and Q 2∝ for T ≈ T c . The physical meaning of the time constant τ and the correction term f( Q) are explained. Fluctuations of the order parameter lead to damping behaviour with explicit dependence on the wavelength of the fluctuation wave and modulation-dependent variations of the lattice strain. Lattice relaxations and activation processes are discussed. Typical rate laws are found to follow 269_2004_Article_BF00311038_TeX2GIFE2.gif begin{gathered} ln Δ Q = rlnΔ t, \\ lnQ/Q + {1\\varepsilon }/{2k_B T}left( {Q^2 - Q_0^2 } right) = {Δ t}/{tau *} \\ which leads for short time intervals to a linear rate law 269_2004_Article_BF00311038_TeX2GIFE3.gif Δ Q ∝ Δ t It is shown that linear terms in the Landau potential are equivalent to a logarithmic decay of the excess entropy Δ S ∝ ln Δ t which is also expected to be the dominant rate law in field-induced pseudo-spin glasses: 269_2004_Article_BF00311038_TeX2GIFE4.gif Δ Q ∝ 1{text{n }}Δ t{text{ and }}1{text{n}}left( {Δ {text{Q}} \\cdot Δ {text{t}}} right) = A{text{ }}Δ t + B Fluctuations lead to spatially heterogeneous distributions of the order parameter. A two phase field is found in this case where the nucleation energy is overcome by fluctuation processes. Random fields, arising, for example, from lattice imperfections, lead also to spacially inhomogeneous material. The dominant microstructure is the lattice modulation mostly in the form of a cross hatched pattern (tweed) but also in the form of incommensurate modulations.

  7. A kinetic study of hypoxanthine oxidation by milk xanthine oxidase.

    PubMed Central

    Escribano, J; Garcia-Canovas, F; Garcia-Carmona, F

    1988-01-01

    The course of the reaction sequence hypoxanthine----xanthine----uric acid catalysed by xanthine:oxygen oxidoreductase from milk was investigated on the basis of u.v. spectra taken during the course of hypoxanthine and xanthine oxidations. It was found that xanthine accumulated in the reaction mixture when hypoxanthine was used as a substrate. The time course of the concentrations of hypoxanthine, xanthine intermediate and uric acid product was simulated numerically. The mathematical model takes into account the competition of substrate, intermediate and product and the accumulation of the intermediate at the enzyme. This type of analysis permits the kinetic parameters of the enzyme for hypoxanthine and xanthine to be obtained. PMID:3196295

  8. A study of the kinetics of isothermal nicotine desorption from silicon dioxide

    NASA Astrophysics Data System (ADS)

    Adnadjevic, Borivoj; Lazarevic, Natasa; Jovanovic, Jelena

    2010-12-01

    The isothermal kinetics of nicotine desorption from silicon dioxide (SiO 2) was investigated. The isothermal thermogravimetric curves of nicotine at temperatures of 115 °C, 130 °C and 152 °C were recorded. The kinetic parameters ( Ea, ln A) of desorption of nicotine were calculated using various methods (stationary point, model constants and differential isoconversion method). By applying the "model-fitting" method, it was found that the kinetic model of nicotine desorption from silicon dioxide was a phase boundary controlled reaction (contracting volume). The values of the kinetic parameters, Ea,α and ln Aα, complexly change with changing degree of desorption and a compensation effect exists. A new mechanism of activation for the desorption of the absorbed molecules of nicotine was suggested in agreement with model of selective energy transfer.

  9. Comparison of dynamic contrast-enhanced MRI parameters of breast lesions at 1.5 and 3.0 T: a pilot study

    PubMed Central

    Pineda, F D; Medved, M; Fan, X; Ivancevic, M K; Abe, H; Shimauchi, A; Newstead, G M

    2015-01-01

    Objective: To compare dynamic contrast-enhanced (DCE) MRI parameters from scans of breast lesions at 1.5 and 3.0 T. Methods: 11 patients underwent paired MRI examinations in both Philips 1.5 and 3.0 T systems (Best, Netherlands) using a standard clinical fat-suppressed, T1 weighted DCE-MRI protocol, with 70–76 s temporal resolution. Signal intensity vs time curves were fit with an empirical mathematical model to obtain semi-quantitative measures of uptake and washout rates as well as time-to-peak enhancement (TTP). Maximum percent enhancement and signal enhancement ratio (SER) were also measured for each lesion. Percent differences between parameters measured at the two field strengths were compared. Results: TTP and SER parameters measured at 1.5 and 3.0 T were similar; with mean absolute differences of 19% and 22%, respectively. Maximum percent signal enhancement was significantly higher at 3 T than at 1.5 T (p = 0.006). Qualitative assessment showed that image quality was significantly higher at 3 T (p = 0.005). Conclusion: Our results suggest that TTP and SER are more robust to field strength change than other measured kinetic parameters, and therefore measurements of these parameters can be more easily standardized than measurements of other parameters derived from DCE-MRI. Semi-quantitative measures of overall kinetic curve shape showed higher reproducibility than do discrete classification of kinetic curve early and delayed phases in a majority of the cases studied. Advances in knowledge: Qualitative measures of curve shape are not consistent across field strength even when acquisition parameters are standardized. Quantitative measures of overall kinetic curve shape, by contrast, have higher reproducibility. PMID:25785918

  10. Optimization and adsorption kinetic studies of aqueous manganese ion removal using chitin extracted from shells of edible Philippine crabs

    NASA Astrophysics Data System (ADS)

    Quimque, Mark Tristan J.; Jimenez, Marvin C.; Acas, Meg Ina S.; Indoc, Danrelle Keth L.; Gomez, Enjelyn C.; Tabuñag, Jenny Syl D.

    2017-01-01

    Manganese is a common contaminant in drinking water along with other metal pollutants. This paper investigates the use of chitin, extracted from crab shells obtained as restaurant throwaway, as an adsorbent in removing manganese ions from aqueous medium. In particular, this aims to optimize the adsorption parameters and look into the kinetics of the process. The adsorption experiments done in this study employed the batch equilibration method. In the optimization, the following parameters were considered: pH and concentration of Mn (II) sorbate solution, particle size and dosage of adsorbent chitin, and adsorbent-adsorbate contact time. At the optimal condition, the order of the adsorption reaction was estimated using kinetic models which describes the process best. It was found out that the adsorption of aqueous Mn (II) ions onto chitin obeys the pseudo-second order model. This model assumes that the adsorption occurred via chemisorption

  11. Estimation of Free Radical Ionization Energies by the Kinetic Method and the Relationship between the Kinetic Method and the Hammett Equation.

    PubMed

    Chen, G; Wong, P; Cooks, R G

    1997-09-01

    Substituted 1,2-diphenylethanes undergo competitive dissociations upon electron ionization (EI) to generate substituted benzyl cation and benzyl radical pairs. Application of the kinetic method to the previous reported EI mass spectra of these covalently bound precursor ions (data are taken from McLafferty et al. J. Am. Chem. Soc. 1970, 92, 6867)) is used to estimate the ionization energies of substituted benzyl free radicals. A correlation is observed between the Hammett σ constant of the substituents and the kinetic method parameter, ln(k(x)/k(H)), where k(x) is the rate of fragmentation to give the substituted product ion and k(H) is the rate to give the benzyl ion itself. Systems involving weakly bound cluster ions, including proton-bound dimers of meta- and para-substituted pyridines and meta- and para-substituted anilines, and electron-bound dimers of meta- and para-substituted nitrobenzenes, also show good correlations between the kinetic method parameter and the Hammett σ constant.

  12. Kinetic synergistic transitions in the Ostwald ripening processes

    NASA Astrophysics Data System (ADS)

    Sachkov, I. N.; Turygina, V. F.; Dolganov, A. N.

    2018-01-01

    There is proposed approach to mathematical description of the kinetic transitions in Ostwald ripening processes of volatile substance in nonuniformly heated porous materials. It is based upon the finite element method. There are implemented computer software. The main feature of the software is to calculate evaporation and condensation fluxes on the walls of a nonuniformly heated cylindrical capillary. Kinetic transitions are detected for three modes of volatile substances migration which are different by condensation zones location. There are controlling dimensionless parameters of the kinetic transition which are revealed during research. There is phase diagram of the Ostwald ripening process modes realization.

  13. Optimization of a direct spectrophotometric method to investigate the kinetics and inhibition of sialidases

    PubMed Central

    2012-01-01

    Backgrounds Streptococcus pneumoniae expresses three distinct sialidases, NanA, NanB, and NanC, that are believed to be key virulence factors and thus, potential important drug targets. We previously reported that the three enzymes release different products from sialosides, but could share a common catalytic mechanism before the final step of product formation. However, the kinetic investigations of the three sialidases have not been systematically done thus far, due to the lack of an easy and steady measurement of sialidase reaction rate. Results In this work, we present further kinetic characterization of pneumococcal sialidases by using a direct spectrophotometric method with the chromogenic substrate p-nitrophenyl-N-acetylneuraminic acid (p-NP-Neu5Ac). Using our assay, the measured kinetic parameters of the three purified pneumococcal sialidase, NanA, NanB and NanC, were obtained and were in perfect agreement with the previously published data. The major advantage of this alternative method resides in the direct measurement of the released product, allowing to readily determine of initial reaction rates and record complete hydrolysis time courses. Conclusion We developed an accurate, fast and sensitive spectrophotometric method to investigate the kinetics of sialidase-catalyzed reactions. This fast, sensitive, inexpensive and accurate method could benefit the study of the kinetics and inhibition of sialidases in general. PMID:23031230

  14. Kinetics of Mixed Microbial Assemblages Enhance Removal of Highly Dilute Organic Substrates

    PubMed Central

    Lewis, David L.; Hodson, Robert E.; Hwang, Huey-Min

    1988-01-01

    Our experiments with selected organic substrates reveal that the rate-limiting process governing microbial degradation rates changes with substrate concentration, S, in such a manner that substrate removal is enhanced at lower values of S. This enhancement is the result of the dominance of very efficient systems for substrate removal at low substrate concentrations. The variability of dominant kinetic parameters over a range of S causes the kinetics of complex assemblages to be profoundly dissimilar to those of systems possessing a single set of kinetic parameters; these findings necessitate taking a new approach to predicting substrate removal rates over wide ranges of S. PMID:16347715

  15. Analysis of blind identification methods for estimation of kinetic parameters in dynamic medical imaging

    NASA Astrophysics Data System (ADS)

    Riabkov, Dmitri

    Compartment modeling of dynamic medical image data implies that the concentration of the tracer over time in a particular region of the organ of interest is well-modeled as a convolution of the tissue response with the tracer concentration in the blood stream. The tissue response is different for different tissues while the blood input is assumed to be the same for different tissues. The kinetic parameters characterizing the tissue responses can be estimated by blind identification methods. These algorithms use the simultaneous measurements of concentration in separate regions of the organ; if the regions have different responses, the measurement of the blood input function may not be required. In this work it is shown that the blind identification problem has a unique solution for two-compartment model tissue response. For two-compartment model tissue responses in dynamic cardiac MRI imaging conditions with gadolinium-DTPA contrast agent, three blind identification algorithms are analyzed here to assess their utility: Eigenvector-based Algorithm for Multichannel Blind Deconvolution (EVAM), Cross Relations (CR), and Iterative Quadratic Maximum Likelihood (IQML). Comparisons of accuracy with conventional (not blind) identification techniques where the blood input is known are made as well. The statistical accuracies of estimation for the three methods are evaluated and compared for multiple parameter sets. The results show that the IQML method gives more accurate estimates than the other two blind identification methods. A proof is presented here that three-compartment model blind identification is not unique in the case of only two regions. It is shown that it is likely unique for the case of more than two regions, but this has not been proved analytically. For the three-compartment model the tissue responses in dynamic FDG PET imaging conditions are analyzed with the blind identification algorithms EVAM and Separable variables Least Squares (SLS). A method of

  16. Kinetic parameters of cholinesterase interactions with organophosphates: retrieval and comparison tools available through ESTHER database: ESTerases, alpha/beta Hydrolase Enzymes and Relatives.

    PubMed

    Chatonnet, A; Hotelier, T; Cousin, X

    1999-05-14

    Cholinesterases are targets for organophosphorus compounds which are used as insecticides, chemical warfare agents and drugs for the treatment of disease such as glaucoma, or parasitic infections. The widespread use of these chemicals explains the growing of this area of research and the ever increasing number of sequences, structures, or biochemical data available. Future advances will depend upon effective management of existing information as well as upon creation of new knowledge. The ESTHER database goal is to facilitate retrieval and comparison of data about structure and function of proteins presenting the alpha/beta hydrolase fold. Protein engineering and in vitro production of enzymes allow direct comparison of biochemical parameters. Kinetic parameters of enzymatic reactions are now included in the database. These parameters can be searched and compared with a table construction tool. ESTHER can be reached through internet (http://www.ensam.inra.fr/cholinesterase). The full database or the specialised X-window Client-server system can be downloaded from our ftp server (ftp://ftp.toulouse.inra.fr./pub/esther). Forms can be used to send updates or corrections directly from the web.

  17. Thermal decomposition and kinetic evaluation of decanted 2,4,6-trinitrotoluene (TNT) for reutilization as composite material

    NASA Astrophysics Data System (ADS)

    Ahmed, M. F.; Hussain, A.; Malik, A. Q.

    2016-08-01

    Use of energetic materials has long been considered for only military purposes. However, it is very recent that their practical applications in wide range of commercial fields such as mining, road building, under water blasting and rocket propulsion system have been considered. About 5mg of 2,4,6-trinitrotoluene (TNT) in serviceable (Svc) as well as unserviceable (Unsvc) form were used for their thermal decomposition and kinetic parameters investigation. Thermogravimetric/ differential thermal analysis (TG/DTA), X-ray diffraction (XRD) and Scanning electron microscope (SEM) were used to characterize two types of TNT. Arrhenius kinetic parameters like activation energy (E) and enthalpy (AH) of both TNT samples were determined using TG curves with the help of Horowitz and Metzger method. Simultaneously, thermal decomposition range was evaluated from DTA curves. Distinct diffraction peaks showing crystalline nature were obtained from XRD analysis. SEM results indicated that Unsvc TNT contained a variety of defects like cracks and porosity. Similarly, it is observed that thermal as well as kinetic behavior of both TNT samples vary to a great extent. Likewise, a prominent change in the activation energies (E) of both samples is observed. This in-depth study provides a way forward in finding solutions for the safe reutilization of decanted TNT.

  18. An automatic scaling method for obtaining the trace and parameters from oblique ionogram based on hybrid genetic algorithm

    NASA Astrophysics Data System (ADS)

    Song, Huan; Hu, Yaogai; Jiang, Chunhua; Zhou, Chen; Zhao, Zhengyu; Zou, Xianjian

    2016-12-01

    Scaling oblique ionogram plays an important role in obtaining ionospheric structure at the midpoint of oblique sounding path. The paper proposed an automatic scaling method to extract the trace and parameters of oblique ionogram based on hybrid genetic algorithm (HGA). The extracted 10 parameters come from F2 layer and Es layer, such as maximum observation frequency, critical frequency, and virtual height. The method adopts quasi-parabolic (QP) model to describe F2 layer's electron density profile that is used to synthesize trace. And it utilizes secant theorem, Martyn's equivalent path theorem, image processing technology, and echoes' characteristics to determine seven parameters' best fit values, and three parameter's initial values in QP model to set up their searching spaces which are the needed input data of HGA. Then HGA searches the three parameters' best fit values from their searching spaces based on the fitness between the synthesized trace and the real trace. In order to verify the performance of the method, 240 oblique ionograms are scaled and their results are compared with manual scaling results and the inversion results of the corresponding vertical ionograms. The comparison results show that the scaling results are accurate or at least adequate 60-90% of the time.

  19. Probabilistic approach to lysozyme crystal nucleation kinetics.

    PubMed

    Dimitrov, Ivaylo L; Hodzhaoglu, Feyzim V; Koleva, Dobryana P

    2015-09-01

    Nucleation of lysozyme crystals in quiescent solutions at a regime of progressive nucleation is investigated under an optical microscope at conditions of constant supersaturation. A method based on the stochastic nature of crystal nucleation and using discrete time sampling of small solution volumes for the presence or absence of detectable crystals is developed. It allows probabilities for crystal detection to be experimentally estimated. One hundred single samplings were used for each probability determination for 18 time intervals and six lysozyme concentrations. Fitting of a particular probability function to experimentally obtained data made possible the direct evaluation of stationary rates for lysozyme crystal nucleation, the time for growth of supernuclei to a detectable size and probability distribution of nucleation times. Obtained stationary nucleation rates were then used for the calculation of other nucleation parameters, such as the kinetic nucleation factor, nucleus size, work for nucleus formation and effective specific surface energy of the nucleus. The experimental method itself is simple and adaptable and can be used for crystal nucleation studies of arbitrary soluble substances with known solubility at particular solution conditions.

  20. Water-Exchange-Modified Kinetic Parameters from Dynamic Contrast-Enhanced MRI as Prognostic Biomarkers of Survival in Advanced Hepatocellular Carcinoma Treated with Antiangiogenic Monotherapy

    PubMed Central

    Lee, Sang Ho; Hayano, Koichi; Zhu, Andrew X.; Sahani, Dushyant V.; Yoshida, Hiroyuki

    2015-01-01

    Background To find prognostic biomarkers in pretreatment dynamic contrast-enhanced MRI (DCE-MRI) water-exchange-modified (WX) kinetic parameters for advanced hepatocellular carcinoma (HCC) treated with antiangiogenic monotherapy. Methods Twenty patients with advanced HCC underwent DCE-MRI and were subsequently treated with sunitinib. Pretreatment DCE-MRI data on advanced HCC were analyzed using five different WX kinetic models: the Tofts-Kety (WX-TK), extended TK (WX-ETK), two compartment exchange, adiabatic approximation to tissue homogeneity (WX-AATH), and distributed parameter (WX-DP) models. The total hepatic blood flow, arterial flow fraction (γ), arterial blood flow (BF A), portal blood flow, blood volume, mean transit time, permeability-surface area product, fractional interstitial volume (v I), extraction fraction, mean intracellular water molecule lifetime (τ C), and fractional intracellular volume (v C) were calculated. After receiver operating characteristic analysis with leave-one-out cross-validation, individual parameters for each model were assessed in terms of 1-year-survival (1YS) discrimination using Kaplan-Meier analysis, and association with overall survival (OS) using univariate Cox regression analysis with permutation testing. Results The WX-TK-model-derived γ (P = 0.022) and v I (P = 0.010), and WX-ETK-model-derived τ C (P = 0.023) and v C (P = 0.042) were statistically significant prognostic biomarkers for 1YS. Increase in the WX-DP-model-derived BF A (P = 0.025) and decrease in the WX-TK, WX-ETK, WX-AATH, and WX-DP-model-derived v C (P = 0.034, P = 0.038, P = 0.028, P = 0.041, respectively) were significantly associated with an increase in OS. Conclusions The WX-ETK-model-derived v C was an effective prognostic biomarker for advanced HCC treated with sunitinib. PMID:26366997

  1. Kinetics of acid base catalyzed transesterification of Jatropha curcas oil.

    PubMed

    Jain, Siddharth; Sharma, M P

    2010-10-01

    Out of various non-edible oil resources, Jatropha curcas oil (JCO) is considered as future feedstock for biodiesel production in India. Limited work is reported on the kinetics of transesterification of high free fatty acids containing oil. The present study reports the results of kinetic study of two-step acid base catalyzed transesterification process carried out at an optimum temperature of 65 °C and 50 °C for esterification and transesterification respectively under the optimum methanol to oil ratio of 3:7 (v/v), catalyst concentration 1% (w/w) for H₂SO₄ and NaOH. The yield of methyl ester (ME) has been used to study the effect of different parameters. The results indicate that both esterification and transesterification reaction are of first order with reaction rate constant of 0.0031 min⁻¹ and 0.008 min⁻¹ respectively. The maximum yield of 21.2% of ME during esterification and 90.1% from transesterification of pretreated JCO has been obtained. Copyright © 2010 Elsevier Ltd. All rights reserved.

  2. A waste characterisation procedure for ADM1 implementation based on degradation kinetics.

    PubMed

    Girault, R; Bridoux, G; Nauleau, F; Poullain, C; Buffet, J; Steyer, J-P; Sadowski, A G; Béline, F

    2012-09-01

    In this study, a procedure accounting for degradation kinetics was developed to split the total COD of a substrate into each input state variable required for Anaerobic Digestion Model n°1. The procedure is based on the combination of batch experimental degradation tests ("anaerobic respirometry") and numerical interpretation of the results obtained (optimisation of the ADM1 input state variable set). The effects of the main operating parameters, such as the substrate to inoculum ratio in batch experiments and the origin of the inoculum, were investigated. Combined with biochemical fractionation of the total COD of substrates, this method enabled determination of an ADM1-consistent input state variable set for each substrate with affordable identifiability. The substrate to inoculum ratio in the batch experiments and the origin of the inoculum influenced input state variables. However, based on results modelled for a CSTR fed with the substrate concerned, these effects were not significant. Indeed, if the optimal ranges of these operational parameters are respected, uncertainty in COD fractionation is mainly limited to temporal variability of the properties of the substrates. As the method is based on kinetics and is easy to implement for a wide range of substrates, it is a very promising way to numerically predict the effect of design parameters on the efficiency of an anaerobic CSTR. This method thus promotes the use of modelling for the design and optimisation of anaerobic processes. Copyright © 2012 Elsevier Ltd. All rights reserved.

  3. Thermogravimetric kinetic study of agricultural residue biomass pyrolysis based on combined kinetics.

    PubMed

    Wang, Xun; Hu, Mian; Hu, Wanyong; Chen, Zhihua; Liu, Shiming; Hu, Zhiquan; Xiao, Bo

    2016-11-01

    Pyrolytic kinetic of an agricultural residue (AR) feedstock, a mixture of plants (cotton, wheat, rich, corn) stems, was investigated based on combined kinetics. The most suitable mechanism for AR one-step pyrolysis was f(α)=(1-α)(1.1816)α(-1.8428) with kinetic parameters of: apparent activation energy 221.7kJ/mol, pre-exponential factor 4.17E16s(-1). Pyrolysis of AR feedstock could not be described by one-step reaction attributes to heterogeneous features of pyrolysis processes. Combined kinetics three-parallel-reaction (CK-TPR) model fitted the pyrolysis experimental data very well. Reaction mechanisms for pseudo hemicelluloses, cellulose, lignin in CK-TPR model was f(α)=(1-α)(1.6244)α(-0.3371)[-ln(1-α)](-0.0515), f(α)=(1-α)(1.0597)α(-0.6909)[-ln(1-α)](0.9026) and f(α)=(1-α)(2.9577)α(-4.7719), respectively. Apparent activation energy of three pseudo components followed the order of Elignin(197.3kJ/mol)>Ecellulose(176.3kJ/mol)>Ehemicelluloses (151.1kJ/mol). Mechanism of hemicelluloses pyrolysis could be further expressed as f(α)=(1-α)(1.4). The pyrolytic mechanism of cellulose met the Nucleation well. However, mechanism of lignin pyrolysis was complex, which possibly was the combined effects of Nucleation, Diffusion, Geometrical contraction, and Power law. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Active matter beyond mean-field: ring-kinetic theory for self-propelled particles.

    PubMed

    Chou, Yen-Liang; Ihle, Thomas

    2015-02-01

    Recently, Hanke et al. [Phys. Rev. E 88, 052309 (2013)] showed that mean-field kinetic theory fails to describe collective motion in soft active colloids and that correlations must not be neglected. Correlation effects are also expected to be essential in systems of biofilaments driven by molecular motors and in swarms of midges. To obtain correlations in an active matter system from first principles, we derive a ring-kinetic theory for Vicsek-style models of self-propelled agents from the exact N-particle evolution equation in phase space. The theory goes beyond mean-field and does not rely on Boltzmann's approximation of molecular chaos. It can handle precollisional correlations and cluster formation, which are both important to understand the phase transition to collective motion. We propose a diagrammatic technique to perform a small-density expansion of the collision operator and derive the first two equations of the Bogoliubov-Born-Green-Kirkwood-Yvon (BBGKY) hierarchy. An algorithm is presented that numerically solves the evolution equation for the two-particle correlations on a lattice. Agent-based simulations are performed and informative quantities such as orientational and density correlation functions are compared with those obtained by ring-kinetic theory. Excellent quantitative agreement between simulations and theory is found at not-too-small noises and mean free paths. This shows that there are parameter ranges in Vicsek-like models where the correlated closure of the BBGKY hierarchy gives correct and nontrivial results. We calculate the dependence of the orientational correlations on distance in the disordered phase and find that it seems to be consistent with a power law with an exponent around -1.8, followed by an exponential decay. General limitations of the kinetic theory and its numerical solution are discussed.

  5. A possible mechanism of metabolic regulation in Gibberella fujikuroi using a mixed carbon source of glucose and corn oil inferred from analysis of the kinetics data obtained in a stirrer tank bioreactor.

    PubMed

    Rios-Iribe, Erika Y; Hernández-Calderón, Oscar M; Reyes-Moreno, C; Contreras-Andrade, I; Flores-Cotera, Luis B; Escamilla-Silva, Eleazar M

    2013-01-01

    A nonstructured model was used to study the dynamics of gibberellic acid production in a stirred tank bioreactor. Experimental data were obtained from submerged batch cultures of Gibberella fujikuroi (CDBB H-984) grown in varying ratios of glucose-corn oil as the carbon source. The nitrogen depletion effect was included in mathematical model by considering the specific kinetic constants as a linear function of the normalized nitrogen consumption rate. The kinetics of biomass growth and consumption of phosphate and nitrogen were based on the logistic model. The traditional first-order kinetic model was used to describe the specific consumption of glucose and corn oil. The nitrogen effect was solely included in the phosphate and corn oil consumption and biomass growth. The model fit was satisfactory, revealing the dependence of the kinetics with respect to the nitrogen assimilation rate. Through simulations, it was possible to make diagrams of specific growth rate and specific rate of substrate consumptions, which was a powerful tool for understanding the metabolic interactions that occurred during the various stages of fermentation process. This kinetic analysis provided the proposal of a possible mechanism of regulation on growth, substrate consumptions, and production of gibberellic acid (GA3 ) in G. fujikuroi. © 2013 American Institute of Chemical Engineers.

  6. Parameter Estimates in Differential Equation Models for Chemical Kinetics

    ERIC Educational Resources Information Center

    Winkel, Brian

    2011-01-01

    We discuss the need for devoting time in differential equations courses to modelling and the completion of the modelling process with efforts to estimate the parameters in the models using data. We estimate the parameters present in several differential equation models of chemical reactions of order n, where n = 0, 1, 2, and apply more general…

  7. Direct recovery of regional tracer kinetics from temporally inconsistent dynamic ECT projections using dimension-reduced time-activity basis

    NASA Astrophysics Data System (ADS)

    Maltz, Jonathan S.

    2000-11-01

    We present an algorithm of reduced computational cost which is able to estimate kinetic model parameters directly from dynamic ECT sinograms made up of temporally inconsistent projections. The algorithm exploits the extreme degree of parameter redundancy inherent in linear combinations of the exponential functions which represent the modes of first-order compartmental systems. The singular value decomposition is employed to find a small set of orthogonal functions, the linear combinations of which are able to accurately represent all modes within the physiologically anticipated range in a given study. The reduced-dimension basis is formed as the convolution of this orthogonal set with a measured input function. The Moore-Penrose pseudoinverse is used to find coefficients of this basis. Algorithm performance is evaluated at realistic count rates using MCAT phantom and clinical 99mTc-teboroxime myocardial study data. Phantom data are modelled as originating from a Poisson process. For estimates recovered from a single slice projection set containing 2.5×105 total counts, recovered tissue responses compare favourably with those obtained using more computationally intensive methods. The corresponding kinetic parameter estimates (coefficients of the new basis) exhibit negligible bias, while parameter variances are low, falling within 30% of the Cramér-Rao lower bound.

  8. Kinetics of arsenite removal by halobacteria from a highland Andean Chilean Salar

    PubMed Central

    2013-01-01

    Background The purpose of this study was to identify arsenite-oxidizing halobacteria in samples obtained from Salar de Punta Negra, II Region of Chile. Seven bacterial isolates, numbered as isolates I to VII, grown in a culture medium with 100 ppm as NaAsO2 (As (III)) were tested. Bacterial growth kinetics and the percent of arsenite removal (PAR) were performed simultaneously with the detection of an arsenite oxidase enzyme through Dot Blot analysis. Results An arsenite oxidase enzyme was detected in all isolates, expressed constitutively after 10 generations grown in the absence of As (III). Bacterial growth kinetics and corresponding PAR values showed significant fluctuations over time. PARs close to 100% were shown by isolates V, VI, and VII, at different times of the bacterial growth phase; while isolate II showed PAR values around 40%, remaining constant over time. Conclusion Halobacteria from Salar de Punta Negra showed promising properties as arsenite removers under control conditions, incubation time being a critical parameter. PMID:23547876

  9. Comparative thermogravimetric analyses of co-combustion of textile dyeing sludge and sugarcane bagasse in carbon dioxide/oxygen and nitrogen/oxygen atmospheres: Thermal conversion characteristics, kinetics, and thermodynamics.

    PubMed

    Xie, Wenhao; Wen, Shaoting; Liu, Jingyong; Xie, Wuming; Kuo, Jiahong; Lu, Xingwen; Sun, Shuiyu; Chang, Kenlin; Buyukada, Musa; Evrendilek, Fatih

    2018-05-01

    Thermodynamic and kinetic parameters of co-combustion of textile dyeing sludge (TDS) and sugarcane bagasse (SB) were studied using thermogravimetric analysis in CO 2 /O 2 and N 2 /O 2 atmospheres. Our results showed that the comprehensive combustion characteristic index (CCI) of the blends was improved by 1.71-4.32 times. With the increased O 2 concentration, co-combustion peak temperature decreased from 329.7 to 318.2 °C, with an increase in its maximum weight loss rate from 10.04 to 14.99%/min and its CCI by 1.31 times (β = 20 °C·min -1 ). To evaluate the co-combustion characteristics, thermodynamic and kinetic parameters (entropy, Gibbs free energy and enthalpy changes, and apparent activation energy) were obtained in the five atmospheres. The lowest apparent activation energy of the TB64 blend was obtained in oxy-fuel atmosphere (CO 2 /O 2  = 7/3). Copyright © 2018 Elsevier Ltd. All rights reserved.

  10. Modeling the growth kinetics of Bacillus cereus as a function of temperature, pH, sodium lactate and sodium chloride concentrations.

    PubMed

    Olmez, Hülya Kaptan; Aran, Necla

    2005-02-01

    Mathematical models describing the growth kinetic parameters (lag phase duration and growth rate) of Bacillus cereus as a function of temperature, pH, sodium lactate and sodium chloride concentrations were obtained in this study. In order to get a residual distribution closer to a normal distribution, the natural logarithm of the growth kinetic parameters were used in modeling. For reasons of parsimony, the polynomial models were reduced to contain only the coefficients significant at a level of pparameters. Predicted data were compared with the predictions from Pathogen Modeling Program (PMP-US Department of Agriculture-Agricultural Research Service) and validated against data extracted from the literature. The mean absolute relative error (MARE) and the median relative error (MRE) of the predicted generation times with the derived model were 25.6% and -16.7%, respectively, showing that the growth rate model accurately and safely predicted the growth kinetics of B. cereus. Results of the modeling study indicated that all of the studied factors had a significant effect on the growth of B. cereus in the experimental range studied.

  11. VO2 Off Transient Kinetics in Extreme Intensity Swimming.

    PubMed

    Sousa, Ana; Figueiredo, Pedro; Keskinen, Kari L; Rodríguez, Ferran A; Machado, Leandro; Vilas-Boas, João P; Fernandes, Ricardo J

    2011-01-01

    Inconsistencies about dynamic asymmetry between the on- and off- transient responses in oxygen uptake are found in the literature. Therefore, the purpose of this study was to characterize the oxygen uptake off-transient kinetics during a maximal 200-m front crawl effort, as examining the degree to which the on/off regularity of the oxygen uptake kinetics response was preserved. Eight high level male swimmers performed a 200-m front crawl at maximal speed during which oxygen uptake was directly measured through breath-by-breath oxymetry (averaged every 5 s). This apparatus was connected to the swimmer by a low hydrodynamic resistance respiratory snorkel and valve system. The on- and off-transient phases were symmetrical in shape (mirror image) once they were adequately fitted by a single-exponential regression models, and no slow component for the oxygen uptake response was developed. Mean (± SD) peak oxygen uptake was 69.0 (± 6.3) mL·kg(-1)·min(-1), significantly correlated with time constant of the off- transient period (r = 0.76, p < 0.05) but not with any of the other oxygen off-transient kinetic parameters studied. A direct relationship between time constant of the off-transient period and mean swimming speed of the 200-m (r = 0.77, p < 0.05), and with the amplitude of the fast component of the effort period (r = 0.72, p < 0.05) were observed. The mean amplitude and time constant of the off-transient period values were significantly greater than the respective on- transient. In conclusion, although an asymmetry between the on- and off kinetic parameters was verified, both the 200-m effort and the respectively recovery period were better characterized by a single exponential regression model. Key pointsThe VO2 slow component was not observed in the recovery period of swimming extreme efforts;The on and off transient periods were better fitted by a single exponential function, and so, these effort and recovery periods of swimming extreme efforts are

  12. Monochloramine Disinfection Kinetics of Nitrosomonas europaea by Propidium Monoazide Quantitative PCR and Live/Dead BacLight Methods▿

    PubMed Central

    Wahman, David G.; Wulfeck-Kleier, Karen A.; Pressman, Jonathan G.

    2009-01-01

    Monochloramine disinfection kinetics were determined for the pure-culture ammonia-oxidizing bacterium Nitrosomonas europaea (ATCC 19718) by two culture-independent methods, namely, Live/Dead BacLight (LD) and propidium monoazide quantitative PCR (PMA-qPCR). Both methods were first verified with mixtures of heat-killed (nonviable) and non-heat-killed (viable) cells before a series of batch disinfection experiments with stationary-phase cultures (batch grown for 7 days) at pH 8.0, 25°C, and 5, 10, and 20 mg Cl2/liter monochloramine. Two data sets were generated based on the viability method used, either (i) LD or (ii) PMA-qPCR. These two data sets were used to estimate kinetic parameters for the delayed Chick-Watson disinfection model through a Bayesian analysis implemented in WinBUGS. This analysis provided parameter estimates of 490 mg Cl2-min/liter for the lag coefficient (b) and 1.6 × 10−3 to 4.0 × 10−3 liter/mg Cl2-min for the Chick-Watson disinfection rate constant (k). While estimates of b were similar for both data sets, the LD data set resulted in a greater k estimate than that obtained with the PMA-qPCR data set, implying that the PMA-qPCR viability measure was more conservative than LD. For N. europaea, the lag phase was not previously reported for culture-independent methods and may have implications for nitrification in drinking water distribution systems. This is the first published application of a PMA-qPCR method for disinfection kinetic model parameter estimation as well as its application to N. europaea or monochloramine. Ultimately, this PMA-qPCR method will allow evaluation of monochloramine disinfection kinetics for mixed-culture bacteria in drinking water distribution systems. PMID:19561179

  13. Port wine oxidation management: a multiparametric kinetic approach.

    PubMed

    Martins, Rui Costa; Monforte, Ana Rita; Silva Ferreira, António

    2013-06-05

    Port wine is a flagship fortified wine of Portugal, which undergoes a particularly long aging period, developing a dynamic sensory profile over time, responsible for several wine categories, which is dependent upon the type of aging (bottle or barrel). Therefore, the quality of the product is dependent upon the chemical mechanisms occurring during the aging process, such as oxidation or Maillard reactions. To attain the desired quality management, it is necessary to understand how technological parameters, such as temperature or oxygen exposure, affect the kinetics of the formation of key odorants, such as sotolon. There is a lack of information about the impact of the storage conditions (oxygen and temperature) on Port wine quality. In this study, the effect of these two parameters were investigated to increase the knowledge database concerning aging management of Port wines. It was found that sotolon formation is highly dependent upon oxygen and temperature. There is however a synergistic effect between these two parameters that could significantly increase the concentration. The kinetic parameters of oxygen, sotolon, and other compounds related to Port aging (cis- and trans-5-hydroxy-2-methyl-1,3-dioxan, 2-furfural, 5-hydroxy-methyl-furfural, and 5-methyl-furfural) are also reported. Kinetic models with Monte Carlo simulations, where the oxygen permeability dispersion and temperature are the parameters under evaluation, were applied. On the basis of the modeling predictions, it would seem that the temperature of a cellar would have a more significant impact on the Port wines stored in containers where the oxygen intake is higher (barrels) when compared to containers with low oxygen permeability (bottles using cork stoppers).

  14. Joint estimation of subject motion and tracer kinetic parameters of dynamic PET data in an EM framework

    NASA Astrophysics Data System (ADS)

    Jiao, Jieqing; Salinas, Cristian A.; Searle, Graham E.; Gunn, Roger N.; Schnabel, Julia A.

    2012-02-01

    Dynamic Positron Emission Tomography is a powerful tool for quantitative imaging of in vivo biological processes. The long scan durations necessitate motion correction, to maintain the validity of the dynamic measurements, which can be particularly challenging due to the low signal-to-noise ratio (SNR) and spatial resolution, as well as the complex tracer behaviour in the dynamic PET data. In this paper we develop a novel automated expectation-maximisation image registration framework that incorporates temporal tracer kinetic information to correct for inter-frame subject motion during dynamic PET scans. We employ the Zubal human brain phantom to simulate dynamic PET data using SORTEO (a Monte Carlo-based simulator), in order to validate the proposed method for its ability to recover imposed rigid motion. We have conducted a range of simulations using different noise levels, and corrupted the data with a range of rigid motion artefacts. The performance of our motion correction method is compared with pairwise registration using normalised mutual information as a voxel similarity measure (an approach conventionally used to correct for dynamic PET inter-frame motion based solely on intensity information). To quantify registration accuracy, we calculate the target registration error across the images. The results show that our new dynamic image registration method based on tracer kinetics yields better realignment of the simulated datasets, halving the target registration error when compared to the conventional method at small motion levels, as well as yielding smaller residuals in translation and rotation parameters. We also show that our new method is less affected by the low signal in the first few frames, which the conventional method based on normalised mutual information fails to realign.

  15. Kinetic evaluation study on the bioactivity of silver doped hydroxyapatite-polyvinyl alcohol nanocomposites.

    PubMed

    Mostafa, Amany A; Oudadesse, Hassane; El Sayed, Mayyada M H; Kamal, Gehan; Kamel, Mohamed; Foad, Enas

    2014-12-01

    This work investigates the effect of adding silver nanoparticles (NPs) in ppm on the bioactivity of hydroxyapatite/polyvinyl alcohol nanocomposites (HAV). HAV prepared by an in situ biomimetic approach was doped with different concentrations of silver NPs (HAV-Ag), and the formed powder samples were characterized by different techniques such as Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-EOS), X-ray diffraction, transmission electron microscope, and Fourier Transform Infrared Spectroscopy. Bioactivity was evaluated in simulated body fluid through studying the kinetics of Ca and P uptake onto the different HAV-Ag nanocomposites. Uptake profiles of Ca and P were well described by a pseudo-second order kinetic model, and the obtained kinetic parameters confirmed that the highest uptake capacities were achieved by adding less than 0.001 ppm of silver NPs which is an amount not detectable by ICP. Furthermore, HAV-Ag nanocomposites were shown to be non-toxic as well as have a strong antibacterial effect. Silver NPs significantly enhanced the bioactivity of HAV nanocomposites and thus the developed nanocomposites promise to be excellent biomaterials for bone and reconstructive surgery applications. © 2014 Wiley Periodicals, Inc.

  16. Revisiting the flocculation kinetics of destabilized asphaltenes.

    PubMed

    Vilas Bôas Fávero, Cláudio; Maqbool, Tabish; Hoepfner, Michael; Haji-Akbari, Nasim; Fogler, H Scott

    2017-06-01

    A comprehensive review of the recently published work on asphaltene destabilization and flocculation kinetics is presented. Four different experimental techniques were used to study asphaltenes undergoing flocculation process in crude oils and model oils. The asphaltenes were destabilized by different n-alkanes and a geometric population balance with the Smoluchowski collision kernel was used to model the asphaltene aggregation process. Additionally, by postulating a relation between the aggregation collision efficiency and the solubility parameter of asphaltenes and the solution, a unified model of asphaltene aggregation model was developed. When the aggregation model is applied to the experimental data obtained from several different crude oil and model oils, the detection time curves collapsed onto a universal single line, indicating that the model successfully captures the underlying physics of the observed process. Copyright © 2016 Elsevier B.V. All rights reserved.

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

    PubMed

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

    2011-10-18

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

  18. Comparative studies on adsorptive removal of heavy metal ions by biosorbent, bio-char and activated carbon obtained from low cost agro-residue.

    PubMed

    Kırbıyık, Çisem; Pütün, Ayşe Eren; Pütün, Ersan

    2016-01-01

    In this study, Fe(III) and Cr(III) metal ion adsorption processes were carried out with three adsorbents in batch experiments and their adsorption performance was compared. These adsorbents were sesame stalk without pretreatment, bio-char derived from thermal decomposition of biomass, and activated carbon which was obtained from chemical activation of biomass. Scanning electron microscopy and Fourier transform-infrared techniques were used for characterization of adsorbents. The optimum conditions for the adsorption process were obtained by observing the influences of solution pH, adsorbent dosage, initial solution concentration, contact time and temperature. The optimum adsorption efficiencies were determined at pH 2.8 and pH 4.0 for Fe(III) and Cr(III) metal ion solutions, respectively. The experimental data were modelled by different isotherm models and the equilibriums were well described by the Langmuir adsorption isotherm model. The pseudo-first-order, pseudo-second-order kinetic, intra-particle diffusion and Elovich models were applied to analyze the kinetic data and to evaluate rate constants. The pseudo-second-order kinetic model gave a better fit than the others. The thermodynamic parameters, such as Gibbs free energy change ΔG°, standard enthalpy change ΔH° and standard entropy change ΔS° were evaluated. The thermodynamic study showed the adsorption was a spontaneous endothermic process.

  19. Complete kinetic mechanism for recycling of the bacterial ribosome

    PubMed Central

    Borg, Anneli; Pavlov, Michael

    2016-01-01

    How EF-G and RRF act together to split a post-termination ribosomal complex into its subunits has remained obscure. Here, using stopped-flow experiments with Rayleigh light scattering detection and quench-flow experiments with radio-detection of GTP hydrolysis, we have clarified the kinetic mechanism of ribosome recycling and obtained precise estimates of its kinetic parameters. Ribosome splitting requires that EF-G binds to an already RRF-containing ribosome. EF-G binding to RRF-free ribosomes induces futile rounds of GTP hydrolysis and inhibits ribosome splitting, implying that while RRF is purely an activator of recycling, EF-G acts as both activator and competitive inhibitor of RRF in recycling of the post-termination ribosome. The ribosome splitting rate and the number of GTPs consumed per splitting event depend strongly on the free concentrations of EF-G and RRF. The maximal recycling rate, here estimated as 25 sec−1, is approached at very high concentrations of EF-G and RRF with RRF in high excess over EF-G. The present in vitro results, suggesting an in vivo ribosome recycling rate of ∼5 sec−1, are discussed in the perspective of rapidly growing bacterial cells. PMID:26527791

  20. A global resource allocation strategy governs growth transition kinetics of Escherichia coli

    PubMed Central

    Erickson, David W; Schink, Severin J.; Patsalo, Vadim; Williamson, James R.; Gerland, Ulrich; Hwa, Terence

    2018-01-01

    A grand challenge of systems biology is to predict the kinetic responses of living systems to perturbations starting from the underlying molecular interactions. Changes in the nutrient environment have long been used to study regulation and adaptation phenomena in microorganisms1–3 and they remain a topic of active investigation4–11. Although much is known about the molecular interactions that govern the regulation of key metabolic processes in response to applied perturbations12–17, they are insufficiently quantified for predictive bottom-up modelling. Here we develop a top-down approach, expanding the recently established coarse-grained proteome allocation models15,18–20 from steady-state growth into the kinetic regime. Using only qualitative knowledge of the underlying regulatory processes and imposing the condition of flux balance, we derive a quantitative model of bacterial growth transitions that is independent of inaccessible kinetic parameters. The resulting flux-controlled regulation model accurately predicts the time course of gene expression and biomass accumulation in response to carbon upshifts and downshifts (for example, diauxic shifts) without adjustable parameters. As predicted by the model and validated by quantitative proteomics, cells exhibit suboptimal recovery kinetics in response to nutrient shifts owing to a rigid strategy of protein synthesis allocation, which is not directed towards alleviating specific metabolic bottlenecks. Our approach does not rely on kinetic parameters, and therefore points to a theoretical framework for describing a broad range of such kinetic processes without detailed knowledge of the underlying biochemical reactions. PMID:29072300

  1. Thermoluminescence kinetics of pyrite (FeS2)

    NASA Astrophysics Data System (ADS)

    Silverman, A. N.; Levy, P. W.; Kierstead, J. A.

    Thermoluminescence of pyrite (FeS2) was investigated to study the kinetics of single peak glow curves. The material used normally exhibits one large and four small peaks. However a glow curve can be obtained with only the large single peak that is suitable for testing thermoluminescence kinetics. Glow curves from aliquots of a single natural pyrite crystal studied in detail contain two low intensity thermoluminescence (TL) peaks at approximately 90 and 250 C, and two chemiluminescence (CL) peaks at approximately 350 and 430 C. The CL peaks are largely removable by initially heating the sample chamber under vacuum, pumping through liquid nitrogen traps, and recording glow curves immediately after helium is introduced, procedures which reduce system contaminants that react with pyrite. The shape, the variation of the temperature of the peak maximum (T(sub max)) with dose, and the retrapping to recombination cross section ratio (sigma) of the large 250 C peak are better described by the general one trap (GOT) kinetic equation, the basic equation from which the 1st and 2nd order kinetic equations are obtained as special cases, than by the 1st and 2nd order equations.

  2. Diffusion Influenced Adsorption Kinetics.

    PubMed

    Miura, Toshiaki; Seki, Kazuhiko

    2015-08-27

    When the kinetics of adsorption is influenced by the diffusive flow of solutes, the solute concentration at the surface is influenced by the surface coverage of solutes, which is given by the Langmuir-Hinshelwood adsorption equation. The diffusion equation with the boundary condition given by the Langmuir-Hinshelwood adsorption equation leads to the nonlinear integro-differential equation for the surface coverage. In this paper, we solved the nonlinear integro-differential equation using the Grünwald-Letnikov formula developed to solve fractional kinetics. Guided by the numerical results, analytical expressions for the upper and lower bounds of the exact numerical results were obtained. The upper and lower bounds were close to the exact numerical results in the diffusion- and reaction-controlled limits, respectively. We examined the validity of the two simple analytical expressions obtained in the diffusion-controlled limit. The results were generalized to include the effect of dispersive diffusion. We also investigated the effect of molecular rearrangement of anisotropic molecules on surface coverage.

  3. Ambulatory measurement of ankle kinetics for clinical applications.

    PubMed

    Rouhani, H; Favre, J; Crevoisier, X; Aminian, K

    2011-10-13

    This study aimed to design and validate the measurement of ankle kinetics (force, moment, and power) during consecutive gait cycles and in the field using an ambulatory system. An ambulatory system consisting of plantar pressure insole and inertial sensors (3D gyroscopes and 3D accelerometers) on foot and shank was used. To test this system, 12 patients and 10 healthy elderly subjects wore shoes embedding this system and walked many times across a gait lab including a force-plate surrounded by seven cameras considered as the reference system. Then, the participants walked two 50-meter trials where only the ambulatory system was used. Ankle force components and sagittal moment of ankle measured by ambulatory system showed correlation coefficient (R) and normalized RMS error (NRMSE) of more than 0.94 and less than 13% in comparison with the references system for both patients and healthy subjects. Transverse moment of ankle and ankle power showed R>0.85 and NRMSE<23%. These parameters also showed high repeatability (CMC>0.7). In contrast, the ankle coronal moment of ankle demonstrated high error and lower repeatability. Except for ankle coronal moment, the kinetic features obtained by the ambulatory system could distinguish the patients with ankle osteoarthritis from healthy subjects when measured in 50-meter trials. The proposed ambulatory system can be easily accessible in most clinics and could assess main ankle kinetics quantities with acceptable error and repeatability for clinical evaluations. This system is therefore suggested for field measurement in clinical applications. Copyright © 2011 Elsevier Ltd. All rights reserved.

  4. Investigation on gas medium parameters for an ArF excimer laser through orthogonal experimental design

    NASA Astrophysics Data System (ADS)

    Song, Xingliang; Sha, Pengfei; Fan, Yuanyuan; Jiang, R.; Zhao, Jiangshan; Zhou, Yi; Yang, Junhong; Xiong, Guangliang; Wang, Yu

    2018-02-01

    Due to complex kinetics of formation and loss mechanisms, such as ion-ion recombination reaction, neutral species harpoon reaction, excited state quenching and photon absorption, as well as their interactions, the performance behavior of different laser gas medium parameters for excimer laser varies greatly. Therefore, the effects of gas composition and total gas pressure on excimer laser performance attract continual research studies. In this work, orthogonal experimental design (OED) is used to investigate quantitative and qualitative correlations between output laser energy characteristics and gas medium parameters for an ArF excimer laser with plano-plano optical resonator operation. Optimized output laser energy with good pulse to pulse stability can be obtained effectively by proper selection of the gas medium parameters, which makes the most of the ArF excimer laser device. Simple and efficient method for gas medium optimization is proposed and demonstrated experimentally, which provides a global and systematic solution. By detailed statistical analysis, the significance sequence of relevant parameter factors and the optimized composition for gas medium parameters are obtained. Compared with conventional route of varying single gas parameter factor sequentially, this paper presents a more comprehensive way of considering multivariables simultaneously, which seems promising in striking an appropriate balance among various complicated parameters for power scaling study of an excimer laser.

  5. Explosive sport training and torque kinetics in children.

    PubMed

    Dotan, Raffy; Mitchell, Cameron J; Cohen, Rotem; Gabriel, David; Klentrou, Panagiota; Falk, Bareket

    2013-07-01

    A high rate of force development (RFD) is often more important than maximal force in daily and sports activities. In children, resistance training has been shown to increase maximal force. It is unclear whether, or to what extent, can children improve RFD and force kinetics. For this study, we compared strength and force kinetics of boy gymnasts with those of untrained boys and untrained men. Eight boy gymnasts (age, 9.5 ± 1.2 y), 20 untrained boys (age, 10.1 ± 1.3 y), and 20 untrained men (age, 22.9 ± 4.4 y) performed maximal, explosive, isometric elbow flexions (EF) and knee flexions (KF). Peak torque (maximal voluntary contraction (MVC)), elapsed times to 10%-100% MVC, peak rate of torque development (RTDpk), and other kinetics parameters were determined. When gymnasts were compared with untrained boys, size-normalized EF MVC was 11%-20% higher, RTDpk was 32% higher, and times to 30% and 80% MVC were 16% and 55% shorter, respectively (p < 0.05). No corresponding differences were observed in KF. Furthermore, although the normalized EF MVC was 28% lower in gymnasts than in men (p < 0.001), their torque kinetics parameters were similar. These findings highlight the specificity of gymnastics training, which markedly elevated the torque kinetics of young, prepubertal boys to adult levels, but only moderately affected peak torque. It is suggested that neurologic adaptations, such as enhanced firing and activation rates or increased type II motor-unit recruitment, as well as changes in musculotendinous stiffness, could explain these findings.

  6. Thermal inactivation kinetics of Lactococcus lactis subsp. lactis bacteriophage pll98-22.

    PubMed

    Sanlibaba, Pinar; Buzrul, S; Akkoç, Nefise; Alpas, H; Akçelik, M

    2009-03-01

    Survival curves of Lactococcus lactis subsp. lactis bacteriophage pll98 inactivated by heat were obtained at seven temperature values (50-80 degrees C) in M17 broth and skim milk. Deviations from first-order kinetics in both media were observed as sigmoidal shapes in the survival curves of pll98. An empirical model with four parameters was used to define the thermal inactivation. Number of parameters of the model was reduced from four to two in order to increase the robustness of the model. The reduced model produced comparable fits to the full model. Both the survival data and the calculations done using the reduced model (time necessary to reduce the number of phage pll98 six- or seven- log10) indicated that skim milk is a more protective medium than M17 broth within the assayed temperature range.

  7. Modelling the growth kinetics of Kocuria marina DAGII as a function of single and binary substrate during batch production of β-Cryptoxanthin.

    PubMed

    Mitra, Ruchira; Chaudhuri, Surabhi; Dutta, Debjani

    2017-01-01

    In the present investigation, growth kinetics of Kocuria marina DAGII during batch production of β-Cryptoxanthin (β-CRX) was studied by considering the effect of glucose and maltose as a single and binary substrate. The importance of mixed substrate over single substrate has been emphasised in the present study. Different mathematical models namely, the Logistic model for cell growth, the Logistic mass balance equation for substrate consumption and the Luedeking-Piret model for β-CRX production were successfully implemented. Model-based analyses for the single substrate experiments suggested that the concentrations of glucose and maltose higher than 7.5 and 10.0 g/L, respectively, inhibited the growth and β-CRX production by K. marina DAGII. The Han and Levenspiel model and the Luong product inhibition model accurately described the cell growth in glucose and maltose substrate systems with a R 2 value of 0.9989 and 0.9998, respectively. The effect of glucose and maltose as binary substrate was further investigated. The binary substrate kinetics was well described using the sum-kinetics with interaction parameters model. The results of production kinetics revealed that the presence of binary substrate in the cultivation medium increased the biomass and β-CRX yield significantly. This study is a first time detailed investigation on kinetic behaviours of K. marina DAGII during β-CRX production. The parameters obtained in the study might be helpful for developing strategies for commercial production of β-CRX by K. marina DAGII.

  8. Calorimetric investigation of precipitation kinetics in Al-Mg-Si-X(Cr,Be) alloys

    NASA Astrophysics Data System (ADS)

    Woo, K. D.; Lee, J. S.; Kim, S. W.

    1999-07-01

    This study has been carried out by differential scanning calorimetry (DSC) to study the kinetics of precipitation and the dissolution of metastable and stable phases in Al-Mg-Si-(Cr,Be) alloys which were heat treated by T6, two-step aging and RRA (retrogression and reaging) treatment. The heat flow variations by phase transformation in the as-quenched specimen were calculated from DSC thermograms obtained from heating rates of 5, 10, 15 and 20°C/min. Four exothermic peaks may be attributed to the precipitation of G.P.I zone, G.P.II zone(β″), β' and β (Mg2Si) phases, and three endothermic peaks may be attributed to the dissolution of G.P.I zone, β″ and the β' phases, respectively. The kinetic equation (dY/dt)=f(Y)koexp(-Q*/RT) can be used to study the precipitation kinetics of Ai-Mg-Si-(Cr, Be) alloys, where Q*, ko, and f(Y)are the activation energy, frequency factors and the function of Y, respectively. The kinetic parameters measured from DSC curves can be used to interpret the transformation kinetics.The formation rate of β″ phase in the Al-Mg-Si alloy increased by the small addition of Be. This is because Be increases the nucleating rate of the β″ phase due to the decrease of the matrix/β″ interface energy. By the addition of Be or Cr and Be in Al-Mg-Si alloy, G.P. zone was easily decomposed during retrogression treatment at 225°C for 3 min. Therefore, maximum hardness can be obtained by RRA (150°C/20 min→225°C/3 min→ 180°C/3O min) in Al-0.8%Mg-1.0%Si-0.05% Be and Al-0.8% Mg-l.0% Si-0.l% Cr-0.05% Be alloys owing to the high density of β″ and β' precipitates.

  9. On the Nonequilibrium Interface Kinetics of Rapid Coupled Eutectic Growth

    NASA Astrophysics Data System (ADS)

    Dong, H.; Chen, Y. Z.; Shan, G. B.; Zhang, Z. R.; Liu, F.

    2017-08-01

    Nonequilibrium interface kinetics (NEIK) is expected to play an important role in coupled growth of eutectic alloys, when solidification velocity is high and intermetallic compound or topologically complex phases form in the crystallized product. In order to quantitatively evaluate the effect of NEIK on the rapid coupled eutectic growth, in this work, two nonequilibrium interface kinetic effects, i.e., atom attachment and solute trapping at the solid-liquid interface, were incorporated into the analyses of the coupled eutectic growth under the rapid solidification condition. First, a coupled growth model incorporating the preceding two nonequilibrium kinetic effects was derived. On this basis, an expression of kinetic undercooling (Δ T k), which is used to characterize the NEIK, was defined. The calculations based on the as-derived couple growth model show good agreement with the reported experimental results achieved in rapidly solidified eutectic Al-Sm alloys consisting of a solid solution phase ( α-Al) and an intermetallic compound phase (Al11Sm3). In terms of the definition of Δ T k defined in this work, the role of NEIK in the coupled growth of the Al-Sm eutectic system was analyzed. The results show that with increasing the coupled growth velocity, Δ T k increases continuously, and its ratio to the total undercooling reaches 0.32 at the maximum growth velocity for coupled eutectic growth. Parametric analyses on two key alloy parameters that influence Δ T k, i.e., interface kinetic parameter ( μ i ) and solute distribution coefficient ( k e ), indicate that both μ i and k e influence the NEIK significantly and the decrease of either these two parameters enhances the NEIK effect.

  10. Preliminary tests on nisin and pediocin production using waste protein sources. Factorial and kinetic studies.

    PubMed

    Vázquez, J A; González, M P; Murado, M A

    2006-03-01

    Lactic acid bacteria, the object of current interest as bacteriocin producers, are microorganisms with complex requirements for peptidic sources, making them appropriate indicators for testing the suitability of formulations based on proteinaceous wastes for use as microbiological media. Different peptones obtained from visceral and fish muscle residues promoted growth of lactic acid bacteria when applied individually or in combination. Kinetic parameters and bacteriocin production were similar and, in some cases (pediocin), far superior (>500%) to those obtained with bactopeptones and commercial media specifically recommended for lactic acid bacteria growth. Visceral residues, especially when subjected to a brief process of autohydrolysis at 20 degrees C, were more efficient for bacterial growth than muscle, even when muscle was treated with pepsin.

  11. Extraction of Antioxidant Phenolic Compounds from Brewer’s Spent Grain: Optimization and Kinetics Modeling

    PubMed Central

    Sologubik, Carlos A.; Fernández, María B.; Manrique, Guillermo D.

    2018-01-01

    The kinetics of polyphenol extraction from brewer’s spent grain (BSG), using a batch system, ultrasound assistance, and microwave assistance and the evolution of antioxidant capacity of these extracts over time, were studied. The main parameters of extraction employed in the batch system were evaluated, and, by applying response surface analysis, the following optimal conditions were obtained: Liquid/solid ratio of 30:1 mL/g at 80 °C, using 72% (v/v) ethanol:water as the solvent system. Under these optimized conditions, ultrasound assistance demonstrated the highest extraction rate and equilibrium yield, as well as shortest extraction times, followed by microwave assistance. Among the mathematical models used, Patricelli’s model proved the most suitable for describing the extraction kinetics for each method tested, and is therefore able to predict the response values and estimate the extraction rates and potential maximum yields in each case. PMID:29570683

  12. Distributed activation energy model parameters of some Turkish coals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gunes, M.; Gunes, S.K.

    2008-07-01

    A multi-reaction model based on distributed activation energy has been applied to some Turkish coals. The kinetic parameters of distributed activation energy model were calculated via computer program developed for this purpose. It was observed that the values of mean of activation energy distribution vary between 218 and 248 kJ/mol, and the values of standard deviation of activation energy distribution vary between 32 and 70 kJ/mol. The correlations between kinetic parameters of the distributed activation energy model and certain properties of coal have been investigated.

  13. Municipal Leachate Treatment by Fenton Process: Effect of Some Variable and Kinetics

    PubMed Central

    Ahmadian, Mohammad; Reshadat, Sohyla; Yousefi, Nader; Mirhossieni, Seyed Hamed; Zare, Mohammad Reza; Ghasemi, Seyed Ramin; Rajabi Gilan, Nader; Khamutian, Razieh; Fatehizadeh, Ali

    2013-01-01

    Due to complex composition of leachate, the comprehensive leachate treatment methods have been not demonstrated. Moreover, the improper management of leachate can lead to many environmental problems. The aim of this study was application of Fenton process for decreasing the major pollutants of landfill leachate on Kermanshah city. The leachate was collected from Kermanshah landfill site and treated by Fenton process. The effect of various parameters including solution pH, Fe2+ and H2O2 dosage, Fe2+/H2O2 molar ratio, and reaction time was investigated. The result showed that with increasing Fe2+ and H2O2 dosage, Fe2+/H2O2 molar ratio, and reaction time, the COD, TOC, TSS, and color removal increased. The maximum COD, TOC, TSS, and color removal were obtained at low pH (pH: 3). The kinetic data were analyzed in term of zero-order, first-order, and second-order expressions. First-order kinetic model described the removal of COD, TOC, TSS, and color from leachate better than two other kinetic models. In spite of extremely difficulty of leachate treatment, the previous results seem rather encouraging on the application of Fenton's oxidation. PMID:23840229

  14. Kinetics and Mechanisms of γ′ Reprecipitation in a Ni-based Superalloy

    PubMed Central

    Masoumi, F.; Shahriari, D.; Jahazi, M.; Cormier, J.; Devaux, A.

    2016-01-01

    The reprecipitation mechanisms and kinetics of γ′ particles during cooling from supersolvus and subsolvus temperatures were studied in AD730TM Ni-based superalloy using Differential Thermal Analysis (DTA). The evolution in the morphology and distribution of reprecipitated γ′ particles was investigated using Field Emission Gun Scanning Electron Microscopy (FEG-SEM). Depending on the cooling rate, γ′ particles showed multi or monomodal distribution. The irregularity growth characteristics observed at lower cooling rates were analyzed in the context of Mullins and Sekerka theory, and allowed the determination of a critical size of γ′ particles above which morphological instability appears. Precipitation kinetics parameters were determined using a non-isothermal JMA model and DTA data. The Avrami exponent was determined to be in the 1.5–2.3 range, suggesting spherical or irregular growth. A methodology was developed to take into account the temperature dependence of the rate coefficient k(T) in the non-isothermal JMA equation. In that regard, a function for k(T) was developed. Based on the results obtained, reprecipitation kinetics models for low and high cooling rates are proposed to quantify and predict the volume fraction of reprecipitated γ′ particles during the cooling process. PMID:27338868

  15. Kinetic model of water disinfection using peracetic acid including synergistic effects.

    PubMed

    Flores, Marina J; Brandi, Rodolfo J; Cassano, Alberto E; Labas, Marisol D

    2016-01-01

    The disinfection efficiencies of a commercial mixture of peracetic acid against Escherichia coli were studied in laboratory scale experiments. The joint and separate action of two disinfectant agents, hydrogen peroxide and peracetic acid, were evaluated in order to observe synergistic effects. A kinetic model for each component of the mixture and for the commercial mixture was proposed. Through simple mathematical equations, the model describes different stages of attack by disinfectants during the inactivation process. Based on the experiments and the kinetic parameters obtained, it could be established that the efficiency of hydrogen peroxide was much lower than that of peracetic acid alone. However, the contribution of hydrogen peroxide was very important in the commercial mixture. It should be noted that this improvement occurred only after peracetic acid had initiated the attack on the cell. This synergistic effect was successfully explained by the proposed scheme and was verified by experimental results. Besides providing a clearer mechanistic understanding of water disinfection, such models may improve our ability to design reactors.

  16. Kinetic study of solid waste pyrolysis using distributed activation energy model.

    PubMed

    Bhavanam, Anjireddy; Sastry, R C

    2015-02-01

    The pyrolysis characteristics of municipal solid waste, agricultural residues such as ground nut shell, cotton husk and their blends are investigated using non-isothermal thermogravimetric analysis (TGA) with in a temperature range of 30-900 °C at different heating rates of 10 °C, 30 °C and 50 °C/min in inert atmosphere. From the thermograms obtained from TGA, it is observed that the maximum rate of degradation occurred in the second stage of the pyrolysis process for all the solid wastes. The distributed activation energy model (DAEM) is used to study the pyrolysis kinetics of the solid wastes. The kinetic parameters E (activation energy), k0 (frequency factor) are calculated from this model. It is found that the range of activation energies for agricultural residues are lower than the municipal solid waste. The activation energies for the municipal solid waste pyrolysis process drastically decreased with addition of agricultural residues. The proposed DAEM is successfully validated with TGA experimental data. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Feedback, Mass Conservation and Reaction Kinetics Impact the Robustness of Cellular Oscillations

    PubMed Central

    Baum, Katharina; Kofahl, Bente; Steuer, Ralf; Wolf, Jana

    2016-01-01

    Oscillations occur in a wide variety of cellular processes, for example in calcium and p53 signaling responses, in metabolic pathways or within gene-regulatory networks, e.g. the circadian system. Since it is of central importance to understand the influence of perturbations on the dynamics of these systems a number of experimental and theoretical studies have examined their robustness. The period of circadian oscillations has been found to be very robust and to provide reliable timing. For intracellular calcium oscillations the period has been shown to be very sensitive and to allow for frequency-encoded signaling. We here apply a comprehensive computational approach to study the robustness of period and amplitude of oscillatory systems. We employ different prototype oscillator models and a large number of parameter sets obtained by random sampling. This framework is used to examine the effect of three design principles on the sensitivities towards perturbations of the kinetic parameters. We find that a prototype oscillator with negative feedback has lower period sensitivities than a prototype oscillator relying on positive feedback, but on average higher amplitude sensitivities. For both oscillator types, the use of Michaelis-Menten instead of mass action kinetics in all degradation and conversion reactions leads to an increase in period as well as amplitude sensitivities. We observe moderate changes in sensitivities if replacing mass conversion reactions by purely regulatory reactions. These insights are validated for a set of established models of various cellular rhythms. Overall, our work highlights the importance of reaction kinetics and feedback type for the variability of period and amplitude and therefore for the establishment of predictive models. PMID:28027301

  18. Kinetics of pack aluminization of nickel

    NASA Technical Reports Server (NTRS)

    Seigle, L. L.; Gupta, B. K.; Shankar, R.; Sarkhel, A. K.

    1978-01-01

    The kinetics of pack aluminization of unalloyed nickel in packs of varying aluminum activity with various halide activators were studied. Surface compositions of the coatings as functions of time, temperature, and pack composition were obtained in order to establish the boundary conditions for diffusion in the system. The structure of the packs was also examined in order to clarify the mechanism of aluminum transport. The results indicate that the kinetics of pack aluminization are controlled jointly by gas diffusion in the pack and solid diffusion in the coating. Levine and Caves' model for gas diffusion was combined with calculations of rates of diffusion in the solid to formulate a more complete theory for the kinetics of pack aluminization.

  19. Kinetics of the Multistep Rupture of Fibrin ‘A-a’ Polymerization Interactions Measured Using Atomic Force Microscopy

    PubMed Central

    Averett, Laurel E.; Schoenfisch, Mark H.; Akhremitchev, Boris B.; Gorkun, Oleg V.

    2009-01-01

    Abstract Fibrin, the structural scaffold of blood clots, spontaneously polymerizes through the formation of ‘A-a’ knob-hole bonds. When subjected to external force, the dissociation of this bond is accompanied by two to four abrupt changes in molecular dimension observable as rupture events in a force curve. Herein, the configuration, molecular extension, and kinetic parameters of each rupture event are examined. The increases in contour length indicate that the D region of fibrinogen can lengthen by ∼50% of the length of a fibrin monomer before rupture of the ‘A-a’ interaction. The dependence of the dissociation rate on applied force was obtained using probability distributions of rupture forces collected at different pull-off velocities. These distributions were fit using a model in which the effects of the shape of the binding potential are used to quantify the kinetic parameters of forced dissociation. We found that the weak initial rupture (i.e., event 1) was not well approximated by these models. The ruptured bonds comprising the strongest ruptures, events 2 and 3, had kinetic parameters similar to those commonly found for the mechanical unfolding of globular proteins. The bonds ruptured in event 4 were well described by these analyses, but were more loosely bound than the bonds in events 2 and 3. We propose that the first event represents the rupture of an unknown interaction parallel to the ‘A-a’ bond, events 2 and 3 represent unfolding of structures in the D region of fibrinogen, and event 4 is the rupture of the ‘A-a’ knob-hole bond weakened by prior structural unfolding. Comparison of the activation energy obtained via force spectroscopy measurements with the thermodynamic free energy of ‘A-a’ bond dissociation indicates that the ‘A-a’ bond may be more resistant to rupture by applied force than to rupture by thermal dissociation. PMID:19917237

  20. Receptor binding kinetics equations: Derivation using the Laplace transform method.

    PubMed

    Hoare, Sam R J

    Measuring unlabeled ligand receptor binding kinetics is valuable in optimizing and understanding drug action. Unfortunately, deriving equations for estimating kinetic parameters is challenging because it involves calculus; integration can be a frustrating barrier to the pharmacologist seeking to measure simple rate parameters. Here, a well-known tool for simplifying the derivation, the Laplace transform, is applied to models of receptor-ligand interaction. The method transforms differential equations to a form in which simple algebra can be applied to solve for the variable of interest, for example the concentration of ligand-bound receptor. The goal is to provide instruction using familiar examples, to enable investigators familiar with handling equilibrium binding equations to derive kinetic equations for receptor-ligand interaction. First, the Laplace transform is used to derive the equations for association and dissociation of labeled ligand binding. Next, its use for unlabeled ligand kinetic equations is exemplified by a full derivation of the kinetics of competitive binding equation. Finally, new unlabeled ligand equations are derived using the Laplace transform. These equations incorporate a pre-incubation step with unlabeled or labeled ligand. Four equations for measuring unlabeled ligand kinetics were compared and the two new equations verified by comparison with numerical solution. Importantly, the equations have not been verified with experimental data because no such experiments are evident in the literature. Equations were formatted for use in the curve-fitting program GraphPad Prism 6.0 and fitted to simulated data. This description of the Laplace transform method will enable pharmacologists to derive kinetic equations for their model or experimental paradigm under study. Application of the transform will expand the set of equations available for the pharmacologist to measure unlabeled ligand binding kinetics, and for other time

  1. [13C]bicarbonate kinetics in humans: intra- vs. interindividual variations.

    PubMed

    Irving, C S; Wong, W W; Shulman, R J; Smith, E O; Klein, P D

    1983-08-01

    A comprehensive multicompartmental analysis of HCO-3 kinetics was carried out on five normal, resting, fasted adults on three separate occasions at 1-wk to 1-mo intervals to obtain a set of bicarbonate kinetic parameters and estimates of their inter- and intraindividual variations for use in the design and analysis of future nutrient oxidation studies. Following a rapid bolus of NaH13CO3 (10 mumol . kg-1 iv), the decay of 13C enrichment of breath CO2 could be described by a three-exponential decay process and a linearly time-dependent term that accounted for changes in the 13C enrichment of metabolic fuels. The data were fitted subsequently to a mammillary multicompartmental model that consisted of a central pool and two peripheral pools of 3,310, 3,490, and 8,070 mumol . kg-1 HCO-3-CO2. Labeled CO2 was eliminated from the central pool by respiratory and nonrespiratory routes at rates of 101 and 97 mumol . kg-1 . min-1, respectively. The within-subject and among-subject variances were similar for the amount of freely exchangeable bicarbonate (14,870 mumol . kg-1), CO2 output (101 mumol . kg-1 . min-1), bicarbonate flux (198 mumol . kg-1 . min-1), and the fraction of administered bicarbonate recovered in breath (0.51). Comparison of variances associated with the assignment of a population mean value to a new subject and the variance associated with the use of a value obtained in the same individual on another day indicated that there was no advantage to making a determination on an alternate day over using a population value. Efforts should be made to compile population values for bicarbonate kinetics in different age groups and metabolic, nutritional, and pathological states for use in interpretation of nutrient oxidation data.

  2. Kinetic modelling of anaerobic hydrolysis of solid wastes, including disintegration processes.

    PubMed

    García-Gen, Santiago; Sousbie, Philippe; Rangaraj, Ganesh; Lema, Juan M; Rodríguez, Jorge; Steyer, Jean-Philippe; Torrijos, Michel

    2015-01-01

    A methodology to estimate disintegration and hydrolysis kinetic parameters of solid wastes and validate an ADM1-based anaerobic co-digestion model is presented. Kinetic parameters of the model were calibrated from batch reactor experiments treating individually fruit and vegetable wastes (among other residues) following a new protocol for batch tests. In addition, decoupled disintegration kinetics for readily and slowly biodegradable fractions of solid wastes was considered. Calibrated parameters from batch assays of individual substrates were used to validate the model for a semi-continuous co-digestion operation treating simultaneously 5 fruit and vegetable wastes. The semi-continuous experiment was carried out in a lab-scale CSTR reactor for 15 weeks at organic loading rate ranging between 2.0 and 4.7 gVS/Ld. The model (built in Matlab/Simulink) fit to a large extent the experimental results in both batch and semi-continuous mode and served as a powerful tool to simulate the digestion or co-digestion of solid wastes. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Kinetics of shear-induced gel deswelling/solvent release.

    PubMed

    Zeo, Undina; Tarabukina, Elena; Budtova, Tatiana

    2005-11-02

    The kinetics of shear-induced deswelling of gel particles based on synthetic (sodium polyacrylate) and natural (alginate) polymers was studied by rheo-optical technique. A swollen spherical gel particle of 100+/-50 microm diameter was placed in silicone oil and the evolution of the gel size as a function of time and shear rate was monitored. Different aqueous polymer solutions were used as synthetic gel solvent: polyvinylpyrrolidone, hydroxypropyl cellulose and glucose-based polymer. The interfacial tension (gel solvent)/(silicone oil), gel degree of swelling, solvent quality and viscosity are the main parameters influencing the kinetics of shear-induced gel deswelling. The kinetics of gel volume loss was approximated by a modified Weibull equation.

  4. Cluster kinetics model for mixtures of glassformers

    NASA Astrophysics Data System (ADS)

    Brenskelle, Lisa A.; McCoy, Benjamin J.

    2007-10-01

    For glassformers we propose a binary mixture relation for parameters in a cluster kinetics model previously shown to represent pure compound data for viscosity and dielectric relaxation as functions of either temperature or pressure. The model parameters are based on activation energies and activation volumes for cluster association-dissociation processes. With the mixture parameters, we calculated dielectric relaxation times and compared the results to experimental values for binary mixtures. Mixtures of sorbitol and glycerol (seven compositions), sorbitol and xylitol (three compositions), and polychloroepihydrin and polyvinylmethylether (three compositions) were studied.

  5. Effect of thermal treatment on TL response of CaSO₄:Dy obtained using a new preparation method.

    PubMed

    González, P R; Cruz-Zaragoza, E; Furetta, C; Azorín, J; Alcántara, B C

    2013-05-01

    We report the effect of thermal treatment on thermoluminescent (TL) sensitivity property of CaSO4:Dy obtained by a new preparation method at Instituto Nacional de Investigaciones Nucleares (ININ) of Mexico. Samples of phosphor powder were subjected to different thermal treatments respectively at 773, 873, 973 and 1,173K for 1h and then irradiated from 0.1 to 1,000 Gy gamma doses. Low energy dependence was analyzed too by irradiating with X-rays in the range of 16-145 keV. The results were normalized to the energy (1,252 keV) of (60)Co and they were compared with those obtained using the commercial dosimeters TLD-100. Also the kinetic parameters were determined by deconvolution of glow curve. Copyright © 2013 Elsevier Ltd. All rights reserved.

  6. Kinetics of enzymatic trans-esterification of glycerides for biodiesel production.

    PubMed

    Calabrò, Vincenza; Ricca, Emanuele; De Paola, Maria Gabriela; Curcio, Stefano; Iorio, Gabriele

    2010-08-01

    In this paper, the reaction of enzymatic trans-esterification of glycerides with ethanol in a reaction medium containing hexane at a temperature of 37 degrees C has been studied. The enzyme was Lipase from Mucor miehei, immobilized on ionic exchange resin, aimed at achieving high catalytic specific surface and recovering, regenerating and reusing the biocatalyst. A kinetic analysis has been carried out to identify the reaction path; the rate equation and kinetic parameters have been also calculated. The kinetic model has been validated by comparison between predicted and experimental results. Mass transport resistances estimation was undertaken in order to verify that the kinetics found was intrinsic. Model potentialities in terms of reactors design and optimization are also shown.

  7. Kinetic compensation effect in logistic distributed activation energy model for lignocellulosic biomass pyrolysis.

    PubMed

    Xu, Di; Chai, Meiyun; Dong, Zhujun; Rahman, Md Maksudur; Yu, Xi; Cai, Junmeng

    2018-06-04

    The kinetic compensation effect in the logistic distributed activation energy model (DAEM) for lignocellulosic biomass pyrolysis was investigated. The sum of square error (SSE) surface tool was used to analyze two theoretically simulated logistic DAEM processes for cellulose and xylan pyrolysis. The logistic DAEM coupled with the pattern search method for parameter estimation was used to analyze the experimental data of cellulose pyrolysis. The results showed that many parameter sets of the logistic DAEM could fit the data at different heating rates very well for both simulated and experimental processes, and a perfect linear relationship between the logarithm of the frequency factor and the mean value of the activation energy distribution was found. The parameters of the logistic DAEM can be estimated by coupling the optimization method and isoconversional kinetic methods. The results would be helpful for chemical kinetic analysis using DAEM. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. Curing kinetics of visible light curing dental resin composites investigated by dielectric analysis (DEA).

    PubMed

    Steinhaus, Johannes; Hausnerova, Berenika; Haenel, Thomas; Großgarten, Mandy; Möginger, Bernhard

    2014-03-01

    During the curing process of light curing dental composites the mobility of molecules and molecule segments is reduced leading to a significant increase of the viscosity as well as the ion viscosity. Thus, the kinetics of the curing behavior of 6 different composites was derived from dielectric analysis (DEA) using especially redesigned flat sensors with interdigit comb electrodes allowing for irradiation at the top side and measuring the ion viscosity at the bottom side. As the ion viscosities of dental composites change 1-3 orders of magnitude during the curing process, DEA provides a sensitive approach to evaluate their curing behavior, especially in the phase of undisturbed chain growth. In order to determine quantitative kinetic parameters a kinetic model is presented and examined for the evaluation of the ion viscosity curves. From the obtained results it is seen that DEA might be employed in the investigation of the primary curing process, the quality assurance of ingredients as well as the control of processing stability of the light curing dental composites. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  9. Use of extant kinetic parameters to predict effluent concentrations of specific organic compounds at full-scale facilities.

    PubMed

    Ellis, Timothy G; Eliosov, Boris

    2004-01-01

    To use the results of kinetic tests to predict effluent concentrations of specific contaminants in activated sludge systems, the fraction of the biomass that has an ability to degrade the test compound (i.e., competent biomass) must be estimated. A calibration procedure was developed to assess the competent biomass concentration because the chemical oxygen demand (COD) fraction tended to underestimate the degrading fraction for three of the four test compounds. Acetone, for instance, had a measured influent COD fraction of 0.08%, and the actual competent fraction was estimated to be 2.3%, based on the model calibration. Once the competent biomass fraction in the mixed liquor was determined, the extant kinetic parameters were subsequently used to predict activated sludge system performance. Predicted effluent concentrations were within 2, 5, and 16% of the average measured concentrations for acetone, linear alkylbenzene sulfonate, and furfural, respectively. Day-to-day predictions for these compounds were less accurate, possibly because of the non-steady-state nature of the activated sludge systems studied. The difference between the fraction of the influent COD contributed by the target compounds and the competent biomass fraction in the mixed liquor was found to be more significant when the target compound contributed less than 1% of the influent organic matter. The chemical structure of the target compound and chemical composition of the influent likely had an effect on the resulting competent biomass concentration. The total maximum growth rate, microX, was observed to be independent of the influent concentration of acetone and furfural, thus suggesting that the competent biomass concentration for these compounds was not affected by the changes in their influent concentrations. Consequently, a majority of competent biomass growth resulted from the degradation of other substrates, resulting in a competent biomass concentration significantly higher than predicted

  10. A comparison of low back kinetic estimates obtained through posture matching, rigid link modeling and an EMG-assisted model.

    PubMed

    Parkinson, R J; Bezaire, M; Callaghan, J P

    2011-07-01

    This study examined errors introduced by a posture matching approach (3DMatch) relative to dynamic three-dimensional rigid link and EMG-assisted models. Eighty-eight lifting trials of various combinations of heights (floor, 0.67, 1.2 m), asymmetry (left, right and center) and mass (7.6 and 9.7 kg) were videotaped while spine postures, ground reaction forces, segment orientations and muscle activations were documented and used to estimate joint moments and forces (L5/S1). Posture matching over predicted peak and cumulative extension moment (p < 0.0001 for all variables). There was no difference between peak compression estimates obtained with posture matching or EMG-assisted approaches (p = 0.7987). Posture matching over predicted cumulative (p < 0.0001) compressive loading due to a bias in standing, however, individualized bias correction eliminated the differences. Therefore, posture matching provides a method to analyze industrial lifting exposures that will predict kinetic values similar to those of more sophisticated models, provided necessary corrections are applied. Copyright © 2010 Elsevier Ltd and The Ergonomics Society. All rights reserved.

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

    PubMed

    Du, Bin; Zielinski, Daniel C; Kavvas, Erol S; Dräger, Andreas; Tan, Justin; Zhang, Zhen; Ruggiero, Kayla E; Arzumanyan, Garri A; Palsson, Bernhard O

    2016-06-06

    The mechanistic description of enzyme kinetics in a dynamic model of metabolism requires specifying the numerical values of a large number of kinetic parameters. The parameterization challenge is often addressed through the use of simplifying approximations to form reaction rate laws with reduced numbers of parameters. Whether such simplified models can reproduce dynamic characteristics of the full system is an important question. In this work, we compared the local transient response properties of dynamic models constructed using rate laws with varying levels of approximation. These approximate rate laws were: 1) a Michaelis-Menten rate law with measured enzyme parameters, 2) a Michaelis-Menten rate law with approximated parameters, using the convenience kinetics convention, 3) a thermodynamic rate law resulting from a metabolite saturation assumption, and 4) a pure chemical reaction mass action rate law that removes the role of the enzyme from the reaction kinetics. We utilized in vivo data for the human red blood cell to compare the effect of rate law choices against the backdrop of physiological flux and concentration differences. We found that the Michaelis-Menten rate law with measured enzyme parameters yields an excellent approximation of the full system dynamics, while other assumptions cause greater discrepancies in system dynamic behavior. However, iteratively replacing mechanistic rate laws with approximations resulted in a model that retains a high correlation with the true model behavior. Investigating this consistency, we determined that the order of magnitude differences among fluxes and concentrations in the network were greatly influential on the network dynamics. We further identified reaction features such as thermodynamic reversibility, high substrate concentration, and lack of allosteric regulation, which make certain reactions more suitable for rate law approximations. Overall, our work generally supports the use of approximate rate laws when

  12. Parameter optimization of electrolytic process of obtaining sodium hypochlorite for disinfection of water

    NASA Astrophysics Data System (ADS)

    Bogoslovskii, S. Yu; Kuznetsov, N. N.; Boldyrev, V. S.

    2017-11-01

    Electrochlorination parameters were optimized in flowing and non-flowing modes for a cell with a volume of 1 l. At a current density of 0.1 A/cm2 in the range of flow rates from 0.8 to 6.0 l/h with a temperature of the initial solution below 20°C the outlet temperature is maintained close to the optimal 40°C. The pH of the solution during electrolysis increases to 8.8 ÷ 9.4. There was studied a process in which a solution with a temperature of 7-8°C and a concentration of sodium chloride of 25 and 35 g/l in non-flowing cell was used. The dependence of the concentration of active chlorine on the electrolysis time varies with the concentration of the initial solution of sodium chloride. In case of chloride concentration of 25 g/l virtually linear relationship makes it easy to choose the time of electrolysis with the aim of obtaining the needed concentration of the product.

  13. Pursuing reliable thermal analysis techniques for energetic materials: decomposition kinetics and thermal stability of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50).

    PubMed

    Muravyev, Nikita V; Monogarov, Konstantin A; Asachenko, Andrey F; Nechaev, Mikhail S; Ananyev, Ivan V; Fomenkov, Igor V; Kiselev, Vitaly G; Pivkina, Alla N

    2016-12-21

    Thermal decomposition of a novel promising high-performance explosive dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50) was studied using a number of thermal analysis techniques (thermogravimetry, differential scanning calorimetry, and accelerating rate calorimetry, ARC). To obtain more comprehensive insight into the kinetics and mechanism of TKX-50 decomposition, a variety of complementary thermoanalytical experiments were performed under various conditions. Non-isothermal and isothermal kinetics were obtained at both atmospheric and low (up to 0.3 Torr) pressures. The gas products of thermolysis were detected in situ using IR spectroscopy, and the structure of solid-state decomposition products was determined by X-ray diffraction and scanning electron microscopy. Diammonium 5,5'-bistetrazole-1,1'-diolate (ABTOX) was directly identified to be the most important intermediate of the decomposition process. The important role of bistetrazole diol (BTO) in the mechanism of TKX-50 decomposition was also rationalized by thermolysis experiments with mixtures of TKX-50 and BTO. Several widely used thermoanalytical data processing techniques (Kissinger, isoconversional, formal kinetic approaches, etc.) were independently benchmarked against the ARC data, which are more germane to the real storage and application conditions of energetic materials. Our study revealed that none of the Arrhenius parameters reported before can properly describe the complex two-stage decomposition process of TKX-50. In contrast, we showed the superior performance of the isoconversional methods combined with isothermal measurements, which yielded the most reliable kinetic parameters of TKX-50 thermolysis. In contrast with the existing reports, the thermal stability of TKX-50 was determined in the ARC experiments to be lower than that of hexogen, but close to that of hexanitrohexaazaisowurtzitane (CL-20).

  14. Kinetics of monomer biodegradation in soil.

    PubMed

    Siotto, Michela; Sezenna, Elena; Saponaro, Sabrina; Innocenti, Francesco Degli; Tosin, Maurizio; Bonomo, Luca; Mezzanotte, Valeria

    2012-01-01

    In modern intensive agriculture, plastics are used in several applications (i.e. mulch films, drip irrigation tubes, string, clips, pots, etc.). Interest towards applying biodegradable plastics to replace the conventional plastics is promising. Ten monomers, which can be applied in the synthesis of potentially biodegradable polyesters, were tested according to ASTM 5988-96 (standard respirometric test to evaluate aerobic biodegradation in soil by measuring the carbon dioxide evolution): adipic acid, azelaic acid, 1,4-butanediol, 1,2-ethanediol, 1,6-hexanediol, lactic acid, glucose, sebacic acid, succinic acid and terephthalic acid. Eight replicates were carried out for each monomer for 27-45 days. The numerical code AQUASIM was applied to process the CO₂ experimental data in order to estimate values for the parameters describing the different mechanisms occurring to the monomers in soil: i) the first order solubilization kinetic constant, K(sol) (d⁻¹); ii) the first order biodegradation kinetic constant, K(b) (d⁻¹); iii) the lag time in biodegradation, t(lag) (d); and iv) the carbon fraction biodegraded but not transformed into CO₂, Y (-). The following range of values were obtained: [0.006 d⁻¹, 6.9 d⁻¹] for K(sol), [0.1 d⁻¹, 1.2 d⁻¹] for K(b), and [0.32-0.58] for Y; t(lag) was observed for azelaic acid, 1,2-ethanediol, and terephthalic acid, with estimated values between 3.0 e 4.9 d. Copyright © 2011 Elsevier Ltd. All rights reserved.

  15. Automated Transition State Theory Calculations for High-Throughput Kinetics.

    PubMed

    Bhoorasingh, Pierre L; Slakman, Belinda L; Seyedzadeh Khanshan, Fariba; Cain, Jason Y; West, Richard H

    2017-09-21

    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.

  16. Microbial respiration and dissolution precipitation reactions of minerals: thermo-kinetics and reactive transport modelling

    NASA Astrophysics Data System (ADS)

    Azaroual, M. M.; Parmentier, M.; Andre, L.; Croiset, N.; Pettenati, M.; Kremer, S.

    2010-12-01

    artificial recharge of deep aquifers system and in a second hand an acid mine drainage system. A large amount of data is available on the old mine site of Cheni (France). This field data on acid mine drainage are compared to a thermokinetic model including biological kinetics, precipitation-dissolution kinetics and surface complexation on ferrihydrite. The kinetic parameters are from literature and from a fitting on batch biological experiments. The integrated approach combining reaction kinetics and biogeochemical thermodynamic constraints is successfully applied to denitrification experiments in the presence of acetate and pyrite conducted in the laboratory for batch and column systems. The powerful of this coupled approach allows a fine description of the different transition species from nitrate to nitrogen. The fitted kinetic parameters established for modelling these laboratory results are thus extended to simulate the denitrification processes in a field case where organic matter and pyrite FeS2 are the electron donors and O2, NO3, Fe(OH)3, SO4 are the electron acceptors in the framework of a continuum UZ - SZ aiming to identify the stabilized redox zones of acid mine drainage. The detailed results obtained on two actual case studies will be presented.

  17. Treadmill based reference running data for healthy subjects is dependent on speed and morphological parameters.

    PubMed

    Schulze, Stephan; Schwesig, René; Edel, Melanie; Fieseler, Georg; Delank, Karl-Stefan; Hermassi, Souhail; Laudner, Kevin G

    2017-10-01

    To obtain spatiotemporal and dynamic running parameters of healthy participants and to identify relationships between running parameters, speed, and physical characteristics. A dynamometric treadmill was used to collect running data among 417 asymptomatic subjects during speeds ranging from 10 to 24km/h. Spatiotemporal and dynamic running parameters were calculated and measured. Results of the analyses showed that assessing running parameters is dependent on running speed. Body height correlated with stride length (r=0.5), cadence (r=-0.5) and plantar forefoot force (r=0.6). Body mass also had a strong relationship to plantar forefoot forces at 14 and 24km/h and plantar midfoot forces at 14 and 24km/h. This reference data base can be used in the kinematic and kinetic evaluation of running under a wide range of speeds. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. V̇O2 and HR kinetics before and after International Space Station missions.

    PubMed

    Hoffmann, U; Moore, A D; Koschate, J; Drescher, U

    2016-03-01

    Heart rate (HR), pulmonary and muscle oxygen uptake ([Formula: see text]O2pulm, [Formula: see text]O2musc) kinetics after changes of work rate (WR) indicate regulatory characteristics related to aerobic metabolism. We analysed whether the kinetics of HR, [Formula: see text]O2pulm and [Formula: see text]O2musc are slowed after missions to the International Space Station (ISS). The changes of the kinetics were correlated with [Formula: see text]O2peak data. 10 astronauts [4 females, 6 males, age: 48.0 ± 3.8 years, height: 176 ± 7 cm, mass: 74.5 ± 15.9 kg (mean ± SD)] performed an incremental test to determine [Formula: see text]O2peak (before missions on L-110 days, after return on R+1/+10/+36 days), and a cardio-respiratory kinetics test (CRKT) with randomized 30-80 W WR changes to determine HR, [Formula: see text]O2pulm and [Formula: see text]O2musc kinetics by time-series analysis (L-236/-73, R+6/+21). Kinetics were summarized by maximum and related lag of cross-correlation function (CCFmax, CCFlag) of WR with the analysed parameter. Statistically, significant changes were also found for CCFmax([Formula: see text]O2musc) between L-236 and R+6 (P = 0.010), L-236 and R+21 (P = 0.030), L-72 and R+6 (P = 0.043). Between pre-to-post mission change in [Formula: see text]O2peak and CCFmax(HR), a correlation was shown (r SP = 0.67, P = 0.017). The [Formula: see text]O2musc kinetics changes indicate aerobic detraining effects which are present up to 21 days following space flight. The correlations between changes in [Formula: see text]O2peak and HR kinetics illustrate the key role of cardiovascular regulation in [Formula: see text]O2peak. The addition of CRKT to ISS flight is recommended to obtain information regarding the potential muscular and cardiovascular deconditioning. This allows a reduction in the frequency of higher intensity testing during flight.

  19. Channel gating kinetics and synaptic efficacy: a hypothesis for expression of long-term potentiation.

    PubMed Central

    Ambros-Ingerson, J; Lynch, G

    1993-01-01

    A kinetic model of the glutamate DL-alpha-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid (AMPA) receptor/channel complex was used to test whether changes in the rate constants describing channel behavior could account for various features of long-term potentiation (LTP). Starting values for the kinetic parameters were set to satisfy experimental data (e.g., affinity, mean open time, mean burst length, etc.) and physical constraints (i.e., microreversibility). The resultant model exhibited a variety of dynamic properties known to be associated with the receptor. Increasing the rate constants governing opening/closing of the channel produced an unexpected increase in the probability of the channel being open shortly after transmitter binding. This would account for the enhanced response size with LTP. Increases in rate constants produced two other aspects of LTP: (i) an alteration of the waveform of the synaptic response and (ii) an interaction with changes in desensitization kinetics. The results obtained with the model corresponded closely to those found in LTP experiments. Thus, an increase in opening/closing rates for the postsynaptic receptor channel provides a single explanation for diverse characteristics of LTP. Finally, the kinetic manipulation reduced the coefficient of variation of synaptic currents in a model involving 250 receptors. This calls into question the use of variance measures for distinguishing pre- vs. postsynaptic sites of potentiation. PMID:8395058

  20. Kinetics of devolatilization and oxidation of a pulverized biomass in an entrained flow reactor under realistic combustion conditions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jimenez, Santiago; Remacha, Pilar; Ballester, Javier

    2008-03-15

    In this paper the results of a complete set of devolatilization and combustion experiments performed with pulverized ({proportional_to}500 {mu}m) biomass in an entrained flow reactor under realistic combustion conditions are presented. The data obtained are used to derive the kinetic parameters that best fit the observed behaviors, according to a simple model of particle combustion (one-step devolatilization, apparent oxidation kinetics, thermally thin particles). The model is found to adequately reproduce the experimental trends regarding both volatile release and char oxidation rates for the range of particle sizes and combustion conditions explored. The experimental and numerical procedures, similar to those recentlymore » proposed for the combustion of pulverized coal [J. Ballester, S. Jimenez, Combust. Flame 142 (2005) 210-222], have been designed to derive the parameters required for the analysis of biomass combustion in practical pulverized fuel configurations and allow a reliable characterization of any finely pulverized biomass. Additionally, the results of a limited study on the release rate of nitrogen from the biomass particle along combustion are shown. (author)« less

  1. Linear and non-linear regression analysis for the sorption kinetics of methylene blue onto activated carbon.

    PubMed

    Kumar, K Vasanth

    2006-10-11

    Batch kinetic experiments were carried out for the sorption of methylene blue onto activated carbon. The experimental kinetics were fitted to the pseudo first-order and pseudo second-order kinetics by linear and a non-linear method. The five different types of Ho pseudo second-order expression have been discussed. A comparison of linear least-squares method and a trial and error non-linear method of estimating the pseudo second-order rate kinetic parameters were examined. The sorption process was found to follow a both pseudo first-order kinetic and pseudo second-order kinetic model. Present investigation showed that it is inappropriate to use a type 1 and type pseudo second-order expressions as proposed by Ho and Blanachard et al. respectively for predicting the kinetic rate constants and the initial sorption rate for the studied system. Three correct possible alternate linear expressions (type 2 to type 4) to better predict the initial sorption rate and kinetic rate constants for the studied system (methylene blue/activated carbon) was proposed. Linear method was found to check only the hypothesis instead of verifying the kinetic model. Non-linear regression method was found to be the more appropriate method to determine the rate kinetic parameters.

  2. Kinetics of particle deposition at heterogeneous surfaces

    NASA Astrophysics Data System (ADS)

    Stojiljković, D. Lj.; Vrhovac, S. B.

    2017-12-01

    The random sequential adsorption (RSA) approach is used to analyze adsorption of spherical particles of fixed diameter d0 on nonuniform surfaces covered by square cells arranged in a square lattice pattern. To characterize such pattern two dimensionless parameters are used: the cell size α and the cell-cell separation β, measured in terms of the particle diameter d0. Adsorption is assumed to occur if the particle (projected) center lies within a cell area. We focus on the kinetics of deposition process in the case when no more than a single disk can be placed onto any square cell (α < 1 /√{ 2 } ≈ 0 . 707). We find that the asymptotic approach of the coverage fraction θ(t) to the jamming limit θJ is algebraic if the parameters α and β satisfy the simple condition, β + α / 2 < 1. If this condition is not satisfied, the late time kinetics of deposition process is not consistent with the power law behavior. However, if the geometry of the pattern approaches towards ;noninteracting conditions; (β > 1), when adsorption on each cell can be decoupled, approach of the coverage fraction θ(t) to θJ becomes closer to the exponential law. Consequently, changing the pattern parameters in the present model allows to interpolate the deposition kinetics between the continuum limit and the lattice-like behavior. Structural properties of the jammed-state coverings are studied in terms of the radial distribution function g(r) and spatial distribution of particles inside the cell. Various, non-trivial spatial distributions are observed depending on the geometry of the pattern.

  3. An algorithm for the kinetics of tire pyrolysis under different heating rates.

    PubMed

    Quek, Augustine; Balasubramanian, Rajashekhar

    2009-07-15

    Tires exhibit different kinetic behaviors when pyrolyzed under different heating rates. A new algorithm has been developed to investigate pyrolysis behavior of scrap tires. The algorithm includes heat and mass transfer equations to account for the different extents of thermal lag as the tire is heated at different heating rates. The algorithm uses an iterative approach to fit model equations to experimental data to obtain quantitative values of kinetic parameters. These parameters describe the pyrolysis process well, with good agreement (r(2)>0.96) between the model and experimental data when the model is applied to three different brands of automobile tires heated under five different heating rates in a pure nitrogen atmosphere. The model agrees with other researchers' results that frequencies factors increased and time constants decreased with increasing heating rates. The model also shows the change in the behavior of individual tire components when the heating rates are increased above 30 K min(-1). This result indicates that heating rates, rather than temperature, can significantly affect pyrolysis reactions. This algorithm is simple in structure and yet accurate in describing tire pyrolysis under a wide range of heating rates (10-50 K min(-1)). It improves our understanding of the tire pyrolysis process by showing the relationship between the heating rate and the many components in a tire that depolymerize as parallel reactions.

  4. SigrafW: An easy-to-use program for fitting enzyme kinetic data.

    PubMed

    Leone, Francisco Assis; Baranauskas, José Augusto; Furriel, Rosa Prazeres Melo; Borin, Ivana Aparecida

    2005-11-01

    SigrafW is Windows-compatible software developed using the Microsoft® Visual Basic Studio program that uses the simplified Hill equation for fitting kinetic data from allosteric and Michaelian enzymes. SigrafW uses a modified Fibonacci search to calculate maximal velocity (V), the Hill coefficient (n), and the enzyme-substrate apparent dissociation constant (K). The estimation of V, K, and the sum of the squares of residuals is performed using a Wilkinson nonlinear regression at any Hill coefficient (n). In contrast to many currently available kinetic analysis programs, SigrafW shows several advantages for the determination of kinetic parameters of both hyperbolic and nonhyperbolic saturation curves. No initial estimates of the kinetic parameters are required, a measure of the goodness-of-the-fit for each calculation performed is provided, the nonlinear regression used for calculations eliminates the statistical bias inherent in linear transformations, and the software can be used for enzyme kinetic simulations either for educational or research purposes. Persons interested in receiving a free copy of the software should contact Dr. F. A. Leone. Copyright © 2005 International Union of Biochemistry and Molecular Biology, Inc.

  5. Activation of Peptide ions by blackbody radiation: factors that lead to dissociation kinetics in the rapid energy exchange limit.

    PubMed

    Price, W D; Williams, E R

    1997-11-20

    Unimolecular rate constants for blackbody infrared radiative dissociation (BIRD) were calculated for the model protonated peptide (AlaGly)(n) (n = 2-32) using a variety of dissociation parameters. Combinations of dissociation threshold energies ranging from 0.8 to 1.7 eV and transition entropies corresponding to Arrhenius preexponential factors ranging from very "tight" (A(infinity) = 10(9.9) s(-1)) to "loose" (A(infinity) = 10(16.8) s(-1)) were selected to represent dissociation parameters within the experimental temperature range (300-520 K) and kinetic window (k(uni) = 0.001-0.20 s(-1)) typically used in the BIRD experiment. Arrhenius parameters were determined from the temperature dependence of these values and compared to those in the rapid energy exchange (REX) limit. In this limit, the internal energy of a population of ions is given by a Boltzmann distribution, and kinetics are the same as those in the traditional high-pressure limit. For a dissociation process to be in this limit, the rate of photon exchange between an ion and the vacuum chamber walls must be significantly greater than the dissociation rate. Kinetics rapidly approach the REX limit either as the molecular size or threshold dissociation energy increases or as the transition-state entropy or experimental temperature decreases. Under typical experimental conditions, peptide ions larger than 1.6 kDa should be in the REX limit. Smaller ions may also be in the REX limit depending on the value of the threshold dissociation energy and transition-state entropy. Either modeling or information about the dissociation mechanism must be known in order to confirm REX limit kinetics for these smaller ions. Three principal factors that lead to the size dependence of REX limit kinetics are identified. With increasing molecular size, rates of radiative absorption and emission increase, internal energy distributions become relatively narrower, and the microcanonical dissociation rate constants increase more

  6. Activation of Peptide Ions by Blackbody Radiation: Factors That Lead to Dissociation Kinetics in the Rapid Energy Exchange Limit

    PubMed Central

    Price, William D.

    2005-01-01

    Unimolecular rate constants for blackbody infrared radiative dissociation (BIRD) were calculated for the model protonated peptide (AlaGly)n (n = 2–32) using a variety of dissociation parameters. Combinations of dissociation threshold energies ranging from 0.8 to 1.7 eV and transition entropies corresponding to Arrhenius preexponential factors ranging from very “tight” (A∞ = 109.9 s−1) to “loose” (A∞ = 1016.8 s−1) were selected to represent dissociation parameters within the experimental temperature range (300–520 K) and kinetic window (kuni = 0.001–0.20 s−1) typically used in the BIRD experiment. Arrhenius parameters were determined from the temperature dependence of these values and compared to those in the rapid energy exchange (REX) limit. In this limit, the internal energy of a population of ions is given by a Boltzmann distribution, and kinetics are the same as those in the traditional high-pressure limit. For a dissociation process to be in this limit, the rate of photon exchange between an ion and the vacuum chamber walls must be significantly greater than the dissociation rate. Kinetics rapidly approach the REX limit either as the molecular size or threshold dissociation energy increases or as the transition-state entropy or experimental temperature decreases. Under typical experimental conditions, peptide ions larger than 1.6 kDa should be in the REX limit. Smaller ions may also be in the REX limit depending on the value of the threshold dissociation energy and transition-state entropy. Either modeling or information about the dissociation mechanism must be known in order to confirm REX limit kinetics for these smaller ions. Three principal factors that lead to the size dependence of REX limit kinetics are identified. With increasing molecular size, rates of radiative absorption and emission increase, internal energy distributions become relatively narrower, and the microcanonical dissociation rate constants increase more slowly

  7. Study of the Kinetics and Equilibrium of the Adsorption of Oils onto Hydrophobic Jute Fiber Modified via the Sol-Gel Method.

    PubMed

    Lv, Na; Wang, Xiaoli; Peng, Shitao; Zhang, Huaqin; Luo, Lei

    2018-05-12

    A new kind of hydrophobic and oil sorbent based on jute fiber was successfully prepared by the integration of silica onto a fiber surface via the sol-gel method and subsequent hydrophobic modification with octadecyltrichlorosilane (OTS). Compared with the hydrophilic raw fiber, the modified fiber had a water contact angle (CA) of 136.2°, suggesting that the material has good hydrophobicity. Furthermore, the ability of oil in the oil/water system (taking diesel for example) to absorb was revealed by the kinetics, the isotherm equation, and the thermodynamic parameters. Adsorption behavior was kinetically investigated using pseudo first-order and pseudo second-order models. The data mostly correlated with the pseudo first-order model. The equilibrium adsorption at 298 K was assessed by using the Langmuir and Freundlich isotherm models. The Freundlich model had greater consistency with the experimental data. The obtained thermodynamic parameters demonstrate that the adsorption of diesel is spontaneous, favorable, and exothermic.

  8. Droplet Growth Kinetics in Various Environments

    NASA Astrophysics Data System (ADS)

    Raatikainen, T. E.; Lathem, T. L.; Moore, R.; Lin, J. J.; Cerully, K. M.; Padro, L.; Lance, S.; Cozic, J.; Anderson, B. E.; Nenes, A.

    2012-12-01

    The largest uncertainties in the effects of atmospherics aerosols on the global radiation budget are related to their indirect effects on cloud properties (IPCC, the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, 2007). Cloud formation is a kinetic process where the resulting cloud properties depend on aerosol properties and meteorological parameters such as updraft velocity (e.g. McFiggans et al., Atmos. Chem. Phys., 6, 2593-2649, 2006). Droplet growth rates are limited by the water vapor diffusion, but additional kinetic limitations, e.g., due to organic surface films, slow solute dissociation or highly viscous or glassy aerosol states have been hypothesized. Significant additional kinetic limitations can lead to increased cloud droplet number concentration, thus the effect is similar to those of increased aerosol number concentration or changes in vertical velocity (e.g. Nenes et al., Geophys. Res. Lett., 29, 1848, 2002). There are a few studies where slow droplet growth has been observed (e.g. Ruehl et al., Geophys. Res. Lett., 36, L15814, 2009), however, little is currently known about their global occurrence and magnitude. Cloud micro-physics models often describe kinetic limitations by an effective water vapor uptake coefficient or similar parameter. Typically, determining aerosol water vapor uptake coefficients requires experimental observations of droplet growth which are interpreted by a numerical droplet growth model where the uptake coefficient is an adjustable parameter (e.g. Kolb et al., Atmos. Chem. Phys., 10, 10561-10605, 2010). Such methods have not been practical for high time-resolution or long term field measurements, until a model was recently developed for analyzing Droplet Measurement Technologies (DMT) cloud condensation nuclei (CCN) counter data (Raatikainen et al., Atmos. Chem. Phys., 12, 4227-4243, 2012). Model verification experiments showed that the calibration aerosol droplet size can be predicted accurately

  9. Chemical mechanism of D-amino acid oxidase from Rhodotorula gracilis: pH dependence of kinetic parameters.

    PubMed Central

    Ramón, F; Castillón, M; De La Mata, I; Acebal, C

    1998-01-01

    The variation of kinetic parameters of d-amino acid oxidase from Rhodotorula gracilis with pH was used to gain information about the chemical mechanism of the oxidation of D-amino acids catalysed by this flavoenzyme. d-Alanine was the substrate used. The pH dependence of Vmax and Vmax/Km for alanine as substrate showed that a group with a pK value of 6.26-7.95 (pK1) must be unprotonated and a group with a pK of 10.8-9.90 (pK2) must be protonated for activity. The lower pK value corresponded to a group on the enzyme involved in catalysis and whose protonation state was not important for binding. The higher pK value was assumed to be the amino group of the substrate. Profiles of pKi for D-aspartate as competitive inhibitor showed that binding is prevented when a group on the enzyme with a pK value of 8.4 becomes unprotonated; this basic group was not detected in Vmax/Km profiles suggesting its involvement in binding of the beta-carboxylic group of the inhibitor. PMID:9461524

  10. Kinetics of resid hydrodesulfurization reactions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mohammed, A.H.A.K.; Abbas, A.A.A.; Al'-Maiya, A.S.K.

    1987-07-01

    In this article the authors examine the results obtained in hydrodesulfurizing an atmospheric resis from Bai-Hassan crude on Ni-Mo/Al/sub 2/O/sub 3/ catalyst at 320-420/sup 0/C, feedstock space velocity 0.37-2.6 h/sup -1/, pressure 6.1 MPa, and hydrogen/feed ratio 300 liters/liter, in a single-pass downflow reactor with a stationary bed of catalyst. Also, they give certain thermodynamic characteristics for desulfurization, demetalization, and deasphalting of this resid. The kinetic model describing most accurately the kinetics of the different reactions will be examined.

  11. Thermal contact through a two-temperature kinetic Ising chain

    NASA Astrophysics Data System (ADS)

    Bauer, M.; Cornu, F.

    2018-05-01

    We consider a model for thermal contact through a diathermal interface between two macroscopic bodies at different temperatures: an Ising spin chain with nearest neighbor interactions is endowed with a Glauber dynamics with different temperatures and kinetic parameters on alternating sites. The inhomogeneity of the kinetic parameter is a novelty with respect to the model of Racz and Zia (1994 Phys. Rev. E 49 139), and we exhibit its influence upon the stationary non equilibrium values of the two-spin correlations at any distance. By mapping to the dynamics of spin domain walls and using free fermion techniques, we determine the scaled generating function for the cumulants of the exchanged heat amounts per unit of time in the long time limit.

  12. Analysis of a kinetic multi-segment foot model part II: kinetics and clinical implications.

    PubMed

    Bruening, Dustin A; Cooney, Kevin M; Buczek, Frank L

    2012-04-01

    Kinematic multi-segment foot models have seen increased use in clinical and research settings, but the addition of kinetics has been limited and hampered by measurement limitations and modeling assumptions. In this second of two companion papers, we complete the presentation and analysis of a three segment kinetic foot model by incorporating kinetic parameters and calculating joint moments and powers. The model was tested on 17 pediatric subjects (ages 7-18 years) during normal gait. Ground reaction forces were measured using two adjacent force platforms, requiring targeted walking and the creation of two sub-models to analyze ankle, midtarsal, and 1st metatarsophalangeal joints. Targeted walking resulted in only minimal kinematic and kinetic differences compared with walking at self selected speeds. Joint moments and powers were calculated and ensemble averages are presented as a normative database for comparison purposes. Ankle joint powers are shown to be overestimated when using a traditional single-segment foot model, as substantial angular velocities are attributed to the mid-tarsal joint. Power transfer is apparent between the 1st metatarsophalangeal and mid-tarsal joints in terminal stance/pre-swing. While the measurement approach presented here is limited to clinical populations with only minimal impairments, some elements of the model can also be incorporated into routine clinical gait analysis. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. Ion kinetic scale in the solar wind observed.

    PubMed

    Śafránková, Jana; Němeček, Zdeněk; Přech, Lubomír; Zastenker, Georgy N

    2013-01-11

    This Letter shows the first results from the solar wind monitor onboard the Spektr-R spacecraft which measures plasma moments with a time resolution of 31 ms. This high-time resolution allows us to make direct observations of solar wind turbulence below ion kinetic length scales. We present examples of the frequency spectra of the density, velocity, and thermal velocity. Our study reveals that although these parameters exhibit the same behavior at the magnetohydrodynamic scale, their spectra are remarkably different at the kinetic scale.

  14. Generalized kinetic-neoclassical closure for parallel viscosity in a tokamak.

    NASA Astrophysics Data System (ADS)

    Smolyakov, A.; Callen, J. D.; Hegna, C.

    2000-10-01

    We develop a drift-kinetic equation for a Chapman Enskog-type calculations of the parallel viscosity in a tokamak. This approach allows us to uniformly obtain closure relations for the parallel viscosity that include the kinetic effects of wave-particle interactions, such as those of Hammet-Perkins closures, as well as standard neoclassical moment closures induced by collisions and the magnetic field strength variation along field lines. Closures for both these cases can be obtained from our expressions; also, their mutual influences can be investigated. The developed equations allow calculation of parallel vicosity in general kinetic-neoclassical regimes while the main conservation properties remain correct even with an approximate treatment of the collisional operator.

  15. Cure Kinetics of Benzoxazine/Cycloaliphatic Epoxy Resin by Differential Scanning Calorimetry

    NASA Astrophysics Data System (ADS)

    Gouni, Sreeja Reddy

    Understanding the curing kinetics of a thermoset resin has a significant importance in developing and optimizing curing cycles in various industrial manufacturing processes. This can assist in improving the quality of final product and minimizing the manufacturing-associated costs. One approach towards developing such an understanding is to formulate kinetic models that can be used to optimize curing time and temperature to reach a full cure state or to determine time to apply pressure in an autoclave process. Various phenomenological reaction models have been used in the literature to successfully predict the kinetic behavior of a thermoset system. The current research work was designed to investigate the cure kinetics of Bisphenol-A based Benzoxazine (BZ-a) and Cycloaliphatic epoxy resin (CER) system under isothermal and nonisothermal conditions by Differential Scanning Calorimetry (DSC). The cure characteristics of BZ-a/CER copolymer systems with 75/25 wt% and 50/50 wt% have been studied and compared to that of pure benzoxazine under nonisothermal conditions. The DSC thermograms exhibited by these BZ-a/CER copolymer systems showed a single exothermic peak, indicating that the reactions between benzoxazine-benzoxazine monomers and benzoxazine-cycloaliphatic epoxy resin were interactive and occurred simultaneously. The Kissinger method and isoconversional methods including Ozawa-Flynn-Wall and Freidman were employed to obtain the activation energy values and determine the nature of the reaction. The cure behavior and the kinetic parameters were determined by adopting a single step autocatalytic model based on Kamal and Sourour phenomenological reaction model. The model was found to suitably describe the cure kinetics of copolymer system prior to the diffusion-control reaction. Analyzing and understanding the thermoset resin system under isothermal conditions is also important since it is the most common practice in the industry. The BZ-a/CER copolymer system with

  16. A Microwave Radiometric Method to Obtain the Average Path Profile of Atmospheric Temperature and Humidity Structure Parameters and Its Application to Optical Propagation System Assessment

    NASA Technical Reports Server (NTRS)

    Manning, Robert M.; Vyhnalek, Brian E.

    2015-01-01

    The values of the key atmospheric propagation parameters Ct2, Cq2, and Ctq are highly dependent upon the vertical height within the atmosphere thus making it necessary to specify profiles of these values along the atmospheric propagation path. The remote sensing method suggested and described in this work makes use of a rapidly integrating microwave profiling radiometer to capture profiles of temperature and humidity through the atmosphere. The integration times of currently available profiling radiometers are such that they are approaching the temporal intervals over which one can possibly make meaningful assessments of these key atmospheric parameters. Since these parameters are fundamental to all propagation conditions, they can be used to obtain Cn2 profiles for any frequency, including those for an optical propagation path. In this case the important performance parameters of the prevailing isoplanatic angle and Greenwood frequency can be obtained. The integration times are such that Kolmogorov turbulence theory and the Taylor frozen-flow hypothesis must be transcended. Appropriate modifications to these classical approaches are derived from first principles and an expression for the structure functions are obtained. The theory is then applied to an experimental scenario and shows very good results.

  17. General methods for analysis of sequential "n-step" kinetic mechanisms: application to single turnover kinetics of helicase-catalyzed DNA unwinding.

    PubMed

    Lucius, Aaron L; Maluf, Nasib K; Fischer, Christopher J; Lohman, Timothy M

    2003-10-01

    Helicase-catalyzed DNA unwinding is often studied using "all or none" assays that detect only the final product of fully unwound DNA. Even using these assays, quantitative analysis of DNA unwinding time courses for DNA duplexes of different lengths, L, using "n-step" sequential mechanisms, can reveal information about the number of intermediates in the unwinding reaction and the "kinetic step size", m, defined as the average number of basepairs unwound between two successive rate limiting steps in the unwinding cycle. Simultaneous nonlinear least-squares analysis using "n-step" sequential mechanisms has previously been limited by an inability to float the number of "unwinding steps", n, and m, in the fitting algorithm. Here we discuss the behavior of single turnover DNA unwinding time courses and describe novel methods for nonlinear least-squares analysis that overcome these problems. Analytic expressions for the time courses, f(ss)(t), when obtainable, can be written using gamma and incomplete gamma functions. When analytic expressions are not obtainable, the numerical solution of the inverse Laplace transform can be used to obtain f(ss)(t). Both methods allow n and m to be continuous fitting parameters. These approaches are generally applicable to enzymes that translocate along a lattice or require repetition of a series of steps before product formation.

  18. Thermoluminescence properties of CaO powder obtained from chicken eggshells

    NASA Astrophysics Data System (ADS)

    Nagabhushana, K. R.; Lokesha, H. S.; Satyanarayana Reddy, S.; Prakash, D.; Veerabhadraswamy, M.; Bhagyalakshmi, H.; Jayaramaiah, J. R.

    2017-09-01

    Eggshell wastage has created serious problem in disposal of the food processing industry which has been triggered the thoughts of researchers to use wasted eggshells as good source of calcium. In the present work, calcium oxide (CaO) has been synthesized by combustion process in furnace (F-CaO) and microwave oven (M-CaO) using the source of chicken eggshells. The obtained F-CaO and M-CaO are characterized by XRD, SEM with EDX and thermoluminescence (TL) technique. XRD pattern of both the samples show cubic phase with crystallite size 45-52 nm. TL glow curves are recorded for various gamma radiation dose (300-4000 Gy). Two TL glows, a small peak at 424 K and stronger peak at 597 K are observed. TL response of M-CaO is 2.67 times higher than F-CaO sample. TL kinetic parameters are calculated by computerized curve deconvolution analysis (CCDA) and discussed.

  19. Kinetic modeling of simultaneous saccharification and fermentation of corn starch for ethanol production.

    PubMed

    Białas, Wojciech; Czerniak, Adrian; Szymanowska-Powałowska, Daria

    2014-01-01

    Fuel ethanol production, using a simultaneous saccharification and fermentation process (SSF) of native starch from corn flour, has been performed using Saccharomyces cerevisiae and a granular starch hydrolyzing enzyme. The quantitative effects of mash concentration, enzyme dose and pH were investigated with the use of a Box-Wilson central composite design protocol. Proceeding from results obtained in optimal fermentation conditions, a kinetics model relating the utilization rates of starch and glucose as well as the production rates of ethanol and biomass was tested. Moreover, scanning electron microscopy (SEM) was applied to investigate corn starch granule surface after the SFF process. A maximum ethanol concentration of 110.36 g/l was obtained for native corn starch using a mash concentration of 25%, which resulted in ethanol yield of 85.71%. The optimal conditions for the above yield were found with an enzyme dose of 2.05 ml/kg and pH of 5.0. These results indicate that by using a central composite design, it is possible to determine optimal values of the fermentation parameters for maximum ethanol production. The investigated kinetics model can be used to describe SSF process conducted with granular starch hydrolyzing enzymes. The SEM micrographs reveal randomly distributed holes on the surface of granules.

  20. Methanogenic degradation kinetics of phenolic compounds in aquifer-derived microcosms

    USGS Publications Warehouse

    Godsy, E.M.; Goerlitz, D.F.; Grbic-Galic, D.

    1992-01-01

    In this segment of a larger multidisciplinary study of the movement and fate of creosote derived compounds in a sand-and-gravel aquifer, we present evidence that the methanogenic degradation of the major biodegradable phenolic compounds and concomitant microbial growth in batch microcosms derived from contaminated aquifer material can be described using Monod kinetics. Substrate depletion and bacterial growth curves were fitted to the Monod equations using nonlinear regression analysis. The method of Marquardt was used for the determination of parameter values that best fit the experimental data by minimizing the residual sum of squares. The Monod kinetic constants (??max, Ks, Y, and kd) that describe phenol, 2-, 3-, and 4-methylphenol degradation and concomitant microbial growth were determined under conditions that were substantially different from those previously reported for microcosms cultured from sewage sludge. The Ks values obtained in this study are approximately two orders of magnitude lower than values obtained for the anaerobic degradation of phenol in digesting sewage sludge, indicating that the aquifer microorganisms have developed enzyme systems that are adapted to low nutrient conditions. The values for kd are much less than ??max, and can be neglected in the microcosms. The extremely low Y values, approximately 3 orders of magnitude lower than for the sewage sludge derived cultures, and the very low numbers of microorganisms in the aquifer derived microcosms suggest that these organisms use some unique strategies to survive in the subsurface environment. ?? 1992 Kluwer Academic Publishers.

  1. Highly resolved fluid flows: "liquid plasmas" at the kinetic level.

    PubMed

    Morfill, Gregor E; Rubin-Zuzic, Milenko; Rothermel, Hermann; Ivlev, Alexei V; Klumov, Boris A; Thomas, Hubertus M; Konopka, Uwe; Steinberg, Victor

    2004-04-30

    Fluid flow around an obstacle was observed at the kinetic (individual particle) level using "complex (dusty) plasmas" in their liquid state. These "liquid plasmas" have bulk properties similar to water (e.g., viscosity), and a comparison in terms of similarity parameters suggests that they can provide a unique tool to model classical fluids. This allows us to study "nanofluidics" at the most elementary-the particle-level, including the transition from fluid behavior to purely kinetic transport. In this (first) experimental investigation we describe the kinetic flow topology, discuss our observations in terms of fluid theories, and follow this up with numerical simulations.

  2. Controlling the Growth of Au on Icosahedral Seeds of Pd by Manipulating the Reduction Kinetics

    DOE PAGES

    Lv, Tian; Yang, Xuan; Zheng, Yiqun; ...

    2016-03-29

    This article reports a systematic study of how Au atoms nucleate and grow on Pd icosahedral seeds with a multiply twinned structure. By manipulating the reduction kinetics, we obtained Pd–Au bimetallic nanocrystals with two distinct shapes and structures. Specifically, Pd@Au core–shell icosahedra were formed when a relatively fast reduction rate was used for the HAuCl 4 precursor. At a slow reduction rate, in contrast, the nucleation and growth of Au atoms were mainly confined to one of the vertices of a Pd icosahedral seed, resulting in the formation of a Au icosahedron by sharing five adjacent faces with the Pdmore » seed. The same growth pattern was observed for Pd icosahedral seeds with both sizes of 32 and 20 nm. Also, we have also investigated the effects of other kinetic parameters, including the concentration of reducing agent and reaction temperature, on the growth pathway undertaken by the Au atoms. In conclusion, we believe that the mechanistic insights obtained from this study can be extended to other systems, including the involvement of different metals and/or seeds with different morphologies.« less

  3. On the thermodynamic and kinetic investigations of a [c2]daisy chain polymer

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hmadeh, Mohamad; Fang, Lei; Trabolsi, Ali

    2010-01-01

    We report a variety of [c2]daisy chain molecules which undergo quantitative, efficient, and fully reversible molecular movements upon the addition of base/acid in organic solvents. Such externally triggered molecular movements can induce the contraction and extension of the [c2]daisy chain molecule as a whole. A linear polymer of such a bistable [c2]daisy chain exerts similar types of movements and can be looked upon as a candidate for the development of artificial muscles. The spectrophotometric investigations of both the monomeric and polymeric bistable [c2]daisy chains, as well as the corresponding model compounds, were performed in MeCN at room temperature, in ordermore » to obtain the thermodynamic parameters for these mechanically interlocked molecules. Based on their spectrophotometric and thermodynamic characteristics, kinetic analysis of the acid/base-induced contraction and extension of the [c2]daisy chain monomer and polymer were conducted by employing a stopped-flow technique. These kinetic data suggest that the rates of contraction and extension for these [c2]daisy chain molecules are determined by the thermodynamic stabilities of the corresponding kinetic intermediates. Faster switching rates for both the contraction and extension processes of the polymeric [c2]daisy chain were observed when compared to those of its monomeric counterpart. These kinetic and thermodynamic investigations on [c2]daisy chain-based muscle-like compounds provide important information for those seeking an understanding of the mechanisms of actuation in mechanically interlocked macromolecules.« less

  4. First-order kinetic gas generation model parameters for wet landfills.

    PubMed

    Faour, Ayman A; Reinhart, Debra R; You, Huaxin

    2007-01-01

    Landfill gas collection data from wet landfill cells were analyzed and first-order gas generation model parameters were estimated for the US EPA landfill gas emissions model (LandGEM). Parameters were determined through statistical comparison of predicted and actual gas collection. The US EPA LandGEM model appeared to fit the data well, provided it is preceded by a lag phase, which on average was 1.5 years. The first-order reaction rate constant, k, and the methane generation potential, L(o), were estimated for a set of landfills with short-term waste placement and long-term gas collection data. Mean and 95% confidence parameter estimates for these data sets were found using mixed-effects model regression followed by bootstrap analysis. The mean values for the specific methane volume produced during the lag phase (V(sto)), L(o), and k were 33 m(3)/Megagrams (Mg), 76 m(3)/Mg, and 0.28 year(-1), respectively. Parameters were also estimated for three full scale wet landfills where waste was placed over many years. The k and L(o) estimated for these landfills were 0.21 year(-1), 115 m(3)/Mg, 0.11 year(-1), 95 m(3)/Mg, and 0.12 year(-1) and 87 m(3)/Mg, respectively. A group of data points from wet landfills cells with short-term data were also analyzed. A conservative set of parameter estimates was suggested based on the upper 95% confidence interval parameters as a k of 0.3 year(-1) and a L(o) of 100 m(3)/Mg if design is optimized and the lag is minimized.

  5. Kinetics, biocompounds, antioxidant activity, and sensory attributes of quinces as affected by drying method.

    PubMed

    Szychowski, Przemysław J; Lech, Krzysztof; Sendra-Nadal, Esther; Hernández, Francisca; Figiel, Adam; Wojdyło, Aneta; Carbonell-Barrachina, Ángel A

    2018-07-30

    Quinces are attracting interest due to their health and nutritional benefits. Drying kinetics, bioactive compounds, antioxidant activity, and the main sensory parameters were determined in dried quinces, cultivar Leskovač, as affected by the drying method. The highest total polyphenols content was observed in dried samples obtained after freeze drying and convective drying at 50 °C. The best drying treatment, considering only sensory attributes, was vacuum-microwave drying at 480 W, because it led to intermediate dark color and high intensities of basic tastes and key flavor attributes. The studied parameters were finally used to recommend convective drying at 60 °C as the most appropriate drying method for quinces, because it had a high content of total phenolic compounds (2nd best treatment out of 10), a good sensory profile, was cheap, and caused no negative effects on nutritional or sensory parameters; the only disadvantage was its long drying time. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Characterization, kinetic, and thermodynamic studies of marine pectinase from Bacillus subtilis.

    PubMed

    Joshi, Manasi; Nerurkar, Madhura; Adivarekar, Ravindra

    2015-01-01

    Characterization, kinetic and thermodynamic parameters of purified pectinase from Bacillus subtilis, isolated from a marine sediment sample collected from Chinchani beach at Tarapore, India, were studied. Marine pectinase produced under submerged growth conditions was purified by ammonium sulfate precipitation followed by gel filtration chromatography using DEAE cellulose. Partial characterization of the marine pectinase was carried out in terms of effect of pH, temperature, substrate concentration, and metal ions. It was found that pectinase from marine B. subtilis showed maximal activity in alkaline buffer at pH 9.0 and at 40°C. It was also found that metal ions, namely, Mn(2+) and Fe(2+), stimulate pectinase activity. Marine pectinase followed Michaelis-Menten kinetics. The kinetics and thermodynamic parameters of the purified marine pectinase from B. subtilis were studied as the characterization of the enzyme is vital for its use in industrial processes.

  7. Kinetics and mechanism of olefin catalytic hydroalumination by organoaluminum compounds

    NASA Astrophysics Data System (ADS)

    Koledina, K. F.; Gubaidullin, I. M.

    2016-05-01

    The complex reaction mechanism of α-olefin catalytic hydroalumination by alkylalanes is investigated via mathematical modeling that involves plotting the kinetic models for the individual reactions that make up a complex system and a separate study of their principles. Kinetic parameters of olefin catalytic hydroalumination are estimated. Activation energies of the possible steps of the schemes of complex reaction mechanisms are compared and possible reaction pathways are determined.

  8. Comparison of ionosphere characteristic parameters obtained by ionosonde with IRI-2007 model over Southeast Asia

    NASA Astrophysics Data System (ADS)

    Wichaipanich, N.; Supnithi, P.; Tsugawa, T.; Maruyama, T.; Nagatsuma, T.

    2013-11-01

    In this work, the foF2 and hmF2 parameters at the conjugate points near the magnetic equator of Southeast Asia are studied and compared with the International Reference Ionosphere (IRI) model. Three ionosondes are installed nearly along the magnetic meridian of 100°E; one at the magnetic equator, namely Chumphon (10.72°N, 99.37°E, dip angle 3.0°N), and the other two at the magnetic conjugate points, namely Chiang Mai (18.76°N, 98.93°E, dip angle 12.7°N) and Kototabang (0.2°S, 100.30°E, dip angle 10.1°S). The monthly hourly medians of the foF2 and hmF2 parameters are calculated and compared with the predictions obtained from the IRI-2007 model from January 2004 to February 2007. Our results show that: the variations of foF2 and hmF2 predicted by the IRI-2007 model generally show the similar feature to the observed data. Both parameters generally show better agreement with the IRI predictions during daytime than during nighttime. For foF2, most of the results show that the IRI model overestimates the observed foF2 at the magnetic equator (Chumphon), underestimates at the northern crest (Chiang Mai) and is close to the measured ones at the southern crest of the EIA (Kototabang). For hmF2, the predicted hmF2 values are close to the hmF2(M3000F2OBS) during daytime. During nighttime, the IRI model gives the underestimation at the magnetic equator and the overestimation at both EIA crests. The results are important for the future improvements of the IRI model for foF2 and hmF2 over Southeast Asia region.

  9. Echographic and kinetic changes in the shoulder joint after manual wheelchair propulsion under two different workload settings.

    PubMed

    Gil-Agudo, Ángel; Solís-Mozos, Marta; Crespo-Ruiz, Beatriz; Del-Ama Eng, Antonio J; Pérez-Rizo, Enrique; Segura-Fragoso, Antonio; Jiménez-Díaz, Fernando

    2014-01-01

    Manual wheelchair users with spinal cord injury (SCI) have a high prevalence of shoulder pain due to the use of the upper extremity for independent mobility, transfers, and other activities of daily living. Indeed, shoulder pain dramatically affects quality of life of these individuals. There is limited evidence obtained through radiographic techniques of a relationship between the forces acting on the shoulder during different propulsion conditions and shoulder pathologies. Today, ultrasound is widely accepted as a precise tool in diagnosis, displaying particularly effectiveness in screening the shoulder rotator cuff. Thus, we set out to perform an ultrasound-based study of the acute changes to the shoulder soft tissues after propelling a manual wheelchair in two workload settings. Shoulder joint kinetics was recorded from 14 manual wheelchair users with SCI while they performed high- and low-intensity wheelchair propulsion tests (constant and incremental). Shoulder joint forces and moments were obtained from inverse dynamic methods, and ultrasound screening of the shoulder was performed before and immediately after the test. Kinetic changes were more relevant after the most intensive task, showing the significance of high-intensity activity, yet no differences were found in ultrasound-related parameters before and after each propulsion task. It therefore appears that further studies will be needed to collect clinical data and correlate data regarding shoulder pain with both ultrasound images and data from shoulder kinetics.

  10. Echographic and Kinetic Changes in the Shoulder Joint after Manual Wheelchair Propulsion Under Two Different Workload Settings

    PubMed Central

    Gil-Agudo, Ángel; Solís-Mozos, Marta; Crespo-Ruiz, Beatriz; del-Ama Eng, Antonio J.; Pérez-Rizo, Enrique; Segura-Fragoso, Antonio; Jiménez-Díaz, Fernando

    2014-01-01

    Manual wheelchair users with spinal cord injury (SCI) have a high prevalence of shoulder pain due to the use of the upper extremity for independent mobility, transfers, and other activities of daily living. Indeed, shoulder pain dramatically affects quality of life of these individuals. There is limited evidence obtained through radiographic techniques of a relationship between the forces acting on the shoulder during different propulsion conditions and shoulder pathologies. Today, ultrasound is widely accepted as a precise tool in diagnosis, displaying particularly effectiveness in screening the shoulder rotator cuff. Thus, we set out to perform an ultrasound-based study of the acute changes to the shoulder soft tissues after propelling a manual wheelchair in two workload settings. Shoulder joint kinetics was recorded from 14 manual wheelchair users with SCI while they performed high- and low-intensity wheelchair propulsion tests (constant and incremental). Shoulder joint forces and moments were obtained from inverse dynamic methods, and ultrasound screening of the shoulder was performed before and immediately after the test. Kinetic changes were more relevant after the most intensive task, showing the significance of high-intensity activity, yet no differences were found in ultrasound-related parameters before and after each propulsion task. It therefore appears that further studies will be needed to collect clinical data and correlate data regarding shoulder pain with both ultrasound images and data from shoulder kinetics. PMID:25566539

  11. Isotherm Modelling, Kinetic Study and Optimization of Batch Parameters Using Response Surface Methodology for Effective Removal of Cr(VI) Using Fungal Biomass

    PubMed Central

    Chidambaram, Ramalingam

    2015-01-01

    Biosorption is a promising alternative method to replace the existing conventional technique for Cr(VI) removal from the industrial effluent. In the present experimental design, the removal of Cr(VI) from the aqueous solution was studied by Aspergillus niger MSR4 under different environmental conditions in the batch systems. The optimum conditions of biosorption were determined by investigating pH (2.0) and temperature (27°C). The effects of parameters such as biomass dosage (g/L), initial Cr(VI) concentration (mg/L) and contact time (min) on Cr(VI) biosorption were analyzed using a three parameter Box–Behnken design (BBD). The experimental data well fitted to the Langmuir isotherm, in comparison to the other isotherm models tested. The results of the D-R isotherm model suggested that a chemical ion-exchange mechanism was involved in the biosorption process. The biosorption process followed the pseudo-second-order kinetic model, which indicates that the rate limiting step is chemisorption process. Fourier transform infrared (FT-IR) spectroscopic studies revealed the possible involvement of functional groups, such as hydroxyl, carboxyl, amino and carbonyl group in the biosorption process. The thermodynamic parameters for Cr(VI) biosorption were also calculated, and the negative ∆Gº values indicated the spontaneous nature of biosorption process. PMID:25786227

  12. Metastable Solution Thermodynamic Properties and Crystal Growth Kinetics

    NASA Technical Reports Server (NTRS)

    Kim, Soojin; Myerson, Allan S.

    1996-01-01

    The crystal growth rates of NH4H2PO4, KH2PO4, (NH4)2SO4, KAl(SO4)2 central dot 12H2O, NaCl, and glycine and the nucleation rates of KBr, KCl, NaBr central dot 2H2O, (NH4)2Cl, and (NH4)2SO4 were expressed in terms of the fundamental driving force of crystallization calculated from the activity of supersaturated solutions. The kinetic parameters were compared with those from the commonly used kinetic expression based on the concentration difference. From the viewpoint of thermodynamics, rate expressions based on the chemical potential difference provide accurate kinetic representation over a broad range of supersaturation. The rates estimated using the expression based on the concentration difference coincide with the true rates of crystallization only in the concentration range of low supersaturation and deviate from the true kinetics as the supersaturation increases.

  13. On the relationships between Michaelis–Menten kinetics, reverse Michaelis–Menten kinetics, Equilibrium Chemistry Approximation kinetics and quadratic kinetics

    DOE PAGES

    Tang, J. Y.

    2015-09-03

    The Michaelis–Menten kinetics and the reverse Michaelis–Menten kinetics are two popular mathematical formulations used in many land biogeochemical models to describe how microbes and plants would respond to changes in substrate abundance. However, the criteria of when to use which of the two are often ambiguous. Here I show that these two kinetics are special approximations to the Equilibrium Chemistry Approximation kinetics, which is the first order approximation to the quadratic kinetics that solves the equation of enzyme-substrate complex exactly for a single enzyme single substrate biogeochemical reaction with the law of mass action and the assumption of quasi-steady-state formore » the enzyme-substrate complex and that the product genesis from enzyme-substrate complex is much slower than the equilibration between enzyme-substrate complexes, substrates and enzymes. In particular, I showed that the derivation of the Michaelis–Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis–Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in the Equilibrium Chemistry Approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis–Menten kinetics was found to persistently under-predict the normalized sensitivity ∂ ln v / ∂ ln k 2 + of the reaction velocity v with respect to the maximum product genesis rate k 2 +, persistently over-predict the normalized sensitivity ∂ ln v / ∂ ln k 1 + of v with respect to the intrinsic substrate affinity k 1 +, persistently over-predict the normalized sensitivity ∂ ln v / ∂ ln [ E ] T of v with respect the total enzyme concentration [ E ] T and persistently under-predict the normalized sensitivity ∂ ln v / ∂ ln [ S ] T of v with respect to the total substrate concentration [ S ] T

  14. Modelling dimercaptosuccinic acid (DMSA) plasma kinetics in humans.

    PubMed

    van Eijkeren, Jan C H; Olie, J Daniël N; Bradberry, Sally M; Vale, J Allister; de Vries, Irma; Meulenbelt, Jan; Hunault, Claudine C

    2016-11-01

    No kinetic models presently exist which simulate the effect of chelation therapy on lead blood concentrations in lead poisoning. Our aim was to develop a kinetic model that describes the kinetics of dimercaptosuccinic acid (DMSA; succimer), a commonly used chelating agent, that could be used in developing a lead chelating model. This was a kinetic modelling study. We used a two-compartment model, with a non-systemic gastrointestinal compartment (gut lumen) and the whole body as one systemic compartment. The only data available from the literature were used to calibrate the unknown model parameters. The calibrated model was then validated by comparing its predictions with measured data from three different experimental human studies. The model predicted total DMSA plasma and urine concentrations measured in three healthy volunteers after ingestion of DMSA 10 mg/kg. The model was then validated by using data from three other published studies; it predicted concentrations within a factor of two, representing inter-human variability. A simple kinetic model simulating the kinetics of DMSA in humans has been developed and validated. The interest of this model lies in the future potential to use it to predict blood lead concentrations in lead-poisoned patients treated with DMSA.

  15. Quantification of 18F-fluorocholine kinetics in patients with prostate cancer.

    PubMed

    Verwer, Eline E; Oprea-Lager, Daniela E; van den Eertwegh, Alfons J M; van Moorselaar, Reindert J A; Windhorst, Albert D; Schwarte, Lothar A; Hendrikse, N Harry; Schuit, Robert C; Hoekstra, Otto S; Lammertsma, Adriaan A; Boellaard, Ronald

    2015-03-01

    Choline kinase is upregulated in prostate cancer, resulting in increased (18)F-fluoromethylcholine uptake. This study used pharmacokinetic modeling to validate the use of simplified methods for quantification of (18)F-fluoromethylcholine uptake in a routine clinical setting. Forty-minute dynamic PET/CT scans were acquired after injection of 204 ± 9 MBq of (18)F-fluoromethylcholine, from 8 patients with histologically proven metastasized prostate cancer. Plasma input functions were obtained using continuous arterial blood-sampling as well as using image-derived methods. Manual arterial blood samples were used for calibration and correction for plasma-to-blood ratio and metabolites. Time-activity curves were derived from volumes of interest in all visually detectable lymph node metastases. (18)F-fluoromethylcholine kinetics were studied by nonlinear regression fitting of several single- and 2-tissue plasma input models to the time-activity curves. Model selection was based on the Akaike information criterion and measures of robustness. In addition, the performance of several simplified methods, such as standardized uptake value (SUV), was assessed. Best fits were obtained using an irreversible compartment model with blood volume parameter. Parent fractions were 0.12 ± 0.4 after 20 min, necessitating individual metabolite corrections. Correspondence between venous and arterial parent fractions was low as determined by the intraclass correlation coefficient (0.61). Results for image-derived input functions that were obtained from volumes of interest in blood-pool structures distant from tissues of high (18)F-fluoromethylcholine uptake yielded good correlation to those for the blood-sampling input functions (R(2) = 0.83). SUV showed poor correlation to parameters derived from full quantitative kinetic analysis (R(2) < 0.34). In contrast, lesion activity concentration normalized to the integral of the blood activity concentration over time (SUVAUC) showed good

  16. A model analysis of halogen kinetics: the ClOOCl catalytic cycle revisited

    NASA Astrophysics Data System (ADS)

    Canty, T. P.; Salawitch, R. J.; Wilmouth, D. M.

    2016-12-01

    We revisit prior analyses of simultaneous in situ observations of [ClO] and [ClOOCl] obtained in the Arctic polar vortex to evaluate recommended updates that govern the kinetics of the ClOOCl catalytic cycle. Available laboratory measurements of the ClOOCl absorption cross sections, the ClO+ClO reaction rate constant, and the ClO/ClOOCl equilibrium constant are considered, along with compendium evaluations of these kinetic parameters. We show that the latest recommendations for the kinetics that govern the partitioning of ClO and ClOOCl put forth by the JPL panel in Spring 2016 (JPL 15-10) are in good agreement with atmospheric observations of [ClO] and [ClOOCl]. Hence, we suggest that studies of polar ozone loss adopt these most recent recommendations. The latest JPL recommendation for the equilibrium constant suggests that ClOOCl is less stable than previously assumed, resulting in a shift in the termination temperature of polar ozone loss due to the ClOOCl catalytic cycle. Remaining uncertainties in our knowledge of the kinetics that govern the partitioning of ClO and ClOOCl within the activated vortex, and hence the efficiency of O3 loss by the ClO+ClO cycle, will be best addressed by future laboratory determinations of the absolute cross section of ClOOCl as well as measurements designed to reduce the uncertainty in the rate constant of the ClO+ClO reaction at cold temperatures characteristic of the polar, lower stratosphere.

  17. Thermodynamically Feasible Kinetic Models of Reaction Networks

    PubMed Central

    Ederer, Michael; Gilles, Ernst Dieter

    2007-01-01

    The dynamics of biological reaction networks are strongly constrained by thermodynamics. An holistic understanding of their behavior and regulation requires mathematical models that observe these constraints. However, kinetic models may easily violate the constraints imposed by the principle of detailed balance, if no special care is taken. Detailed balance demands that in thermodynamic equilibrium all fluxes vanish. We introduce a thermodynamic-kinetic modeling (TKM) formalism that adapts the concepts of potentials and forces from irreversible thermodynamics to kinetic modeling. In the proposed formalism, the thermokinetic potential of a compound is proportional to its concentration. The proportionality factor is a compound-specific parameter called capacity. The thermokinetic force of a reaction is a function of the potentials. Every reaction has a resistance that is the ratio of thermokinetic force and reaction rate. For mass-action type kinetics, the resistances are constant. Since it relies on the thermodynamic concept of potentials and forces, the TKM formalism structurally observes detailed balance for all values of capacities and resistances. Thus, it provides an easy way to formulate physically feasible, kinetic models of biological reaction networks. The TKM formalism is useful for modeling large biological networks that are subject to many detailed balance relations. PMID:17208985

  18. Kinetic and thermodynamic studies of the Co(II) and Ni(II) ions removal from aqueous solutions by Ca-Mg phosphates.

    PubMed

    Ivanets, A I; Srivastava, V; Kitikova, N V; Shashkova, I L; Sillanpää, M

    2017-03-01

    The aim of this work was to study the sorption kinetics and thermodynamics of Co(II) and Ni(II) from aqueous solutions by sorbents on the basis of hydrogen (PD-1) and tertiary (PD-2) Ca-Mg phosphates depending on the solution temperature and sorbents chemical composition. Kinetic studies of adsorption of Co(II) and Ni(II) ions onto samples of phosphate sorbents were performed in batch experiment at the temperatures 288, 303, 318 and 333 K. The sorbent dose was fixed at 10 g L -1 , initial pH value 2.6, and contact time varied from 5 to 600 min. The kinetics of Co(II) and Ni(II) adsorption were analyzed by using pseudo-first order, pseudo-second order and intraparticle diffusion models. Thermodynamic parameters (ΔG°, ΔH° and ΔS°) for the sorption of Co(II) and Ni(II) were determined using the Gibbs-Helmholtz equation. The calculated kinetic parameters and corresponding correlation coefficients revealed that Co(II) and Ni(II) uptake process followed the pseudo-second order rate expression. Thermodynamic studies confirmed the spontaneous and endothermic nature of removal process which indicate that sorption of Co(II) and Ni(II) ions onto both phosphate sorbents is favoured at higher temperatures and has the chemisorptive mechanism. The data thus obtained would be useful for practical application of the low cost and highly effective Ca-Mg phosphate sorbents. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Kinetic energy and the equivalence principle

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Carlip, S.

    1998-05-01

    According to the general theory of relativity, kinetic energy contributes to gravitational mass. Surprisingly, the observational evidence for this prediction does not seem to be discussed in the literature. I reanalyze existing experimental data to test the equivalence principle for the kinetic energy of atomic electrons, and show that fairly strong limits on possible violations can be obtained. I discuss the relationship of this result to the occasional claim that {open_quotes}light falls with twice the acceleration of ordinary matter.{close_quotes} {copyright} {ital 1998 American Association of Physics Teachers.}

  20. Oil-generation kinetics for organic facies with Type-II and -IIS kerogen in the Menilite Shales of the Polish Carpathians

    USGS Publications Warehouse

    Lewan, M.D.; Kotarba, M.J.; Curtis, John B.; Wieclaw, D.; Kosakowski, P.

    2006-01-01

    The Menilite Shales (Oligocene) of the Polish Carpathians are the source of low-sulfur oils in the thrust belt and some high-sulfur oils in the Carpathian Foredeep. These oil occurrences indicate that the high-sulfur oils in the Foredeep were generated and expelled before major thrusting and the low-sulfur oils in the thrust belt were generated and expelled during or after major thrusting. Two distinct organic facies have been observed in the Menilite Shales. One organic facies has a high clastic sediment input and contains Type-II kerogen. The other organic facies has a lower clastic sediment input and contains Type-IIS kerogen. Representative samples of both organic facies were used to determine kinetic parameters for immiscible oil generation by isothermal hydrous pyrolysis and S2 generation by non-isothermal open-system pyrolysis. The derived kinetic parameters showed that timing of S2 generation was not as different between the Type-IIS and -II kerogen based on open-system pyrolysis as compared with immiscible oil generation based on hydrous pyrolysis. Applying these kinetic parameters to a burial history in the Skole unit showed that some expelled oil would have been generated from the organic facies with Type-IIS kerogen before major thrusting with the hydrous-pyrolysis kinetic parameters but not with the open-system pyrolysis kinetic parameters. The inability of open-system pyrolysis to determine earlier petroleum generation from Type-IIS kerogen is attributed to the large polar-rich bitumen component in S2 generation, rapid loss of sulfur free-radical initiators in the open system, and diminished radical selectivity and rate constant differences at higher temperatures. Hydrous-pyrolysis kinetic parameters are determined in the presence of water at lower temperatures in a closed system, which allows differentiation of bitumen and oil generation, interaction of free-radical initiators, greater radical selectivity, and more distinguishable rate constants as

  1. Parameter estimation in tree graph metabolic networks.

    PubMed

    Astola, Laura; Stigter, Hans; Gomez Roldan, Maria Victoria; van Eeuwijk, Fred; Hall, Robert D; Groenenboom, Marian; Molenaar, Jaap J

    2016-01-01

    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.

  2. Evaluation of Photopolymerization Kinetics by Means of Transmittance Measurements

    NASA Astrophysics Data System (ADS)

    Bovesecchi, G.; Coppa, P.; Armellin, E.; Cerroni, L.

    2018-04-01

    Polymeric resins are widely used for dental reconstruction, and most resins use camphorquinone as activator of the polymerization reaction, through the absorption of light at a defined wavelength range (from 400 nm to 460 nm). During the photopolymerization curing, transparency of these resins changes and transmittance variation can be detected by photodiode and bolometer measurements. This change can be used as an index of the reaction rate, and the kinetic parameter k (reaction rate) can be evaluated from transmittance data by means of nonlinear regression. The relation between k and the light intensity impinging on the resin sample can thus be obtained. In the present work, tests were carried out using the resin Enamel Plus HFO GE2. Results reveal the presence of two different polymerization reactions at two different intensity ranges. The obtained k values were used to predict the most suited curing times for different light intensities. The proposed methodology can be applied to different dental reconstruction materials, provided that the material is partially transparent and that its transparency changes during the polymerization reaction.

  3. Effective potential kinetic theory for strongly coupled plasmas

    NASA Astrophysics Data System (ADS)

    Baalrud, Scott D.; Daligault, Jérôme

    2016-11-01

    The effective potential theory (EPT) is a recently proposed method for extending traditional plasma kinetic and transport theory into the strongly coupled regime. Validation from experiments and molecular dynamics simulations have shown it to be accurate up to the onset of liquid-like correlation parameters (corresponding to Γ ≃ 10-50 for the one-component plasma, depending on the process of interest). Here, this theory is briefly reviewed along with comparisons between the theory and molecular dynamics simulations for self-diffusivity and viscosity of the one-component plasma. A number of new results are also provided, including calculations of friction coefficients, energy exchange rates, stopping power, and mobility. The theory is also cast in the Landau and Fokker-Planck kinetic forms, which may prove useful for enabling efficient kinetic computations.

  4. 4-wave dynamics in kinetic wave turbulence

    NASA Astrophysics Data System (ADS)

    Chibbaro, Sergio; Dematteis, Giovanni; Rondoni, Lamberto

    2018-01-01

    A general Hamiltonian wave system with quartic resonances is considered, in the standard kinetic limit of a continuum of weakly interacting dispersive waves with random phases. The evolution equation for the multimode characteristic function Z is obtained within an ;interaction representation; and a perturbation expansion in the small nonlinearity parameter. A frequency renormalization is performed to remove linear terms that do not appear in the 3-wave case. Feynman-Wyld diagrams are used to average over phases, leading to a first order differential evolution equation for Z. A hierarchy of equations, analogous to the Boltzmann hierarchy for low density gases is derived, which preserves in time the property of random phases and amplitudes. This amounts to a general formalism for both the N-mode and the 1-mode PDF equations for 4-wave turbulent systems, suitable for numerical simulations and for investigating intermittency. Some of the main results which are developed here in detail have been tested numerically in a recent work.

  5. Kinetics from Replica Exchange Molecular Dynamics Simulations.

    PubMed

    Stelzl, Lukas S; Hummer, Gerhard

    2017-08-08

    Transitions between metastable states govern many fundamental processes in physics, chemistry and biology, from nucleation events in phase transitions to the folding of proteins. The free energy surfaces underlying these processes can be obtained from simulations using enhanced sampling methods. However, their altered dynamics makes kinetic and mechanistic information difficult or impossible to extract. Here, we show that, with replica exchange molecular dynamics (REMD), one can not only sample equilibrium properties but also extract kinetic information. For systems that strictly obey first-order kinetics, the procedure to extract rates is rigorous. For actual molecular systems whose long-time dynamics are captured by kinetic rate models, accurate rate coefficients can be determined from the statistics of the transitions between the metastable states at each replica temperature. We demonstrate the practical applicability of the procedure by constructing master equation (Markov state) models of peptide and RNA folding from REMD simulations.

  6. Production of a sterile species: Quantum kinetics

    NASA Astrophysics Data System (ADS)

    Boyanovsky, D.; Ho, C. M.

    2007-10-01

    Production of a sterile species is studied within an effective model of active-sterile neutrino mixing in a medium in thermal equilibrium. The quantum kinetic equations for the distribution functions and coherences are obtained from two independent methods: the effective action and the quantum master equation. The decoherence time scale for active-sterile oscillations is τdec=2/Γaa, but the evolution of the distribution functions is determined by the two different time scales associated with the damping rates of the quasiparticle modes in the medium: Γ1=Γaacos⁡2θm; Γ2=Γaasin⁡2θm where Γaa is the interaction rate of the active species in the absence of mixing and θm the mixing angle in the medium. These two time scales are widely different away from Mikheyev-Smirnov-Wolfenstein resonances and preclude the kinetic description of active-sterile production in terms of a simple rate equation. We give the complete set of quantum kinetic equations for the active and sterile populations and coherences and discuss in detail the various approximations. A generalization of the active-sterile transition probability in a medium is provided via the quantum master equation. We derive explicitly the usual quantum kinetic equations in terms of the “polarization vector” and show their equivalence to those obtained from the quantum master equation and effective action.

  7. Influence of NiO on the crystallization kinetics of near stoichiometric cordierite glasses nucleated with TiO2

    NASA Astrophysics Data System (ADS)

    Goel, Ashutosh; Shaaban, Essam R.; Ribeiro, Manuel J.; Melo, Francisco C. L.; Ferreira, José M. F.

    2007-09-01

    This work presents the effect of NiO on the thermal behavior and the crystallization kinetics of glasses lying near the stoichiometric cordierite composition nucleated with TiO2. Three glasses with NiO content varying between 1 and 5 mol% have been synthesized in Pt crucibles. Activation energies for structural relaxation and viscous flow have been calculated using the data obtained from differential thermal analysis (DTA). Kinetic fragility of the glasses along with other thermal parameters has been calculated. Non-isothermal crystallization kinetic studies have been employed to study the mechanism of crystallization in all three glasses. The crystallization sequence in the glasses has been followed by x-ray diffraction analysis of the heat treated glass samples in the temperature range of 800-1200 °C. μ-cordierite has been observed to be the first crystalline phase in all the glass samples after heat treatment at 850 °C, while NiO plays an important role in determining the crystallization sequence at higher temperatures, leading to the formation of α-cordierite.

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

    PubMed

    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.

  9. The effect of heart motion on parameter bias in dynamic cardiac SPECT

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ross, S.G.; Gullberg, G.T.; Huesman, R.H.

    1996-12-31

    Dynamic cardiac SPECT can be used to estimate kinetic rate parameters which describe the wash-in and wash-out of tracer activity between the blood and the myocardial tissue. These kinetic parameters can in turn be correlated to myocardial perfusion. There are, however, many physical aspects associated with dynamic SPECT which can introduce errors into the estimates. This paper describes a study which investigates the effect of heart motion on kinetic parameter estimates. Dynamic SPECT simulations are performed using a beating version of the MCAT phantom. The results demonstrate that cardiac motion has a significant effect on the blood, tissue, and backgroundmore » content of regions of interest. This in turn affects estimates of wash-in, while it has very little effect on estimates of wash-out. The effect of cardiac motion on parameter estimates appears not to be as great as effects introduced by photon noise and geometric collimator response. It is also shown that cardiac motion results in little extravascular contamination of the left ventricle blood region of interest.« less

  10. On the relationships between the Michaelis–Menten kinetics, reverse Michaelis–Menten kinetics, equilibrium chemistry approximation kinetics, and quadratic kinetics

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tang, J. Y.

    The Michaelis–Menten kinetics and the reverse Michaelis–Menten kinetics are two popular mathematical formulations used in many land biogeochemical models to describe how microbes and plants would respond to changes in substrate abundance. However, the criteria of when to use either of the two are often ambiguous. Here I show that these two kinetics are special approximations to the equilibrium chemistry approximation (ECA) kinetics, which is the first-order approximation to the quadratic kinetics that solves the equation of an enzyme–substrate complex exactly for a single-enzyme and single-substrate biogeochemical reaction with the law of mass action and the assumption of a quasi-steadymore » state for the enzyme–substrate complex and that the product genesis from enzyme–substrate complex is much slower than the equilibration between enzyme–substrate complexes, substrates, and enzymes. In particular, I show that the derivation of the Michaelis–Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis–Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in deriving the equilibrium chemistry approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis–Menten kinetics was found to persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln k 2 + of the reaction velocity v with respect to the maximum product genesis rate k 2 +, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln k 1 + of v with respect to the intrinsic substrate affinity k 1 +, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln [ E] T of v with respect the total enzyme concentration [ E] T, and persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln [ S] T of v with respect to the total substrate

  11. On the relationships between the Michaelis–Menten kinetics, reverse Michaelis–Menten kinetics, equilibrium chemistry approximation kinetics, and quadratic kinetics

    DOE PAGES

    Tang, J. Y.

    2015-12-01

    The Michaelis–Menten kinetics and the reverse Michaelis–Menten kinetics are two popular mathematical formulations used in many land biogeochemical models to describe how microbes and plants would respond to changes in substrate abundance. However, the criteria of when to use either of the two are often ambiguous. Here I show that these two kinetics are special approximations to the equilibrium chemistry approximation (ECA) kinetics, which is the first-order approximation to the quadratic kinetics that solves the equation of an enzyme–substrate complex exactly for a single-enzyme and single-substrate biogeochemical reaction with the law of mass action and the assumption of a quasi-steadymore » state for the enzyme–substrate complex and that the product genesis from enzyme–substrate complex is much slower than the equilibration between enzyme–substrate complexes, substrates, and enzymes. In particular, I show that the derivation of the Michaelis–Menten kinetics does not consider the mass balance constraint of the substrate, and the reverse Michaelis–Menten kinetics does not consider the mass balance constraint of the enzyme, whereas both of these constraints are taken into account in deriving the equilibrium chemistry approximation kinetics. By benchmarking against predictions from the quadratic kinetics for a wide range of substrate and enzyme concentrations, the Michaelis–Menten kinetics was found to persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln k 2 + of the reaction velocity v with respect to the maximum product genesis rate k 2 +, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln k 1 + of v with respect to the intrinsic substrate affinity k 1 +, persistently overpredict the normalized sensitivity ∂ ln v / ∂ ln [ E] T of v with respect the total enzyme concentration [ E] T, and persistently underpredict the normalized sensitivity ∂ ln v / ∂ ln [ S] T of v with respect to the total substrate

  12. Budgets of divergent and rotational kinetic energy during two periods of intense convection

    NASA Technical Reports Server (NTRS)

    Buechler, D. E.; Fuelberg, H. E.

    1986-01-01

    The derivations of the energy budget equations for divergent and rotational components of kinetic energy are provided. The intense convection periods studied are: (1) synoptic scale data of 3 or 6 hour intervals and (2) mesoalphascale data every 3 hours. Composite energies and averaged budgets for the periods are presented; the effects of random data errors on derived energy parameters is investigated. The divergent kinetic energy and rotational kinetic energy budgets are compared; good correlation of the data is observed. The kinetic energies and budget terms increase with convective development; however, the conversion of the divergent and rotational energies are opposite.

  13. Kinetic modeling of active plasma resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Oberrath, Jens

    2016-09-01

    The term ``active plasma resonance spectroscopy'' (APRS) refers to a plasma diagnostic method which employs the natural ability of plasmas to resonate close to the plasma frequency. Essential for this method is an appropriate model to determine the relation between the resonance parameters and demanded plasma parameters. Measurements with these probes in plasmas of a few Pa typically show a broadening of the spectrum that cannot be predicted by a fluid model. Thus, a kinetic model is necessary. A general kinetic model of APRS probes, which can be described in electorstatic approximation, valid for all pressures has been presented. This model is used to analyze the dynamic behavior of such probes by means of functional analytic methods. One of the main results is, that the system response function Y (ω) is given in terms of the matrix elements of the resolvent of the dynamic operator evaluated for values on the imaginary axis. The spectrum of this operator is continuous which implies a new phenomenon related to anomalous or non-collisional dissipation. Based on the scalar product, which is motivated by the kinetic free energy, the non-collisional damping can be interpreted: In a periodic state, the probe constantly emits plasma waves which propagate to ``infinity''. The free energy simply leaves the ``observation range'' of the probe which is recorded as damping. The kinetic damping, which depends on the mean kinetic energy of the electrons, is responsible for the broadening of a resonance peak in the measured spectrum of APRS probes. The ultimate goal is to determine explicit formulas for the relation between the broadening of the resonance peak and the ``equivalent electron temperature'', especially in the case of the spherical Impedance Probe and the Multipole Resonance Probe. Gratitude is expressed to the internal funding of Leuphana University, the BMBF via PluTO+, the DFG via Collaborative Research Center TR 87, and the Ruhr University Research School.

  14. Thermal stability and degradation kinetics of kenaf/sol-gel silica hybrid

    NASA Astrophysics Data System (ADS)

    Yusof, F. A. M.; Hashim, A. S.; Tajudin, Z.

    2017-12-01

    Thermal stability and degradation kinetics of kenaf/sol-gel silica hybrid materials was investigated by thermogravimetric analysis (TGA). Model-free iso-conversion Flynn-Wall-Ozawa (FWO) and Coats-Redfern-modified (CRm) were chosen to evaluate the activation energy of the kenaf (KF) and kenaf/sol-gel silica (KFS) at heating rates (β) of 10, 20, 30 and 40 °C/min. The results shows that an apparent activation energy was increased for the kenaf/sol-gel silica hybrid (211.59 kJ/mol for FWO and 191.55 kJ/mol for CRm) as compared to kenaf fiber (202.84 kJ/mol for FWO and 186.20 kJ/mol for CRm). Other parameters such as integral procedure decomposition temperature (IPDT), final residual weight (Rf), temperature of maximum degradation rate (Tmax) and residual at maximum temperature (RTmax) were obtained from TGA curves, additionally confirmed the thermal stability of the kenaf/sol-gel silica hybrid. These activation energy values and other findings developed the simplified approach in order to understand the thermal stability and degradation kinetics behavior of kenaf/sol-gel silica hybrid materials.

  15. Quantitative Evaluation of the Total Magnetic Moments of Colloidal Magnetic Nanoparticles: A Kinetics-based Method.

    PubMed

    Liu, Haiyi; Sun, Jianfei; Wang, Haoyao; Wang, Peng; Song, Lina; Li, Yang; Chen, Bo; Zhang, Yu; Gu, Ning

    2015-06-08

    A kinetics-based method is proposed to quantitatively characterize the collective magnetization of colloidal magnetic nanoparticles. The method is based on the relationship between the magnetic force on a colloidal droplet and the movement of the droplet under a gradient magnetic field. Through computational analysis of the kinetic parameters, such as displacement, velocity, and acceleration, the magnetization of colloidal magnetic nanoparticles can be calculated. In our experiments, the values measured by using our method exhibited a better linear correlation with magnetothermal heating, than those obtained by using a vibrating sample magnetometer and magnetic balance. This finding indicates that this method may be more suitable to evaluate the collective magnetism of colloidal magnetic nanoparticles under low magnetic fields than the commonly used methods. Accurate evaluation of the magnetic properties of colloidal nanoparticles is of great importance for the standardization of magnetic nanomaterials and for their practical application in biomedicine. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Growth of vertically aligned nanowires in metal-oxide nanocomposites: kinetic Monte-Carlo modeling versus experiments.

    PubMed

    Hennes, M; Schuler, V; Weng, X; Buchwald, J; Demaille, D; Zheng, Y; Vidal, F

    2018-04-26

    We employ kinetic Monte-Carlo simulations to study the growth process of metal-oxide nanocomposites obtained via sequential pulsed laser deposition. Using Ni-SrTiO3 (Ni-STO) as a model system, we reduce the complexity of the computational problem by choosing a coarse-grained approach mapping Sr, Ti and O atoms onto a single effective STO pseudo-atom species. With this ansatz, we scrutinize the kinetics of the sequential synthesis process, governed by alternating deposition and relaxation steps, and analyze the self-organization propensity of Ni atoms into straight vertically aligned nanowires embedded in the surrounding STO matrix. We finally compare the predictions of our binary toy model with experiments and demonstrate that our computational approach captures fundamental aspects of self-assembled nanowire synthesis. Despite its simplicity, our modeling strategy successfully describes the impact of relevant parameters like the concentration or laser frequency on the final nanoarchitecture of metal-oxide thin films grown via pulsed laser deposition.

  17. Effects of Different PER Translational Kinetics on the Dynamics of a Core Circadian Clock Model

    PubMed Central

    Nieto, Paula S.; Revelli, Jorge A.; Garbarino-Pico, Eduardo; Condat, Carlos A.; Guido, Mario E.; Tamarit, Francisco A.

    2015-01-01

    Living beings display self-sustained daily rhythms in multiple biological processes, which persist in the absence of external cues since they are generated by endogenous circadian clocks. The period (per) gene is a central player within the core molecular mechanism for keeping circadian time in most animals. Recently, the modulation PER translation has been reported, both in mammals and flies, suggesting that translational regulation of clock components is important for the proper clock gene expression and molecular clock performance. Because translational regulation ultimately implies changes in the kinetics of translation and, therefore, in the circadian clock dynamics, we sought to study how and to what extent the molecular clock dynamics is affected by the kinetics of PER translation. With this objective, we used a minimal mathematical model of the molecular circadian clock to qualitatively characterize the dynamical changes derived from kinetically different PER translational mechanisms. We found that the emergence of self-sustained oscillations with characteristic period, amplitude, and phase lag (time delays) between per mRNA and protein expression depends on the kinetic parameters related to PER translation. Interestingly, under certain conditions, a PER translation mechanism with saturable kinetics introduces longer time delays than a mechanism ruled by a first-order kinetics. In addition, the kinetic laws of PER translation significantly changed the sensitivity of our model to parameters related to the synthesis and degradation of per mRNA and PER degradation. Lastly, we found a set of parameters, with realistic values, for which our model reproduces some experimental results reported recently for Drosophila melanogaster and we present some predictions derived from our analysis. PMID:25607544

  18. Effects of different per translational kinetics on the dynamics of a core circadian clock model.

    PubMed

    Nieto, Paula S; Revelli, Jorge A; Garbarino-Pico, Eduardo; Condat, Carlos A; Guido, Mario E; Tamarit, Francisco A

    2015-01-01

    Living beings display self-sustained daily rhythms in multiple biological processes, which persist in the absence of external cues since they are generated by endogenous circadian clocks. The period (per) gene is a central player within the core molecular mechanism for keeping circadian time in most animals. Recently, the modulation PER translation has been reported, both in mammals and flies, suggesting that translational regulation of clock components is important for the proper clock gene expression and molecular clock performance. Because translational regulation ultimately implies changes in the kinetics of translation and, therefore, in the circadian clock dynamics, we sought to study how and to what extent the molecular clock dynamics is affected by the kinetics of PER translation. With this objective, we used a minimal mathematical model of the molecular circadian clock to qualitatively characterize the dynamical changes derived from kinetically different PER translational mechanisms. We found that the emergence of self-sustained oscillations with characteristic period, amplitude, and phase lag (time delays) between per mRNA and protein expression depends on the kinetic parameters related to PER translation. Interestingly, under certain conditions, a PER translation mechanism with saturable kinetics introduces longer time delays than a mechanism ruled by a first-order kinetics. In addition, the kinetic laws of PER translation significantly changed the sensitivity of our model to parameters related to the synthesis and degradation of per mRNA and PER degradation. Lastly, we found a set of parameters, with realistic values, for which our model reproduces some experimental results reported recently for Drosophila melanogaster and we present some predictions derived from our analysis.

  19. [Comparison of kinematic and kinetic parameters between the locomotion patterns in nordic walking, walking and running].

    PubMed

    Kleindienst, F I; Michel, K J; Schwarz, J; Krabbe, B

    2006-03-01

    Based on a higher cardio-pulmonary and cardio-vascular benefit and a promised reduction of mechanical load of the musculoskeletal system Nordic Walking (NW) shows an increased market potential. The present study should investigate whether there are biomechanical differences between the locomotion patterns NW, walking and running. Moreover possible resultant load differences should be determined. Eleven subjects, who were already experienced with the NW-technique, participated in this experiment. The kinematic data were collected using two high-speed camera systems from posterior and from lateral at the same time. Simultaneously the ground reaction forces were recorded. The kinematic and the kinetic data reveal differences between the three analyzed locomotion patterns. For NW as well as walking the mechanical load of the lower extremity is lower compared to running. None of the kinematic parameters suggest a "physiological benefit" of NW compared to walking. Moreover NW shows higher vertical and horizontal forces during landing. Exclusively the lower vertical force peak during push off indicates a lower mechanical load for NW in comparison to walking. Consequently it is questionable is NW -- based on its promised "biomechanical benefits" compared to walking -- should be still recommended for overweight people and for people with existing musculoskeletal problems of the lower limb.

  20. Incorporation of MRI-AIF Information For Improved Kinetic Modelling of Dynamic PET Data

    NASA Astrophysics Data System (ADS)

    Sari, Hasan; Erlandsson, Kjell; Thielemans, Kris; Atkinson, David; Ourselin, Sebastien; Arridge, Simon; Hutton, Brian F.

    2015-06-01

    In the analysis of dynamic PET data, compartmental kinetic analysis methods require an accurate knowledge of the arterial input function (AIF). Although arterial blood sampling is the gold standard of the methods used to measure the AIF, it is usually not preferred as it is an invasive method. An alternative method is the simultaneous estimation method (SIME), where physiological parameters and the AIF are estimated together, using information from different anatomical regions. Due to the large number of parameters to estimate in its optimisation, SIME is a computationally complex method and may sometimes fail to give accurate estimates. In this work, we try to improve SIME by utilising an input function derived from a simultaneously obtained DSC-MRI scan. With the assumption that the true value of one of the six parameter PET-AIF model can be derived from an MRI-AIF, the method is tested using simulated data. The results indicate that SIME can yield more robust results when the MRI information is included with a significant reduction in absolute bias of Ki estimates.