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Sample records for yield kinetic parameters

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

    PubMed

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

    2012-01-01

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

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

    PubMed

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

    2017-03-02

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

  3. Kinetic parameters from thermogravimetric analysis

    NASA Technical Reports Server (NTRS)

    Kiefer, Richard L.

    1993-01-01

    High performance polymeric materials are finding increased use in aerospace applications. Proposed high speed aircraft will require materials to withstand high temperatures in an oxidative atmosphere for long periods of time. It is essential that accurate estimates be made of the performance of these materials at the given conditions of temperature and time. Temperatures of 350 F (177 C) and times of 60,000 to 100,000 hours are anticipated. In order to survey a large number of high performance polymeric materials on a reasonable time scale, some form of accelerated testing must be performed. A knowledge of the rate of a process can be used to predict the lifetime of that process. Thermogravimetric analysis (TGA) has frequently been used to determine kinetic information for degradation reactions in polymeric materials. Flynn and Wall studied a number of methods for using TGA experiments to determine kinetic information in polymer reactions. Kinetic parameters, such as the apparent activation energy and the frequency factor, can be determined in such experiments. Recently, researchers at the McDonnell Douglas Research Laboratory suggested that a graph of the logarithm of the frequency factor against the apparent activation energy can be used to predict long-term thermo-oxidative stability for polymeric materials. Such a graph has been called a kinetic map. In this study, thermogravimetric analyses were performed in air to study the thermo-oxidative degradation of several high performance polymers and to plot their kinetic parameters on a kinetic map.

  4. Obtaining and estimating kinetic parameters from the literature.

    PubMed

    Neves, Susana R

    2011-09-13

    This Teaching Resource provides lecture notes, slides, and a student assignment for a lecture on strategies for the development of mathematical models. Many biological processes can be represented mathematically as systems of ordinary differential equations (ODEs). Simulations with these mathematical models can provide mechanistic insight into the underlying biology of the system. A prerequisite for running simulations, however, is the identification of kinetic parameters that correspond closely with the biological reality. This lecture presents an overview of the steps required for the development of kinetic ODE models and describes experimental methods that can yield kinetic parameters and concentrations of reactants, which are essential for the development of kinetic models. Strategies are provided to extract necessary parameters from published data. The homework assignment requires students to find parameters appropriate for a well-studied biological regulatory system, convert these parameters into appropriate units, and interpret how different values of these parameters may lead to different biological behaviors.

  5. Determination of kinetic parameters for biomass combustion.

    PubMed

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

    2016-09-01

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

  6. Kinetic parameters for source driven systems

    SciTech Connect

    Dulla, S.; Ravetto, P.; Carta, M.; D'Angelo, A.

    2006-07-01

    The definition of the characteristic kinetic parameters of a subcritical source-driven system constitutes an interesting problem in reactor physics with important consequences for practical applications. Consistent and physically meaningful values of the parameters allow to obtain accurate results from kinetic simulation tools and to correctly interpret kinetic experiments. For subcritical systems a preliminary problem arises for the adoption of a suitable weighting function to be used in the projection procedure to derive a point model. The present work illustrates a consistent factorization-projection procedure which leads to the definition of the kinetic parameters in a straightforward manner. The reactivity term is introduced coherently with the generalized perturbation theory applied to the source multiplication factor ks, which is thus given a physical role in the kinetic model. The effective prompt lifetime is introduced on the assumption that a neutron generation can be initiated by both the fission process and the source emission. Results are presented for simplified configurations to fully comprehend the physical features and for a more complicated highly decoupled system treated in transport theory. (authors)

  7. Kinetic parameters estimation in an anaerobic digestion process using successive quadratic programming.

    PubMed

    Aceves-Lara, C A; Aguilar-Garnica, E; Alcaraz-González, V; González-Reynoso, O; Steyer, J P; Dominguez-Beltran, J L; González-Alvarez, V

    2005-01-01

    In this work, an optimization method is implemented in an anaerobic digestion model to estimate its kinetic parameters and yield coefficients. This method combines the use of advanced state estimation schemes and powerful nonlinear programming techniques to yield fast and accurate estimates of the aforementioned parameters. In this method, we first implement an asymptotic observer to provide estimates of the non-measured variables (such as biomass concentration) and good guesses for the initial conditions of the parameter estimation algorithm. These results are then used by the successive quadratic programming (SQP) technique to calculate the kinetic parameters and yield coefficients of the anaerobic digestion process. The model, provided with the estimated parameters, is tested with experimental data from a pilot-scale fixed bed reactor treating raw industrial wine distillery wastewater. It is shown that SQP reaches a fast and accurate estimation of the kinetic parameters despite highly noise corrupted experimental data and time varying inputs variables. A statistical analysis is also performed to validate the combined estimation method. Finally, a comparison between the proposed method and the traditional Marquardt technique shows that both yield similar results; however, the calculation time of the traditional technique is considerable higher than that of the proposed method.

  8. Kinetic parameters for the thermal inactivation of quality-related enzymes in carrots and potatoes.

    PubMed

    Anthon, Gordon E; Barrett, Diane M

    2002-07-03

    Kinetic parameters for the thermal inactivation of several enzymes in carrot and potato homogenates have been determined. In carrots the most heat-resistant activity was polygalacturonase, followed by peroxidase and pectinmethylesterase. In potatoes peroxidase was the most resistant, followed by pectin methylesterase, polyphenol oxidase, and lipoxygenase. There were several notable similarities between the inactivation kinetics in the two vegetables. In both cases peroxidase activity gave simple first-order inactivation kinetics but yielded a curved Arrhenius plot for the temperature dependence. Pectin methylesterase in both commodities consisted of a labile and a resistant form. The relative amounts of the two forms and the temperature dependences for their inactivation were also similar.

  9. 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.

  10. A model of crosslink kinetics in the expanding plant cell wall: yield stress and enzyme action

    PubMed Central

    Dyson, R.J.; Band, L.R.; Jensen, O.E.

    2012-01-01

    The plant primary cell wall is a composite material containing stiff cellulose microfibrils that are embedded within a pectin matrix and crosslinked through a network of hemicellulose polymers. This microstructure endows the wall with nonlinear anisotropic mechanical properties and allows enzymatic regulation of expansive cell growth. We present a mathematical model of hemicellulose crosslink dynamics in an expanding cell wall incorporating strain-enhanced breakage and enzyme-mediated crosslink kinetics. The model predicts the characteristic yielding behaviour in the relationship between stress and strain-rate seen experimentally, and suggests how the effective yield and extensibility of the wall depend on microstructural parameters and on the action of enzymes of the XTH and expansin families. The model suggests that the yielding behaviour encapsulated in the classical Lockhart equation can be explained by the strongly nonlinear dependence of crosslink breakage rate on crosslink elongation. The model also demonstrates how enzymes that target crosslink binding can be effective in softening the wall in its pre-yield state, whereas its post-yield extensibility is determined primarily by the pectin matrix. PMID:22584249

  11. The kinetic origin of delayed yielding in metallic glasses

    NASA Astrophysics Data System (ADS)

    Ye, Y. F.; Liu, X. D.; Wang, S.; Fan, J.; Liu, C. T.; Yang, Y.

    2016-06-01

    Recent experiments showed that irreversible structural change or plasticity could occur in metallic glasses (MGs) even within the apparent elastic limit after a sufficiently long waiting time. To explain this phenomenon, a stochastic shear transformation model is developed based on a unified rate theory to predict delayed yielding in MGs, which is validated afterwards through extensive atomistic simulations carried out on different MGs. On a fundamental level, an analytic framework is established in this work that links time, stress, and temperature altogether into a general yielding criterion for MGs.

  12. Devolatilization kinetic parameters of beneficiated coal-based products

    SciTech Connect

    Patel, R.L.; Nsakala, N.Y.; Raymond, D.R.; Hargrove, M.J.

    1993-12-31

    A comprehensive program sponsored by the Department of Energy`s Pittsburgh Energy Technology Center (PETC) is being carried out by Combustion Engineering, Inc. (CE), to assess the performance and economic impacts of firing beneficiated coal-based fuels (BCFs) in pre-NSPS coal-fired boilers and existing oil and gas fired boilers. The BCFs are produced from several advanced coal cleaning processes developed by other contractors under the DOE Coal Preparation Program. CE`s laminar-flow Drop Tube Furnace System-1 (DTFS-1) was used to test six BCFs produced from three Eastern bituminous coals (from Illinois No. 6, Pittsburgh 18 and Upper Freeport seams) in two advanced coal cleaning processes (microbubble Flotation Process and Selective Oil Agglomeration Process). Testing consisted of thermally decomposing size-graded BCF products in nitrogen atmosphere in the 1900-2650{degrees}F temperature range and residence times of up to about 0.8 sec. These data were used to derive the devolatilization kinetic parameters of the BCF products. Oxidation kinetic parameters also had been derived in the DTFS-1 from these six fuels. Test conditions under all circumstances were designed to simulate some of the conditions prevailing in suspension firing of pulverized coal. This paper summarizes the devolatilization kinetic parameter results obtained from this study. The results are compared with those obtained previously in this laboratory and with some of the results presented in the open literature. These devolatilization kinetic parameters are of generic nature and, as such, can be used by anyone engaged in mathematical modeling of combustion processes.

  13. Kinetics and Yields of Pesticide Biodegradation at Low Substrate Concentrations and under Conditions Restricting Assimilable Organic Carbon

    PubMed Central

    Hammes, Frederik; Egli, Thomas; Kohler, Hans-Peter E.

    2014-01-01

    The fundamentals of growth-linked biodegradation occurring at low substrate concentrations are poorly understood. Substrate utilization kinetics and microbial growth yields are two critically important process parameters that can be influenced by low substrate concentrations. Standard biodegradation tests aimed at measuring these parameters generally ignore the ubiquitous occurrence of assimilable organic carbon (AOC) in experimental systems which can be present at concentrations exceeding the concentration of the target substrate. The occurrence of AOC effectively makes biodegradation assays conducted at low substrate concentrations mixed-substrate assays, which can have profound effects on observed substrate utilization kinetics and microbial growth yields. In this work, we introduce a novel methodology for investigating biodegradation at low concentrations by restricting AOC in our experiments. We modified an existing method designed to measure trace concentrations of AOC in water samples and applied it to systems in which pure bacterial strains were growing on pesticide substrates between 0.01 and 50 mg liter−1. We simultaneously measured substrate concentrations by means of high-performance liquid chromatography with UV detection (HPLC-UV) or mass spectrometry (MS) and cell densities by means of flow cytometry. Our data demonstrate that substrate utilization kinetic parameters estimated from high-concentration experiments can be used to predict substrate utilization at low concentrations under AOC-restricted conditions. Further, restricting AOC in our experiments enabled accurate and direct measurement of microbial growth yields at environmentally relevant concentrations for the first time. These are critical measurements for evaluating the degradation potential of natural or engineered remediation systems. Our work provides novel insights into the kinetics of biodegradation processes and growth yields at low substrate concentrations. PMID:24317077

  14. Reconstruction of linear kinetic parameters directly from projection PET data

    NASA Astrophysics Data System (ADS)

    Angelis, G. I.; Tziortzi, A. C.; Tsoumpas, C.

    2011-09-01

    Dynamic Positron Emission Tomography (PET) data provide functional information. Usually, this is measured in the form of pharmacokinetic parameters derived from the temporal response of each region. Recent trends have shown that when pharmacokinetic parameters are estimated directly from the projection data, they are less affected by noise. This work investigates an existing parametric maximum likelihood expectation maximization algorithm applied to [18F]DOPA data using reference-tissue input function. The study reveals how direct reconstruction of pharmacokinetic parameters from the measured data can be performed optimally. It explains how to optimize the speed of the standard iterative algorithm and it compares the results with the existing FBP method. The improvement of the quality of the parametric images preserving quantification suggests the usefulness of direct estimation of the kinetic parameters. This algorithm is freely available within the open-source library STIR 2.1.

  15. 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.

  16. [Photosynthetic Parameters Inversion Algorithm Study Based on Chlorophyll Fluorescence Induction Kinetics Curve].

    PubMed

    Qiu, Xiao-han; Zhang, Yu-jun; Yin, Gao-fang; Shi, Chao-yi; Yu, Xiao-ya; Zhao, Nan-jing; Liu, Wen-qing

    2015-08-01

    The fast chlorophyll fluorescence induction curve contains rich information of photosynthesis. It can reflect various information of vegetation, such as, the survival status, the pathological condition and the physiology trends under the stress state. Through the acquisition of algae fluorescence and induced optical signal, the fast phase of chlorophyll fluorescence kinetics curve was fitted. Based on least square fitting method, we introduced adaptive minimum error approaching method for fast multivariate nonlinear regression fitting toward chlorophyll fluorescence kinetics curve. We realized Fo (fixedfluorescent), Fm (maximum fluorescence yield), σPSII (PSII functional absorption cross section) details parameters inversion and the photosynthetic parameters inversion of Chlorella pyrenoidosa. And we also studied physiological variation of Chlorella pyrenoidosa under the stress of Cu(2+).

  17. 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.

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

    SciTech Connect

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

    2012-01-01

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

  19. Measurement of the slope parameter for the {eta}{yields}3{pi}{sup 0} decay in the pp{yields}pp{eta} reaction

    SciTech Connect

    Bashkanov, M.; Clement, H.; Meier, R.; Skorodko, T.; Wagner, G. J.; Bogoslawsky, D.; Ivanov, G.; Jiganov, E.; Kuznetsov, A.; Morosov, B.; Petukhov, Y.; Povtorejko, A.; Tikhomirov, V.; Calen, H.; Ekstroem, C.; Fransson, K.; Kupsc, A.; Marciniewski, P.; Ruber, R. J. M. Y.; Capellaro, F.

    2007-10-15

    The CELSIUS-WASA setup is used to measure the 3{pi}{sup 0} decay of {eta} mesons produced in pp interactions with beam kinetic energies of 1.36 and 1.45 GeV. The efficiency-corrected Dalitz plot and density distributions for this decay are shown, together with a fit of the quadratic slope parameter {alpha} yielding {alpha}=-0.026{+-}0.010(stat){+-}0.010(syst). This value is compared to recent experimental results and theoretical predictions.

  20. Pyrolysis of Sawdust, Rice Husk and Sugarcane Bagasse: Kinetic Modeling and Estimation of Kinetic Parameters using Different Optimization Tools

    NASA Astrophysics Data System (ADS)

    Khonde, Ruta Dhanram; Chaurasia, Ashish Subhash

    2015-04-01

    The present study provides the kinetic model to describe the pyrolysis of sawdust, rice-husk and sugarcane bagasse as biomass. The kinetic scheme used for modelling of primary pyrolysis consisting of the two parallel reactions giving gaseous volatiles and solid char. Estimation of kinetic parameters for pyrolysis process has been carried out for temperature range of 773-1,173 K. As there are serious issues regarding non-convergence of some of the methods or solutions converging to local-optima, the proposed kinetic model is optimized to predict the best values of kinetic parameters for the system using three approaches—Two-dimensional surface fitting non-linear regression technique, MS-Excel Solver Tool and COMSOL software. The model predictions are in agreement with experimental data over a wide range of pyrolysis conditions. The estimated value of kinetic parameters are compared with earlier researchers and found to be matching well.

  1. Estimation of kinetic model parameters in fluorescence optical diffusion tomography.

    PubMed

    Milstein, Adam B; Webb, Kevin J; Bouman, Charles A

    2005-07-01

    We present a technique for reconstructing the spatially dependent dynamics of a fluorescent contrast agent in turbid media. The dynamic behavior is described by linear and nonlinear parameters of a compartmental model or some other model with a deterministic functional form. The method extends our previous work in fluorescence optical diffusion tomography by parametrically reconstructing the time-dependent fluorescent yield. The reconstruction uses a Bayesian framework and parametric iterative coordinate descent optimization, which is closely related to Gauss-Seidel methods. We demonstrate the method with a simulation study.

  2. Cell kinetics and biochemical parameters in breast cancer.

    PubMed

    Becciolini, A; Porciani, S; Balzi, M; Lanini, A; Scubla, E; Pacini, P; Benucci, A; Distante, V

    1992-01-01

    The study analyzes biochemical and cell kinetic parameters to characterize solid tumor growth in humans. The concentrations of polyamines, CEA, the thymidine labeling index (T.L.I.) and the mitotic index (M.I.) were determined on fragments of neoplastic tissue from 18 patients with breast carcinoma. Urinary polyamines were evaluated in the same patients. Two groups of patients were distinguished according to the median value of the with high T.L.I., M.I. and tissue polyamines were significantly higher than in the group with low T.L.I., whereas tissue CEA was lower, though in a not statistically significant way. Urinary polyamines showed no variations between groups. These preliminary results showed that T.L.I. levels were higher in patients who relapsed during a 4-year follow-up than in patients achieving complete remission and remaining disease free. Results concerning polyamine concentration showed that the tissue polyamine level in breast carcinoma indicated proliferative activity, but this does not seem to be valuable for current prognostic purposes.

  3. Co-pyrolysis characteristics of microalgae Isochrysis and Chlorella: Kinetics, biocrude yield and interaction.

    PubMed

    Zhao, Bingwei; Wang, Xin; Yang, Xiaoyi

    2015-12-01

    Co-pyrolysis characteristics of Isochrysis (high lipid) and Chlorella (high protein) were investigated qualitatively and quantitatively based on DTG curves, biocrude yield and composition by individual pyrolysis and co-pyrolysis. DTG curves in co-pyrolysis have been compared accurately with those in individual pyrolysis. An interaction has been detected at 475-500°C in co-pyrolysis based on biocrude yields, and co-pyrolysis reaction mechanism appear three-dimensional diffusion in comparison with random nucleation followed by growth in individual pyrolysis based on kinetic analysis. There is no obvious difference in the maximum biocrude yields for individual pyrolysis and co-pyrolysis, but carboxylic acids (IC21) decreased and N-heterocyclic compounds (IC12) increased in co-pyrolysis. Simulation results of biocrude yield by Components Biofuel Model and Kinetics Biofuel Model indicate that the processes of co-pyrolysis comply with those of individual pyrolysis in solid phase by and large. Variation of percentage content in co-pyrolysis and individual pyrolysis biocrude indicated interaction in gas phase.

  4. Influence of the coating level on the heterogeneous ozonolysis kinetics and product yields of chlorpyrifos ethyl adsorbed on sand particles.

    PubMed

    El Masri, Ahmad; Laversin, Hélène; Chakir, Abdelkhaleq; Roth, Estelle

    2016-12-01

    Heterogeneous oxidation of chlorpyrifos ethyl (CLP) coated sand particles by gaseous ozone was studied. Mono-size sand was coated with CLP at different coating levels between 10 and 100 μg g(-1) and exposed to ozone. Results were analyzed thanks to Gas Surface Reaction and Surface Layer Reaction Models. Kinetic parameters derived from these models were analyzed and led to several conclusions. The equilibrium constant of O3 between the gas phase and the CLP-coated sand was independent on the sand contamination level. Ozone seems to have similar affinity for coated or uncoated sand surface. Meanwhile, the kinetic parameters decreased with an increasing coating level. Chlorpyrifos Oxon, (CLPO) has been identified and quantified as an ozonolysis product. The product yield of CLPO remains constant (53 ± 10%) for the different coating level. The key parameter influencing the CLP reactivity towards ozone was the CLP-coating level. This dependence had a great influence on the lifetime of the CLP coated on sand particles, with respect to ozone, which could reach several years at high contamination level.

  5. High-yield hydrogen production from biomass by in vitro metabolic engineering: Mixed sugars coutilization and kinetic modeling

    PubMed Central

    Rollin, Joseph A.; Martin del Campo, Julia; Myung, Suwan; Sun, Fangfang; You, Chun; Bakovic, Allison; Castro, Roberto; Chandrayan, Sanjeev K.; Wu, Chang-Hao; Adams, Michael W. W.; Senger, Ryan S.; Zhang, Y.-H. Percival

    2015-01-01

    The use of hydrogen (H2) as a fuel offers enhanced energy conversion efficiency and tremendous potential to decrease greenhouse gas emissions, but producing it in a distributed, carbon-neutral, low-cost manner requires new technologies. Herein we demonstrate the complete conversion of glucose and xylose from plant biomass to H2 and CO2 based on an in vitro synthetic enzymatic pathway. Glucose and xylose were simultaneously converted to H2 with a yield of two H2 per carbon, the maximum possible yield. Parameters of a nonlinear kinetic model were fitted with experimental data using a genetic algorithm, and a global sensitivity analysis was used to identify the enzymes that have the greatest impact on reaction rate and yield. After optimizing enzyme loadings using this model, volumetric H2 productivity was increased 3-fold to 32 mmol H2⋅L−1⋅h−1. The productivity was further enhanced to 54 mmol H2⋅L−1⋅h−1 by increasing reaction temperature, substrate, and enzyme concentrations—an increase of 67-fold compared with the initial studies using this method. The production of hydrogen from locally produced biomass is a promising means to achieve global green energy production. PMID:25848015

  6. High-yield hydrogen production from biomass by in vitro metabolic engineering: Mixed sugars coutilization and kinetic modeling

    DOE PAGES

    Rollin, Joseph A.; Martin del Campo, Julia; Myung, Suwan; ...

    2015-04-06

    The use of hydrogen (H2) as a fuel offers enhanced energy conversion efficiency and tremendous potential to decrease greenhouse gas emissions, but producing it in a distributed, carbon-neutral, low-cost manner requires new technologies. Herein we demonstrate the complete conversion of glucose and xylose from plant biomass to H2 and CO2 based on an in vitro synthetic enzymatic pathway. Glucose and xylose were simultaneously converted to H2 with a yield of two H2 per carbon, the maximum possible yield. Parameters of a nonlinear kinetic model were fitted with experimental data using a genetic algorithm, and a global sensitivity analysis was usedmore » to identify the enzymes that have the greatest impact on reaction rate and yield. After optimizing enzyme loadings using this model, volumetric H2 productivity was increased 3-fold to 32 mmol H2∙L₋1∙h₋1. The productivity was further enhanced to 54 mmol H2∙L₋1∙h₋1 by increasing reaction temperature, substrate, and enzyme concentrations—an increase of 67-fold compared with the initial studies using this method. The production of hydrogen from locally produced biomass is a promising means to achieve global green energy production.« less

  7. High-yield hydrogen production from biomass by in vitro metabolic engineering: Mixed sugars coutilization and kinetic modeling

    SciTech Connect

    Rollin, Joseph A.; Martin del Campo, Julia; Myung, Suwan; Sun, Fangfang; You, Chun; Bakovic, Allison; Castro, Roberto; Chandrayan, Sanjeev K.; Wu, Chang-Hao; Adams, Michael W. W.; Senger, Ryan S.; Zhang, Y. -H. Percival

    2015-04-06

    The use of hydrogen (H2) as a fuel offers enhanced energy conversion efficiency and tremendous potential to decrease greenhouse gas emissions, but producing it in a distributed, carbon-neutral, low-cost manner requires new technologies. Herein we demonstrate the complete conversion of glucose and xylose from plant biomass to H2 and CO2 based on an in vitro synthetic enzymatic pathway. Glucose and xylose were simultaneously converted to H2 with a yield of two H2 per carbon, the maximum possible yield. Parameters of a nonlinear kinetic model were fitted with experimental data using a genetic algorithm, and a global sensitivity analysis was used to identify the enzymes that have the greatest impact on reaction rate and yield. After optimizing enzyme loadings using this model, volumetric H2 productivity was increased 3-fold to 32 mmol H2∙L₋1∙h₋1. The productivity was further enhanced to 54 mmol H2∙L₋1∙h₋1 by increasing reaction temperature, substrate, and enzyme concentrations—an increase of 67-fold compared with the initial studies using this method. The production of hydrogen from locally produced biomass is a promising means to achieve global green energy production.

  8. Dilute-sulfuric acid pretreatment of corn stover in pilot-scale reactor: investigation of yields, kinetics, and enzymatic digestibilities of solids.

    PubMed

    Schell, Daniel J; Farmer, Jody; Newman, Millie; McMillan, James D

    2003-01-01

    Corn stover is a domestic feedstock that has potential to produce significant quantities of fuel ethanol and other bioenergy and biobased products. However, comprehensive yield and carbon mass balance information and validated kinetic models for dilute-sulfuric acid (H2SO4) pretreatment of corn stover have not been available. This has hindered the estimation of process economics and also limited the ability to perform technoeconomic modeling to guide research. To better characterize pretreatment and assess its kinetics, we pretreated corn stover in a continuous 1 t/d reactor. Corn stover was pretreated at 20% (w/w) solids concentration over a range of conditions encompassing residence times of 3-12 min, temperatures of 165- 195 degrees C, and H2SO4 concentrations of 0.5-1.4% (w/w). Xylan conversion yield and carbon mass balance data were collected at each run condition. Performance results were used to estimate kinetic model parameters assuming biphasic hemicellulose hydrolysis and a hydrolysis mechanism incorporating formation of intermediate xylo-oligomers. In addition, some of the pretreated solids were tested in a simultaneous saccharification and fermentation (SSF) process to measure the reactivity of their cellulose component to enzymatic digestion by cellulase enzymes. Monomeric xylose yields of 69-71% and total xylose yields (monomers and oligomers) of 70-77% were achieved with performance level depending on pretreatment severity. Cellulose conversion yields in SSF of 80-87% were obtained for some of the most digestible pretreated solids.

  9. 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.

  10. Engineering topology and kinetics of sucrose metabolism in Saccharomyces cerevisiae for improved ethanol yield.

    PubMed

    Basso, Thiago O; de Kok, Stefan; Dario, Marcelo; do Espirito-Santo, Júlio Cézar A; Müller, Gabriela; Schlölg, Paulo S; Silva, Carlos P; Tonso, Aldo; Daran, Jean-Marc; Gombert, Andreas K; van Maris, Antonius J A; Pronk, Jack T; Stambuk, Boris U

    2011-11-01

    Sucrose is a major carbon source for industrial bioethanol production by Saccharomyces cerevisiae. In yeasts, two modes of sucrose metabolism occur: (i) extracellular hydrolysis by invertase, followed by uptake and metabolism of glucose and fructose, and (ii) uptake via sucrose-proton symport followed by intracellular hydrolysis and metabolism. Although alternative start codons in the SUC2 gene enable synthesis of extracellular and intracellular invertase isoforms, sucrose hydrolysis in S. cerevisiae predominantly occurs extracellularly. In anaerobic cultures, intracellular hydrolysis theoretically enables a 9% higher ethanol yield than extracellular hydrolysis, due to energy costs of sucrose-proton symport. This prediction was tested by engineering the promoter and 5' coding sequences of SUC2, resulting in predominant (94%) cytosolic localization of invertase. In anaerobic sucrose-limited chemostats, this iSUC2-strain showed an only 4% increased ethanol yield and high residual sucrose concentrations indicated suboptimal sucrose-transport kinetics. To improve sucrose-uptake affinity, it was subjected to 90 generations of laboratory evolution in anaerobic, sucrose-limited chemostat cultivation, resulting in a 20-fold decrease of residual sucrose concentrations and a 10-fold increase of the sucrose-transport capacity. A single-cell isolate showed an 11% higher ethanol yield on sucrose in chemostat cultures than an isogenic SUC2 reference strain, while transcriptome analysis revealed elevated expression of AGT1, encoding a disaccharide-proton symporter, and other maltose-related genes. After deletion of both copies of the duplicated AGT1, growth characteristics reverted to that of the unevolved SUC2 and iSUC2 strains. This study demonstrates that engineering the topology of sucrose metabolism is an attractive strategy to improve ethanol yields in industrial processes.

  11. Yields and decay kinetics of the solvated electron in pulse radiolysis of 1-alkanols

    NASA Astrophysics Data System (ADS)

    Kalachandra, S.; Farhataziz; Foyt, David C.

    The products of the yields of the solvated electron in 1-alkanols, G(e alk-, and the extinction coefficient of e alk- at its absorption maximum, ɛ(e alk-) max, relative to the same product for the hydrated electron, G(e aq-)ɛ(e aq-) max, for a 60 nsec irradiation at room temperature are given in parentheses after the name of each 1-alkanol: methanol (0.38), ethanol (0.42), 1-propanol (0.33), 1-butanol (0.30), 1-pentanol (0.28), 1-hexanol (0.31), 1-heptanol (0.27), 1-octanol (0.29), 1-nonanol (0.26), and 1-decanol (0.24). The decay kinetics of e alk- after 60 or 400 nsec of pulse irradiation of 1-alkanols, C 1-C 10, fit competitive pseudo-first order and second order (initial concentrations of both reactants the same) processes. Except for 1-propanol to 1-pentanol, the observed second order specific rates are a function of the dose per pulse. A mechanism is proposed for the above given decay kinetics of e alk- in C 1C 10 1-alkanols.

  12. 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…

  13. Determination of μd chemistry kinetic parameters for the MuSun Experiment

    NASA Astrophysics Data System (ADS)

    Raha, Nandita

    2014-09-01

    The MuSun experiment at PSI will measure the muon doublet capture rate Λd in ultra pure deuterium gas to 1.5% precision from the measured decay-electron time distribution. This reaction cleanly determines the strength of the two-nucleon weak axial current interaction. The kinetic parameters of the μd chemistry are essential for extracting Λd, which in turn are determined from the process of muon catalyzed fusion in deuterium. This process yields 3 He recoils and 2.45 MeV monoenergetic neutrons from the reaction ddμ -->3 He + n + μ . Encoded in the time dependence of the fusion products are the ddμ molecular formation rates from the F = 1 / 2 , 3 / 2 hyperfine states (λd and λq) and the hyperfine transition rate (λqd) from the higher-energy F = 3 / 2 state to the lower-energy F = 1 / 2 state. This work concentrates on the analysis of the fusion neutrons, which are detected by an array of eight neutron detectors. Pulse shape discrimination was used to distinguish neutrons from background gamma rays. A least squared fit to the time spectrum of the fusion neutrons determines the μd chemistry kinetic parameters λqd and the ratio λq / λd. The MuSun experiment at PSI will measure the muon doublet capture rate Λd in ultra pure deuterium gas to 1.5% precision from the measured decay-electron time distribution. This reaction cleanly determines the strength of the two-nucleon weak axial current interaction. The kinetic parameters of the μd chemistry are essential for extracting Λd, which in turn are determined from the process of muon catalyzed fusion in deuterium. This process yields 3 He recoils and 2.45 MeV monoenergetic neutrons from the reaction ddμ -->3 He + n + μ . Encoded in the time dependence of the fusion products are the ddμ molecular formation rates from the F = 1 / 2 , 3 / 2 hyperfine states (λd and λq) and the hyperfine transition rate (λqd) from the higher-energy F = 3 / 2 state to the lower-energy F = 1 / 2 state. This work concentrates

  14. Parameter Optimization for Enhancement of Ethanol Yield by Atmospheric Pressure DBD-Treated Saccharomyces cerevisiae

    NASA Astrophysics Data System (ADS)

    Dong, Xiaoyu; Yuan, Yulian; Tang, Qian; Dou, Shaohua; Di, Lanbo; Zhang, Xiuling

    2014-01-01

    In this study, Saccharomyces cerevisiae (S. cerevisiae) was exposed to dielectric barrier discharge plasma (DBD) to improve its ethanol production capacity during fermentation. Response surface methodology (RSM) was used to optimize the discharge-associated parameters of DBD for the purpose of maximizing the ethanol yield achieved by DBD-treated S. cerevisiae. According to single factor experiments, a mathematical model was established using Box-Behnken central composite experiment design, with plasma exposure time, power supply voltage, and exposed-sample volume as impact factors and ethanol yield as the response. This was followed by response surface analysis. Optimal experimental parameters for plasma discharge-induced enhancement in ethanol yield were plasma exposure time of 1 min, power voltage of 26 V, and an exposed sample volume of 9 mL. Under these conditions, the resulting yield of ethanol was 0.48 g/g, representing an increase of 33% over control.

  15. DD3MAT - a code for yield criteria anisotropy parameters identification.

    NASA Astrophysics Data System (ADS)

    Barros, P. D.; Carvalho, P. D.; Alves, J. L.; Oliveira, M. C.; Menezes, L. F.

    2016-08-01

    This work presents the main strategies and algorithms adopted in the DD3MAT inhouse code, specifically developed for identifying the anisotropy parameters. The algorithm adopted is based on the minimization of an error function, using a downhill simplex method. The set of experimental values can consider yield stresses and r -values obtained from in-plane tension, for different angles with the rolling direction (RD), yield stress and r -value obtained for biaxial stress state, and yield stresses from shear tests performed also for different angles to RD. All these values can be defined for a specific value of plastic work. Moreover, it can also include the yield stresses obtained from in-plane compression tests. The anisotropy parameters are identified for an AA2090-T3 aluminium alloy, highlighting the importance of the user intervention to improve the numerical fit.

  16. Parameter Optimization of Nitriding Process Using Chemical Kinetics

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  17. 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.

  18. Simulating large-scale crop yield by using perturbed-parameter ensemble method

    NASA Astrophysics Data System (ADS)

    Iizumi, T.; Yokozawa, M.; Sakurai, G.; Nishimori, M.

    2010-12-01

    Toshichika Iizumi, Masayuki Yokozawa, Gen Sakurai, Motoki Nishimori Agro-Meteorology Division, National Institute for Agro-Environmental Sciences, Japan Abstract One of concerning issues of food security under changing climate is to predict the inter-annual variation of crop production induced by climate extremes and modulated climate. To secure food supply for growing world population, methodology that can accurately predict crop yield on a large scale is needed. However, for developing a process-based large-scale crop model with a scale of general circulation models (GCMs), 100 km in latitude and longitude, researchers encounter the difficulties in spatial heterogeneity of available information on crop production such as cultivated cultivars and management. This study proposed an ensemble-based simulation method that uses a process-based crop model and systematic parameter perturbation procedure, taking maize in U.S., China, and Brazil as examples. The crop model was developed modifying the fundamental structure of the Soil and Water Assessment Tool (SWAT) to incorporate the effect of heat stress on yield. We called the new model PRYSBI: the Process-based Regional-scale Yield Simulator with Bayesian Inference. The posterior probability density function (PDF) of 17 parameters, which represents the crop- and grid-specific features of the crop and its uncertainty under given data, was estimated by the Bayesian inversion analysis. We then take 1500 ensemble members of simulated yield values based on the parameter sets sampled from the posterior PDF to describe yearly changes of the yield, i.e. perturbed-parameter ensemble method. The ensemble median for 27 years (1980-2006) was compared with the data aggregated from the county yield. On a country scale, the ensemble median of the simulated yield showed a good correspondence with the reported yield: the Pearson’s correlation coefficient is over 0.6 for all countries. In contrast, on a grid scale, the correspondence

  19. Steam pressure disruption of municipal solid waste enhances anaerobic digestion kinetics and biogas yield.

    PubMed

    Liu, H W; Walter, H K; Vogt, G M; Vogt, H S; Holbein, B E

    2002-01-20

    Biomass waste, including municipal solid waste (MSW), contains lignocellulosic-containing fiber components that are not readily available as substrates for anaerobic digestion due to the physical shielding of cellulose imparted by the nondigestible lignin. Consequently, a substantial portion of the potentially available carbon is not converted to methane and the incompletely digested residues from anaerobic digestion generally require additional processing prior to their return to the environment. We investigated and developed steam pressure disruption as a treatment step to render lignocellulosic-rich biomass more digestible and as a means for increasing methane energy recovery. The rapid depressurization after steam heating (240 degrees C, 5 min.) of the nondigested residues following a 30-day primary digestion of MSW caused a visible disruption of fibers and release of soluble organic components. The disrupted material, after reinoculation, provided a rapid burst in methane production at rates double those observed in the initial digestion. This secondary digestion proceeded without a lag phase in gas production, provided approximately 40% additional methane yields, and was accompanied by a approximately 40% increase in volatile solids reduction. The secondary digestate was found to be enriched in lignin and significantly depleted in cellulose and hemi-cellulose components when compared to primary digestate. Thus, steam pressure disruption treatment rendered lignocellulosic substrates readily accessible to anaerobic digestion bacteria and improved both the kinetics of biogas production and the overall methane yield from MSW. Steam pressure disruption is central to a new anaerobic digestion process approach including sequential digestion stages and integrated energy recovery, to improve process yields, provide cogenerated energy for process needs, and to provide effective reuse and recycling of waste biomass materials.

  20. 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

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

    NASA Astrophysics Data System (ADS)

    Brito, Paula; Antunes, Fernando

    2014-10-01

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

  2. Estimation of kinetic and thermodynamic ligand-binding parameters using computational strategies.

    PubMed

    Deganutti, Giuseppe; Moro, Stefano

    2017-03-31

    Kinetic and thermodynamic ligand-protein binding parameters are gaining growing importance as key information to consider in drug discovery. The determination of the molecular structures, using particularly x-ray and NMR techniques, is crucial for understanding how a ligand recognizes its target in the final binding complex. However, for a better understanding of the recognition processes, experimental studies of ligand-protein interactions are needed. Even though several techniques can be used to investigate both thermodynamic and kinetic profiles for a ligand-protein complex, these procedures are very often laborious, time consuming and expensive. In the last 10 years, computational approaches have enormous potential in providing insights into each of the above effects and in parsing their contributions to the changes in both kinetic and thermodynamic binding parameters. The main purpose of this review is to summarize the state of the art of computational strategies for estimating the kinetic and thermodynamic parameters of a ligand-protein binding.

  3. Kinetics of batch anaerobic co-digestion of poultry litter and wheat straw including a novel strategy of estimation of endogenous decay and yield coefficients using numerical integration.

    PubMed

    Shen, Jiacheng; Zhu, Jun

    2016-10-01

    The kinetics of anaerobic co-digestion of poultry litter and wheat straw has not been widely reported in the literature. Since endogenous decay and yield coefficients are two basic parameters for the design of anaerobic digesters, they are currently estimated only by continues experiments. In this study, numerical integration was employed to develop a novel strategy to estimate endogenous decay and yield coefficients using initial and final liquid data combined with methane volumes produced over time in batch experiments. To verify this method, the kinetics of batch anaerobic co-digestion of poultry litter and wheat straw at different TS and VS levels was investigated, with the corresponding endogenous decay and (non-observed) yield coefficients in the exponential periods determined to be between 0.74 × 10(-3) and 6.1 × 10(-3) d(-1), and between 0.0259 and 0.108 g VSS (g VS)(-1), respectively. A general Gompertz model developed early for bio-product could be used to simulate the methane volume profile in the co-digestion. The same model parameters obtained from the methane model combined with the corresponding yield coefficients could also be used to describe the VSS generation and VS destruction.

  4. 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…

  5. Mathematical and statistical analysis of the effect of boron on yield parameters of wheat

    SciTech Connect

    Rawashdeh, Hamzeh; Sala, Florin; Boldea, Marius

    2015-03-10

    The main objective of this research is to investigate the effect of foliar applications of boron at different growth stages on yield and yield parameters of wheat. The contribution of boron in achieving yield parameters is described by second degree polynomial equations, with high statistical confidence (p<0.01; F theoretical < F calculated, according to ANOVA test, for Alfa = 0.05). Regression analysis, based on R{sup 2} values obtained, made it possible to evaluate the particular contribution of boron to the realization of yield parameters. This was lower for spike length (R{sup 2} = 0.812), thousand seeds weight (R{sup 2} = 0.850) and higher in the case of the number of spikelets (R{sup 2} = 0.936) and the number of seeds on a spike (R{sup 2} = 0.960). These results confirm that boron plays an important part in achieving the number of seeds on a spike in the case of wheat, as the contribution of this element to the process of flower fertilization is well-known. In regards to productivity elements, the contribution of macroelements to yield quantity is clear, the contribution of B alone being R{sup 2} = 0.868.

  6. Validity of repeated initial rise thermoluminescence kinetic parameter determinations

    SciTech Connect

    Kierstead, J.A.; Levy, P.W.

    1990-01-01

    The validity of thermoluminescence (TL) analysis by repeated initial rise measurements has been studied by computer simulation. Thermoluminescence described by 1st Order, 2nd Order, General One Trap and Interactive TL Kinetics was investigated. In the simulation each of the repeated temperature increase and decrease cycles contains a linear temperature increase followed by a decrease appropriate for radiative cooling, i.e. the latter is approximated by a decreasing exponential. The activation energies computed from the simulated emission are readily compared with those used to compute the TL emission. In all cases studied, the repeated initial rise technique provides reliable results only for single peak glow curves or for glow curves containing peaks that do not overlap and, if sufficiently separated, the lowest temperature peak in multipeak curves. Also the temperatures, or temperature cycles corresponding to correct activation energies occur on the low temperature side of the normal glow curve, often well below the peak temperature. A variety of misleading and/or incorrect results an be obtained when the repeated initial rise technique is applied to TL systems that produce overlapping peaks in the usual glow curve. 6 refs., 10 figs.

  7. Performance, blood parameters and meat yield in broiler chickens supplemented with Mexican oregano oil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This study was conducted to evaluate the inclusion of Mexican oregano oil (MOO) Lippia berlandieri Schauer in broiler diets during grow-out on performance, blood parameters, and meat yield. One hundred and sixty-two one-day-old broilers, randomly divided into three equal groups (treatments): CON =...

  8. Surrogate models for identifying robust, high yield regions of parameter space for ICF implosion simulations

    NASA Astrophysics Data System (ADS)

    Humbird, Kelli; Peterson, J. Luc; Brandon, Scott; Field, John; Nora, Ryan; Spears, Brian

    2016-10-01

    Next-generation supercomputer architecture and in-transit data analysis have been used to create a large collection of 2-D ICF capsule implosion simulations. The database includes metrics for approximately 60,000 implosions, with x-ray images and detailed physics parameters available for over 20,000 simulations. To map and explore this large database, surrogate models for numerous quantities of interest are built using supervised machine learning algorithms. Response surfaces constructed using the predictive capabilities of the surrogates allow for continuous exploration of parameter space without requiring additional simulations. High performing regions of the input space are identified to guide the design of future experiments. In particular, a model for the yield built using a random forest regression algorithm has a cross validation score of 94.3% and is consistently conservative for high yield predictions. The model is used to search for robust volumes of parameter space where high yields are expected, even given variations in other input parameters. Surrogates for additional quantities of interest relevant to ignition are used to further characterize the high yield regions. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344, Lawrence Livermore National Security, LLC. LLNL-ABS-697277.

  9. Radiative Corrections to Asymmetry Parameter in the {Omega}{sup -{yields}{Lambda}}+K{sup -} Decay

    SciTech Connect

    Queijeiro, A.

    2010-07-29

    We compute the radiative corrections, to first order in the fine structure constant {alpha}, to the asymmetry parameter {alpha}{sub {Omega}}of the {Omega}{sup -{yields}{Lambda}}+K{sup -} decay. We use previous results where Sirlin's procedure is used to separate the radiative corrections into two parts, one independent model contribution and a model dependent one.

  10. Determination of Kinetic Parameters from Steady-State Microdisk Voltammograms

    DTIC Science & Technology

    1988-01-01

    characteristic parameters of voltammetric curves (i.e., constants without special expertise, instruments, or mathematical limiting current, half -wave...was then used to calculate based and subjects suitable data to alternative ways of analysis. the reversible half -wave potential (eq 14) assuming DR/Do...apparent half -wave potential to more positive values (for oxidations) and decreases the slope and lineant, Irk 0of the plot. Equation II may be used in two

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

    PubMed

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

    2017-04-01

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

  12. Variability of kinetic parameters due to biomass acclimation: case of para-nitrophenol biodegradation.

    PubMed

    Rezouga, Fériel; Hamdi, Moktar; Sperandio, Mathieu

    2009-11-01

    The study regards para-nitrophenol (p-NP) removal by a mixed culture in a batch reactor under aerobic conditions performed at low ratio substrate (p-NP) to p-NP degrading microorganisms (0.09 < I(0)/(X(B,PNP))(0) < 0.80 g COD(PNP)g VSS(-1)). p-NP biodegradation was modelled with a dual-biomass kinetic including Haldane formalism. The purpose was to examine the effect of operating conditions of acclimation phases in the kinetic parameters estimated by respirometric measurements. The experiments were conducted with a series of successive additions of p-NP and a biogenic substrate (Ss) in different proportions (0 < R = Ss/I < 6.6). To place emphasis on decisive role played by frequency and amount of p-NP supply, a parallel was drawn with continuous processes, characterising acclimation cycles by different organic loading rate (207 < OLR < 1490 mg COD(PNP) l(-1) d(-1)). During acclimation, results showed progressively decreasing half saturation constant (K(s)(PNP)) values (11.4-1.21 mg CODl(-1)) whereas inhibition coefficient K(I)(PNP) increased (72.4-289 mg CODl(-1)), as the specific degradation rate increased. The inverse behaviour was observed during starvation periods. At the end of acclimation, higher values of growth yield (0.39 < Y(PNP) < 0.63 mg COD(X) mg COD(PNP)(-1)) and maximum growth rate (1.09 < mu(max)(PNP) < 2.01 d(-1)) were obtained for cycles with low R.

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

    SciTech Connect

    Wemhoff, A P; Burnham, A K; de Supinski, B; Sexton, J; Gunnels, J

    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 been provided to guide the reader through a general calibrating process.

  14. Theory of kinetic arrest, elasticity, and yielding in dense binary mixtures of rods and spheres.

    PubMed

    Jadrich, Ryan; Schweizer, Kenneth S

    2012-12-01

    We extend the quiescent and stressed versions of naïve mode coupling theory to treat the dynamical arrest, shear modulus, and absolute yielding of particle mixtures where one or more species is a nonrotating nonspherical object. The theory is applied in detail to dense isotropic "chemically matched" mixtures of variable aspect ratio rods and spheres that interact via repulsive and short range attractive site-site pair potentials. A remarkably rich ideal kinetic arrest behavior is predicted with up to eight "dynamical phases" emerging: an ergodic fluid, partially localized states where the spheres remain fluid but the rods can be a gel, repulsive glass or attractive glass, doubly localized glasses and gels, a porous rod gel plus sphere glass, and a narrow window where a type of rod glass and gel localization coexist. Dynamical complexity increases with rod length and the introduction of attractive forces between all species which both enhance gel network formation. Multiple dynamic reentrant features and triple points are predicted, and each dynamic phase has unique particle localization characteristics and mechanical properties. Orders of magnitude variation of the linear shear modulus and absolute yield stress are found as rod length, mixture composition and the detailed nature of interparticle attractions are varied. The interplay of total (high) mixture packing fraction and composition at fixed temperature is also briefly studied. The present work provides a foundation to study more complex rod-sphere mixtures of both biological and synthetic interest that include physical features such as interaction site size asymmetry, rod-sphere specific attractions, and/or Coulomb repulsion.

  15. Theory of kinetic arrest, elasticity, and yielding in dense binary mixtures of rods and spheres

    NASA Astrophysics Data System (ADS)

    Jadrich, Ryan; Schweizer, Kenneth S.

    2012-12-01

    We extend the quiescent and stressed versions of naïve mode coupling theory to treat the dynamical arrest, shear modulus, and absolute yielding of particle mixtures where one or more species is a nonrotating nonspherical object. The theory is applied in detail to dense isotropic “chemically matched” mixtures of variable aspect ratio rods and spheres that interact via repulsive and short range attractive site-site pair potentials. A remarkably rich ideal kinetic arrest behavior is predicted with up to eight “dynamical phases” emerging: an ergodic fluid, partially localized states where the spheres remain fluid but the rods can be a gel, repulsive glass or attractive glass, doubly localized glasses and gels, a porous rod gel plus sphere glass, and a narrow window where a type of rod glass and gel localization coexist. Dynamical complexity increases with rod length and the introduction of attractive forces between all species which both enhance gel network formation. Multiple dynamic reentrant features and triple points are predicted, and each dynamic phase has unique particle localization characteristics and mechanical properties. Orders of magnitude variation of the linear shear modulus and absolute yield stress are found as rod length, mixture composition and the detailed nature of interparticle attractions are varied. The interplay of total (high) mixture packing fraction and composition at fixed temperature is also briefly studied. The present work provides a foundation to study more complex rod-sphere mixtures of both biological and synthetic interest that include physical features such as interaction site size asymmetry, rod-sphere specific attractions, and/or Coulomb repulsion.

  16. A comparison of continuum and kinetic simulations of microplasmas integrated with high secondary yield cathodes

    NASA Astrophysics Data System (ADS)

    Alamatsaz, Arghavan; Verma, Abhishek Kumar; Venkattraman, Ayyaswamy

    2016-10-01

    During the last two decades, microplasmas have become an active area of research in the field of low-temperature plasma science and engineering with a wide range of applications including electronics, nanomaterial synthesis and metamaterials to name a few. Kinetic and continuum methods are commonly employed numerical simulation techniques to study the low temperature plasmas. The uncertainty and imprecision associated with input parameters used in these models impose a constraint on fidelity of the simulation results. In this work, these computational techniques are compared in the context of modeling microplasmas driven by cathodes with high secondary electron emission coefficient. Simulations of argon microplasmas operating at a moderate pd (pressure*distance between electrodes) are performed using particle-in-cell with Monte Carlo collisions (PIC-MCC), and fluid model using the full momentum equations for both electrons and ions. Results obtained for plasma density, potential, electric field and electron temperature using continuum simulations are compared with the corresponding PIC-MCC simulations as benchmark. These numerical experiments provide insights on importance of input parameters in fluid model for high fidelity simulation of microplasma applications.

  17. Respirometric assays of two different MBR (microfiltration and ultrafiltration) to obtain kinetic and stoichiometric parameters.

    PubMed

    Ruiz, L M; Arévalo, J; Parada, J; González, D; Moreno, B; Pérez, J; Gómez, M A

    2011-01-01

    A comparison of two different medium scale MBRs (ultrafiltration and microfiltration) using respirometric methods has been achieved. The ultrafiltration membrane plant (0.034 microm pore size) maintained recirculation sludge flow at seven times the influent flow, and membranes were backwashed every 5 min and chemically cleaned weekly. The microfiltration membrane plant (0.4 microm pore size) maintained recirculation sludge flow at four times the influent flow, membrane-relax was applied after the production phase and membranes were chemically cleaned in the event of high trans-membrane pressure. Both technologies showed a similar performance with regard to heterotrophic kinetic and stoichiometric parameters and organic matter effluent concentrations. The influent was characterized by means of its COD fractions and the average removal percentages for COD concentrations were around 97% for both plants in spite of influent COD fluctuation, temperature variations and sludge retention time (SRT) evolution. Both SRT evolution and temperature affect the heterotrophic yield (Y(H)) and the decay coefficient (bH) in the same range for both plants. Y(H) values of over 0.8 mg COD/mg COD were obtained during the unsteady periods, while under steady state conditions these values fell to less than 0.4 mg COD/mg COD. bH by contrast reached values of less than 0.05 d(-1).

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

    PubMed

    Chen, Dengyu; Zhou, Jianbin; Zhang, Qisheng

    2014-10-01

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

  19. Genetic parameters for milk, fat and protein yields in Murrah buffaloes (Bubalus bubalis Artiodactyla, Bovidae)

    PubMed Central

    2010-01-01

    The objective of the present study was to estimate genetic parameters for test-day milk, fat and protein yields and 305-day-yields in Murrah buffaloes. 4,757 complete lactations of Murrah buffaloes were analyzed. Co-variance components were estimated by the restricted maximum likelihood method. The models included additive direct genetic and permanent environmental effects as random effects, and the fixed effects of contemporary group, milking number and age of the cow at calving as linear and quadratic covariables. Contemporary groups were defined by herd-year-month of test for test-day yields and by herd-year-season of calving for 305-day yields. The heritability estimates obtained by two-trait analysis ranged from 0.15 to 0.24 for milk, 0.16 to 0.23 for protein and 0.13 to 0.22 for fat, yields. Genetic and phenotypic correlations were all positive. The observed population additive genetic variation indicated that selection might be an effective tool in changing population means in milk, fat and protein yields. PMID:21637608

  20. A robust methodology for kinetic model parameter estimation for biocatalytic reactions.

    PubMed

    Al-Haque, Naweed; Santacoloma, Paloma A; Neto, Watson; Tufvesson, Pär; Gani, Rafiqul; Woodley, John M

    2012-01-01

    Effective estimation of parameters in biocatalytic reaction kinetic expressions are very important when building process models to enable evaluation of process technology options and alternative biocatalysts. The kinetic models used to describe enzyme-catalyzed reactions generally include several parameters, which are strongly correlated with each other. State-of-the-art methodologies such as nonlinear regression (using progress curves) or graphical analysis (using initial rate data, for example, the Lineweaver-Burke plot, Hanes plot or Dixon plot) often incorporate errors in the estimates and rarely lead to globally optimized parameter values. In this article, a robust methodology to estimate parameters for biocatalytic reaction kinetic expressions is proposed. The methodology determines the parameters in a systematic manner by exploiting the best features of several of the current approaches. The parameter estimation problem is decomposed into five hierarchical steps, where the solution of each of the steps becomes the input for the subsequent step to achieve the final model with the corresponding regressed parameters. The model is further used for validating its performance and determining the correlation of the parameters. The final model with the fitted parameters is able to describe both initial rate and dynamic experiments. Application of the methodology is illustrated with a case study using the ω-transaminase catalyzed synthesis of 1-phenylethylamine from acetophenone and 2-propylamine.

  1. 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)

  2. Determination of electron transfer kinetic parameters by fourier transform electrochemical impedance spectroscopic analysis.

    PubMed

    Chang, Byoung-Yong; Hong, Sung-Young; Yoo, Jung-Suk; Park, Su-Moon

    2006-10-05

    A new attempt to obtain electron transfer kinetic parameters at an electrified electrode/electrolyte interface using Fourier transform electrochemical impedance spectroscopic (FTEIS) analyses of small potential step chronoamperometric currents is presented. The kinetic parameters thus obtained allowed mass transport free voltammograms to be constructed in an overpotential region, where the diffusion limits the electron transfer reaction, using the Butler-Volmer (B-V) relation. The B-V voltammograms clearly distinguish electrode reactions that are not much different in their electron transfer kinetic parameters, thus showing very similar normal linear sweep voltammetric (SCV) behaviors. Electrochemical reduction of p-benzoquinone, which displays nearly the same SCV responses at a gold electrode regardless whether the electrode is covered by a thiolated beta-cyclodextrin self-assembled monolayer, was taken as an example for the demonstration. The results show that the two voltametrically similar systems display very different electron transfer characteristics.

  3. 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

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

    PubMed

    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.

  5. 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.

  6. Effects of secondary yield parameter variation on predicted equilibrium potential of an object in a charging environment. [using computerized simulation

    NASA Technical Reports Server (NTRS)

    Purvis, C. K.

    1979-01-01

    The sensitivity of predicted equilibrium potential to changes in secondary electron yield parameters was investigated using MATCHG, a simple charging code which incorporates the NASCAP material property formulations. The equilibrium potential was found to be a sensitive function of one of the two parameters specifying secondary electron yield due to proton impact and of essentially all the parameters specifying yield due to electron impact. The information on the electron generated secondary yield parameters was discovered to be obtainable from monoenergetic beam charging data if charging rates as well as equilibrium potentials are accurately recorded.

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

    PubMed

    Satya, Eswari Jujjavarapu; Venkateswarlu, Chimmiri

    2013-09-01

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

  8. Thermodynamic Characterization of Five Key Kinetic Parameters that Define Neuronal Nitric Oxide Synthase Catalysis

    PubMed Central

    Haque, Mohammad Mahfuzul; Tejero, Jesús; Bayachou, Mekki; Wang, Zhi-Qiang; Fadlalla, Mohammed; Stuehr, Dennis J.

    2013-01-01

    NO synthase (NOS) enzymes convert L-arginine to NO in two sequential reactions whose rates (kcat1 and kcat2) are both limited by the rate of ferric heme reduction (kr). An enzyme ferric heme-NO complex forms as an immediate product complex and then undergoes either dissociation (at a rate that we denote as kd) to release NO in a productive manner, or reduction (kr) to form a ferrous heme-NO complex (FeIINO) that must react with O2 (at a rate that we denote as kox) in a NO dioxygenase reaction that regenerates the ferric enzyme. The interplay of these five kinetic parameters (kcat1, kcat2, kr, kd, and kox) determine NOS specific activity, O2 concentration response, and pulsatile versus steady-state NO generation. Here we utilized stopped-flow spectroscopy and single catalytic turnover methods to characterize the individual temperature dependencies of the five kinetic parameters of rat neuronal NOS (nNOS). We then incorporated the measured kinetic values into computer simulations of the nNOS reaction using a global kinetic model to comprehensively model its temperature-dependent catalytic behaviors. Our results provide new mechanistic insights and also reveal that the different temperature dependencies of the five kinetic parameters significantly alter nNOS catalytic behaviors and NO release efficiency as a function of temperature. PMID:23789902

  9. Genetic parameters for the weights and yields of carcass cuts in Chianina cattle.

    PubMed

    Sarti, F M; Pieramati, C; Lubricchio, E; Giontella, A; Lasagna, E; Panella, F

    2013-09-01

    Chianina is the tallest and heaviest beef cattle breed in the world and 1 of the most appreciated breeds on the Italian meat market. A selection program focused on improving Chianina carcass quality could provide a further economic advantage to Chianina breeders. However, the current European carcass scoring system [i.e., the SEUROP (S=superior, E=excellent, U= very good, R=good, O=fair, and P=poor) grid] is not suitable for use in selective breeding programs; methods based on carcass cuts would be much more efficient. Here, the genetic parameters of weights and yields (percentage of carcass weight) of the main commercial cuts were estimated on 842 Chianina carcasses (heifers and bullocks) using a mixed model that takes into account the fixed effects of herd, year of slaughter, and sex and the random additive effect of the animal; the carcass weight was also considered in cuts yield. The average carcass weights were 492.6 ± 86.52 kg (males) and 312.1 ± 68.74 kg (females), and the largest cut was the round, with a weight of 58.6 ± 19.35 kg and yield of 24.4 ± 1.28% in males and 40.2 ± 17.59 kg and 25.3 ± 1.41% in females. The variability in cut weight was greater than that in yield percentage. The cut weight heritabilities ranged from 0.74 (chuck) to 0.21 (short plate) whereas the yield heritabilities ranged from 0.88 (loin) to 0.40 (brisket). The genetic correlations were generally high and positive between weights; correlation values with yields were lower and could be positive or negative. These findings suggest that a selection program to improve the carcass quality of Chianina beef using cuts data could potentially achieve good results.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  11. 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…

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

    PubMed

    Goudar, Chetan T

    2011-10-01

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

  13. 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.

  14. Identification of regulatory structure and kinetic parameters of biochemical networks via mixed-integer dynamic optimization

    PubMed Central

    2013-01-01

    Background Recovering the network topology and associated kinetic parameter values from time-series data are central topics in systems biology. Nevertheless, methods that simultaneously do both are few and lack generality. Results Here, we present a rigorous approach for simultaneously estimating the parameters and regulatory topology of biochemical networks from time-series data. The parameter estimation task is formulated as a mixed-integer dynamic optimization problem with: (i) binary variables, used to model the existence of regulatory interactions and kinetic effects of metabolites in the network processes; and (ii) continuous variables, denoting metabolites concentrations and kinetic parameters values. The approach simultaneously optimizes the Akaike criterion, which captures the trade-off between complexity (measured by the number of parameters), and accuracy of the fitting. This simultaneous optimization mitigates a possible overfitting that could result from addition of spurious regulatory interactions. Conclusion The capabilities of our approach were tested in one benchmark problem. Our algorithm is able to identify a set of plausible network topologies with their associated parameters. PMID:24176044

  15. Control of ozonolysis kinetics and aerosol yield by nuances in the molecular structure of volatile organic compounds

    NASA Astrophysics Data System (ADS)

    Harvey, Rebecca M.; Petrucci, Giuseppe A.

    2015-12-01

    Secondary organic aerosol (SOA) plays integral roles in climate and human health, yet there remains a limited understanding of the mechanisms that lead to its formation and ultimate fate, as evidenced by a disparity between modeled atmospheric SOA loadings and field measurements. This disparity highlights the need for a more accurate representation of the molecular-level interactions between SOA sources and oxidative pathways. Due to the paucity of detailed chemical data for most SOA precursors of atmospheric relevance, models generally predict SOA loadings using structure activity relationships generalized to classes of SOA precursors. However, the kinetics and SOA forming potential of molecules are nuanced by seemingly minor structural differences in parent molecules that may be neglected in models. Laboratory chamber studies were used to measure SOA yields and rate constants for the ozonolysis of several linear, cyclic and oxygenated C5-C7 alkenes whose molecular structure vary in the site of unsaturation and/or the presence/position of functional groups and that represent atmospherically relevant classes of molecules. For the alkenes studied in this work, we found greater SOA yields for cyclic compounds compared to their linear analogs. For 1-alkenes, SOA yield increased with carbon number but was also dependent on the position of the double bond (internal vs terminal). Both the identity and position of oxygenated functional groups influenced SOA yield and kinetics through steric and electronic effects. Additionally, terminal alkenes generally resulted in a greater SOA yield than analogous internal alkenes, indicating that the position of the double bond in alkenes plays an important role in its atmospheric fate. Herein, we demonstrate the nuanced behavior of these ozonolysis reactions and discuss relationships between parent compound molecular structure and SOA yield and kinetics.

  16. Prediction of biogas yield and its kinetics in reed canary grass using near infrared reflectance spectroscopy and chemometrics.

    PubMed

    Kandel, Tanka P; Gislum, René; Jørgensen, Uffe; Lærke, Poul E

    2013-10-01

    A rapid method is needed to assess biogas and methane yield potential of various kinds of substrate prior to anaerobic digestion. This study reports near infrared reflectance spectroscopy (NIRS) as a rapid alternative method to the conventional batch methods for prediction of specific biogas yield (SBY), specific methane yield (SMY) and kinetics of biogas yield (k-SBY) of reed canary grass (RCG) biomass. Dried and powdered RCG biomass with different level of maturity was used for biochemical composition analysis, batch assays and NIRS analysis. Calibration models were developed using partial least square (PLS) regression from NIRS spectra. The calibration models for SBY (R(2)=0.68, RPD=1.83) and k-SBY (R(2)=0.71, RPD=1.75) were better than the model for SMY (R(2)=0.53, RPD=1.49). Although the PLS model for SMY was less successful, the model performance was better compared to the models based on chemical composition.

  17. Mass yields and kinetic energy of fragments from fission of highly-excited nuclei with A≲220

    NASA Astrophysics Data System (ADS)

    Denisov, V. Yu.; Margitych, T. O.; Sedykh, I. Yu.

    2017-02-01

    It is shown that the potential energy surface of the two separated fragments has the saddle point, which takes place at small distance between the surfaces of well-deformed fragments. The height of this two-body saddle point is larger than the height of one-body fission barrier for nuclei with A ≲ 220. The mass yields of the fission fragments, which are appearing at the fission of nuclei with A ≲ 220, are related to the number of states of the two-fragment systems at the two-body saddle points. The characteristics of kinetic energy of fragments are described by using the trajectory motion equations with the dissipation terms. The Gaussian distribution of the final kinetic energy around the classical value of this energy induced by the stochastic fluctuations is taken into account at an evaluation of the total kinetic energy distributions of the fission fragments.

  18. Biosolar cells: global artificial photosynthesis needs responsive matrices with quantum coherent kinetic control for high yield.

    PubMed

    Purchase, R L; de Groot, H J M

    2015-06-06

    This contribution discusses why we should consider developing artificial photosynthesis with the tandem approach followed by the Dutch BioSolar Cells consortium, a current operational paradigm for a global artificial photosynthesis project. We weigh the advantages and disadvantages of a tandem converter against other approaches, including biomass. Owing to the low density of solar energy per unit area, artificial photosynthetic systems must operate at high efficiency to minimize the land (or sea) area required. In particular, tandem converters are a much better option than biomass for densely populated countries and use two photons per electron extracted from water as the raw material into chemical conversion to hydrogen, or carbon-based fuel when CO2 is also used. For the average total light sum of 40 mol m(-2) d(-1) for The Netherlands, the upper limits are many tons of hydrogen or carbon-based fuel per hectare per year. A principal challenge is to forge materials for quantitative conversion of photons to chemical products within the physical limitation of an internal potential of ca 2.9 V. When going from electric charge in the tandem to hydrogen and back to electricity, only the energy equivalent to 1.23 V can be stored in the fuel and regained. A critical step is then to learn from nature how to use the remaining difference of ca 1.7 V effectively by triple use of one overpotential for preventing recombination, kinetic stabilization of catalytic intermediates and finally generating targeted heat for the release of oxygen. Probably the only way to achieve this is by using bioinspired responsive matrices that have quantum-classical pathways for a coherent conversion of photons to fuels, similar to what has been achieved by natural selection in evolution. In appendix A for the expert, we derive a propagator that describes how catalytic reactions can proceed coherently by a convergence of time scales of quantum electron dynamics and classical nuclear dynamics. We

  19. Biosolar cells: global artificial photosynthesis needs responsive matrices with quantum coherent kinetic control for high yield

    PubMed Central

    Purchase, R. L.; de Groot, H. J. M.

    2015-01-01

    This contribution discusses why we should consider developing artificial photosynthesis with the tandem approach followed by the Dutch BioSolar Cells consortium, a current operational paradigm for a global artificial photosynthesis project. We weigh the advantages and disadvantages of a tandem converter against other approaches, including biomass. Owing to the low density of solar energy per unit area, artificial photosynthetic systems must operate at high efficiency to minimize the land (or sea) area required. In particular, tandem converters are a much better option than biomass for densely populated countries and use two photons per electron extracted from water as the raw material into chemical conversion to hydrogen, or carbon-based fuel when CO2 is also used. For the average total light sum of 40 mol m−2 d−1 for The Netherlands, the upper limits are many tons of hydrogen or carbon-based fuel per hectare per year. A principal challenge is to forge materials for quantitative conversion of photons to chemical products within the physical limitation of an internal potential of ca 2.9 V. When going from electric charge in the tandem to hydrogen and back to electricity, only the energy equivalent to 1.23 V can be stored in the fuel and regained. A critical step is then to learn from nature how to use the remaining difference of ca 1.7 V effectively by triple use of one overpotential for preventing recombination, kinetic stabilization of catalytic intermediates and finally generating targeted heat for the release of oxygen. Probably the only way to achieve this is by using bioinspired responsive matrices that have quantum–classical pathways for a coherent conversion of photons to fuels, similar to what has been achieved by natural selection in evolution. In appendix A for the expert, we derive a propagator that describes how catalytic reactions can proceed coherently by a convergence of time scales of quantum electron dynamics and classical nuclear dynamics

  20. Genetic parameters of test-day milk yield in Guzerá cattle under tropical conditions.

    PubMed

    Cruz, D A C; Peixoto, M G C D; Bruneli, F A T; Bignardi, A B; El Faro, L

    2015-10-29

    The objective of this study was to estimate genetic parameters for test-day milk yield (TDMY) in Guzerá cows using random regression models. Additive and permanent environmental random effects were modeled by random regression on fourth- and fifth-order orthogonal Legendre polynomials, respectively. The residual variances were heterogeneous, with seven classes. Heritability estimates for TDMY ranged from 0.24 to 0.52, with higher heritabilities for yields during early lactation. Genetic correlations between TDMYs ranged from -0.03 to 0.95. The phenotypic and permanent environmental correlations were all positive, and the highest estimates were between adjacent TDMYs. The results suggest that TDMYs obtained with random regression models may be used as selection criteria for Guzerá cattle.

  1. Estimating maize grain yield from crop biophysical parameters using remote sensing

    NASA Astrophysics Data System (ADS)

    Guindin-Garcia, Noemi

    The overall objective of this investigation was to develop a robust technique to predict maize (Zea mays L.) grain yield that could be applied at a regional level using remote sensing with or without a simple crop growth simulation model. This study evaluated capabilities and limitations of the Moderate Resolution Imaging Spectroradiometer (MODIS) Vegetation Index 250-m and MODIS surface reflectance 500-m products to track and retrieve information over maize fields. Results demonstrated the feasibility of using MODIS data to estimate maize green leaf area index (LAIg). Estimates of maize LAIg obtained from Wide Dynamic Range Vegetation Index using data retrieved from MODIS 250-m products (e.g. MOD13Q1) can be incorporated in crop simulation models to improve LAIg simulations by the Muchow-Sinclair-Bennet (MSB) model reducing the RMSE of LAIg simulations for all years of study under irrigation. However, more accurate estimates of LAIg did not necessarily imply better final yield (FY) predictions in the MSB maize model. The approach of incorporating better LAIg estimates into crop simulation models may not offer a panacea for problem solving; this approach is limited in its ability to simulate other factors influencing crop yields. On the other hand, the approach of relating key crop biophysical parameters at the optimum stage with maize grain final yields is a robust technique to early FY estimation over large areas. Results suggest that estimates of LAI g obtained during the mid-grain filling period can used to detect variability of maize grain yield and this technique offers a rapid and accurate (RMSE < 900 kg ha-1) method to detect FY at county level using MODIS 250-m products.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  3. Combustion of pistachio shell: physicochemical characterization and evaluation of kinetic parameters.

    PubMed

    da Silva, Jean Constantino Gomes; Alves, José Luiz Francisco; Galdino, Wendell Venicio de Araujo; Moreira, Regina de Fátima Peralta Muniz; José, Humberto Jorge; de Sena, Rennio Felix; Andersen, Silvia Layara Floriani

    2017-04-06

    The study of different renewable energy sources has been intensifying due to the current climate changes; therefore, the present work had the objective to characterize physicochemically the pistachio shell waste and evaluate kinetic parameters of its combustion. The pistachio shell was characterized through proximate analysis, ultimate analysis, SEM, and FTIR. The thermal and kinetic behaviors were evaluated by a thermogravimetric analyzer under oxidant atmosphere between room temperature and 1000 °C, in which the process was performed in three different heating rates (20, 30, and 40 °C min(-1)). The combustion of the pistachio shell presented two regions in the derivative thermogravimetric curves, where the first represents the devolatilization of volatile matter compounds and the second one is associated to the biochar oxidation. These zones were considered for the evaluation of the kinetic parameters E a , A, and f(α) by the modified method of Coats-Redfern, compensation effect, and master plot, respectively. The kinetic parameters for zone 1 were E a1 = 84.11 kJ mol(-1), A 1 = 6.39 × 10(6) min(-1), and f(α)1 = 3(1 - α)(2/3), while for zone 2, the kinetic parameters were E a2 = 37.47 kJ mol(-1), A 2 = 57.14 min(-1), and f(α)2 = 2(1 - α)(1/2).

  4. Genetic Parameters for Milk Yield and Lactation Persistency Using Random Regression Models in Girolando Cattle.

    PubMed

    Canaza-Cayo, Ali William; Lopes, Paulo Sávio; da Silva, Marcos Vinicius Gualberto Barbosa; de Almeida Torres, Robledo; Martins, Marta Fonseca; Arbex, Wagner Antonio; Cobuci, Jaime Araujo

    2015-10-01

    A total of 32,817 test-day milk yield (TDMY) records of the first lactation of 4,056 Girolando cows daughters of 276 sires, collected from 118 herds between 2000 and 2011 were utilized to estimate the genetic parameters for TDMY via random regression models (RRM) using Legendre's polynomial functions whose orders varied from 3 to 5. In addition, nine measures of persistency in milk yield (PSi) and the genetic trend of 305-day milk yield (305MY) were evaluated. The fit quality criteria used indicated RRM employing the Legendre's polynomial of orders 3 and 5 for fitting the genetic additive and permanent environment effects, respectively, as the best model. The heritability and genetic correlation for TDMY throughout the lactation, obtained with the best model, varied from 0.18 to 0.23 and from -0.03 to 1.00, respectively. The heritability and genetic correlation for persistency and 305MY varied from 0.10 to 0.33 and from -0.98 to 1.00, respectively. The use of PS7 would be the most suitable option for the evaluation of Girolando cattle. The estimated breeding values for 305MY of sires and cows showed significant and positive genetic trends. Thus, the use of selection indices would be indicated in the genetic evaluation of Girolando cattle for both traits.

  5. [Effects of water stress on red-edge parameters and yield in wheat cropping].

    PubMed

    He, Ke-Xun; Zaho, Shu-He; Lai, Jian-Bin; Luo, Yun-Xiao; Qin, Zhi-Hao

    2013-08-01

    The objective of the present paper is to study the influence of water stress on wheat spectrum red edge parameters by using field wheat spectrum data obtained from water stress experiment. Firstly, the authors analyzed the influence of water stress on wheat spectrum reflectance. Then the authors got the wheat red edge position and red edge peak through calculating wheat spectrum first-order differential and analyzed the influence of water stress on wheat red edge parameters. Finally the authors discussed the relationship between red peak and wheat yield. The results showed that the wheat red edge position shows "red shift" at the beginning of the wheat growth period and "blue shift" at the later period of the wheat growth period under the water stress experiment. Also, the red edge peak of the wheat showed that red edge peak increased with the water stress sharpening at the beginning of the wheat growth period, and then the red edge peak reduced with the water stress sharpening. The wheat red edge peak presented positive correlation with the wheat yield before the elongation period, and exhibited negative correlation after that period.

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

    PubMed

    Rogers, Michael A; Marangoni, Alejandro G

    2016-12-06

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

  7. Effects of various process parameters on struvite precipitation kinetics and subsequent determination of rate constants.

    PubMed

    Rahaman, M S; Ellis, N; Mavinic, D S

    2008-01-01

    In this paper, struvite (MgNH(4)PO(4).6H(2)O) precipitation kinetics were studied with different operating conditions (varying supersaturation, pH, Mg:P ratio, degree of mixing and seeding conditions) and relevant rate constants were determined by fitting a slightly modified first-order kinetic model to the experimental data obtained. The rate of change of ortho-P concentration in the bulk solutions increases with increasing supersaturation ratio. The estimated rate constants are 2.034, 1.716 and 0.690 hr(-1) for the supersaturation ratio of 9.64, 4.83, and 2.44, respectively. Kinetic parameters were also evaluated for the Mg:P ratio between the ranges of 1.0 and 1.6, indicating higher phosphorus removal efficiency with increasing Mg:P ratio. The rate constants were found to be 0.942, 2.034 and 2.712 hr(-1) for Mg:P ratios of 1.0, 1.3 and 1.6, respectively. The experimental observations for kinetic study of struvite precipitation with different stirrer speeds clearly show that the mixing intensity used had little effect on the intrinsic rate constants. K values found to be 2.034 and 1.902 h(-1) for 100 and 70 rpm, respectively. Seeding, with 250-500 microm of seed crystals during the struvite precipitation kinetics test, was found to have very little effect on the ortho-P removal.

  8. Calcium-binding parameter of Bacillus amyloliquefaciens alpha-amylase determined by inactivation kinetics.

    PubMed Central

    Tanaka, Atsushi; Hoshino, Eiichi

    2002-01-01

    The irreversible thermal inactivation and the thermodynamics of calcium ion binding of Bacillus amyloliquefaciens alpha-amylase in the absence of substrates were studied. The enzyme inactivation on heating was apparently followed by first-order kinetics. The enzyme was stabilized with an increased concentration of calcium ion and thus the inactivation was highly dependent on the state of calcium binding. The activation parameter for the inactivation suggests an unfolding of the enzyme protein upon heating. Values of both the activation enthalpy and entropy were increased with a higher calcium ion concentration. An inactivation kinetic model is based on the assumption of a two-stage unfolding transition in which the bivalent ion dissociation occurs in the first step followed by the secondary structural unfolding. This simple kinetic model provides both a qualitative and quantitative interpretation of calcium ion binding to the enzyme and its effect on the inactivation properties. The specific approximations of the kinetic model were strictly followed in the analysis to calculate the apparent inactivation rate at each calcium ion concentration in terms of the calcium-binding parameters. The enthalpy and entropy changes for the calcium ion binding were calculated to be -149 kJ/mol and -360 J.mol(-1).K(-1) respectively and these values suggest a strong enthalpic affinity for the bivalent ion binding to the enzyme protein. The thermodynamical interpretation attempts to provide clear relations between the terms of an apparent inactivation rate and the calcium binding. PMID:12049626

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

    PubMed

    Passalía, Claudio; Alfano, Orlando M; Brandi, Rodolfo J

    2012-04-15

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

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

    PubMed

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

    2014-04-01

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

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

    NASA Astrophysics Data System (ADS)

    Ickes, Luisa; Welti, André; Lohmann, Ulrike

    2017-02-01

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

  12. Effects of J couplings and unobservable minor states on kinetics parameters extracted from CEST data

    NASA Astrophysics Data System (ADS)

    Zhou, Yang; Yang, Daiwen

    2014-12-01

    Chemical exchange saturation transfer (CEST) experiments have emerged as a powerful tool for characterizing dynamics and sparse populated conformers of protein in slow exchanging systems. We show that J couplings and 'invisible' minor states can cause systematic errors in kinetics parameters and chemical shifts extracted from CEST data. For weakly coupled spin systems, the J coupling effect can be removed using an approximation method. This method is warranted through detailed theoretical derivation, supported by results from simulations and experiments on an acyl carrier protein domain. Simulations demonstrate that the effect of 'invisible' minor states on the extracted kinetics parameters depends on the chemical shifts, populations, exchange rates of the 'invisible' states to the observed major or minor state and exchange models. Moreover, the extracted chemical shifts of the observed minor state can also be influenced by the "invisible" minor states. The presence of an off-pathway folding intermediate in the acyl carrier protein domain explains why the exchange rates obtained with a two-state model from individual residues that displayed only two obvious CEST dips varied significantly and the extracted exchange rates for 15N and 13CO spins located in the same peptide bond could be very different. The approximation method described here simplifies CEST data analysis in many situations where the coupling effect cannot be ignored and decoupling techniques are not desirable. In addition, this study also raises alerts for 'invisible' minor states which can cause errors in not only kinetics parameters but also chemical shifts of the observed minor state.

  13. Genetic parameters for buffalo milk yield and milk quality traits using Bayesian inference.

    PubMed

    Aspilcueta-Borquis, R R; Araujo Neto, F R; Baldi, F; Bignardi, A B; Albuquerque, L G; Tonhati, H

    2010-05-01

    The availability of accurate genetic parameters for important economic traits in milking buffaloes is critical for implementation of a genetic evaluation program. In the present study, heritabilities and genetic correlations for fat (FY305), protein (PY305), and milk (MY305) yields, milk fat (%F) and protein (%P) percentages, and SCS were estimated using Bayesian methodology. A total of 4,907 lactations from 1,985 cows were used. The (co)variance components were estimated using multiple-trait analysis by Bayesian inference method, applying an animal model, through Gibbs sampling. The model included the fixed effects of contemporary groups (herd-year and calving season), number of milking (2 levels), and age of cow at calving as (co)variable (quadratic and linear effect). The additive genetic, permanent environmental, and residual effects were included as random effects in the model. The posterior means of heritability distributions for MY305, FY305, PY305, %F, P%, and SCS were 0.22, 0.21, 0.23, 0.33, 0.39, and 0.26, respectively. The genetic correlation estimates ranged from -0.13 (between %P and SCS) to 0.94 (between MY305 and PY305). The permanent environmental correlation estimates ranged from -0.38 (between MY305 and %P) to 0.97 (between MY305 and PY305). Residual and phenotypic correlation estimates ranged from -0.26 (between PY305 and SCS) to 0.97 (between MY305 and PY305) and from -0.26 (between MY305 and SCS) to 0.97 (between MY305 and PY305), respectively. Milk yield, milk components, and milk somatic cells counts have enough genetic variation for selection purposes. The genetic correlation estimates suggest that milk components and milk somatic cell counts would be only slightly affected if increasing milk yield were the selection goal. Selecting to increase FY305 or PY305 will also increase MY305, %P, and %F.

  14. Kinetic parameters of thermally stimulated light emission phenomenon in CaF2 doped with Tm(3+) ions.

    PubMed

    González, P R; Cruz-Zaragoza, E; Furetta, C

    2016-11-01

    The characterization of new materials thermoluminescent used in radiation dosimetry, require the determination of kinetic parameters, which are associated with the number and shape of the peaks which presents its glow curve, among the most important are: the activation energy, E, or depth of the traps, the frequency factor, s, and the kinetics order, b. These parameters are necessary to predict the stability of thermoluminescent information after irradiation of the material. In this work, we present the results obtained for the determination of kinetic parameters of Tm(3+)-doped CaF2, the methods used for the determination of kinetic parameters were; initial growth signal TL, General order Chen method, and Deconvolution of glow curve. The results showed that the glow curve of CaF2 presents three glow peaks, 492K main peak and two smaller peaks, one at 430K and another to 566K. The dosimetric glow peak fits to the general-order kinetics model.

  15. Fit to moments of inclusive B{yields}X{sub c}l{nu} and B{yields}X{sub s}{gamma} decay distributions using heavy quark expansions in the kinetic scheme

    SciTech Connect

    Buchmueller, O.L.; Flaecher, H. U.

    2006-04-01

    We present a fit to measured moments of inclusive distributions in B{yields}X{sub c}l{nu} and B{yields}X{sub s}{gamma} decays to extract values for the Cabibbo-Kobayashi-Maskawa (CKM) matrix element |V{sub cb}|, the b- and c-quark masses, and higher-order parameters that appear in the heavy quark expansion. The fit is carried out using theoretical calculations in the kinetic scheme and includes moment measurements of the BABAR, Belle, CDF, CLEO, and DELPHI collaborations for which correlation matrices have been published. We find |V{sub cb}|=(41.96{+-}0.23{sub exp}{+-}0.35{sub HQE}{+-}0.59{sub {gamma}{sub S}{sub L}})x10{sup -3} and m{sub b}=4.590{+-}0.025{sub exp}{+-}0.030{sub HQE} GeV where the errors are experimental and theoretical respectively. We also derive values for the heavy quark distribution function parameters m{sub b} and {mu}{sub {pi}}{sup 2} in different theoretical schemes that can be used as input for the determination of |V{sub ub}|.

  16. Genetic parameters for milk fatty acids, milk yield and quality traits of a Holstein cattle population reared under tropical conditions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Information about genetic parameters is essential for selection decisions and genetic evaluation. Those estimates are population specific, but few studies are available for dairy cattle populations reared under tropical and subtropical conditions. Heritability and genetic correlations for milk yield...

  17. Tailoring wet explosion process parameters for the pretreatment of cocksfoot grass for high sugar yields.

    PubMed

    Njoku, S I; Ahring, B K; Uellendahl, H

    2013-08-01

    The pretreatment of lignocellulosic biomass is crucial for efficient subsequent enzymatic hydrolysis and ethanol fermentation. In this study, wet explosion (WEx) pretreatment was applied to cocksfoot grass and pretreatment conditions were tailored for maximizing the sugar yields using response surface methodology. The WEx process parameters studied were temperature (160-210 °C), retention time (5-20 min), and dilute sulfuric acid concentration (0.2-0.5 %). The pretreatment parameter set E, applying 210 °C for 5 min and 0.5 % dilute sulfuric acid, was found most suitable for achieving a high glucose release with low formation of by-products. Under these conditions, the cellulose and hemicellulose sugar recovery was 94 % and 70 %, respectively. The efficiency of the enzymatic hydrolysis of cellulose under these conditions was 91 %. On the other hand, the release of pentose sugars was higher when applying less severe pretreatment conditions C (160 °C, 5 min, 0.2 % dilute sulfuric acid). Therefore, the choice of the most suitable pretreatment conditions is depending on the main target product, i.e., hexose or pentose sugars.

  18. Thermoluminescence kinetic parameters of different amount La-doped ZnB₂O₄.

    PubMed

    Kucuk, Nil; Gozel, Aziz Halit; Yüksel, Mehmet; Dogan, Tamer; Topaksu, Mustafa

    2015-10-01

    The kinetic parameters of 1%, 2%, 3% and 4% La-doped ZnB2O4 phosphors (i.e. ZnB2O4:0.01La, ZnB2O4:0.02La, ZnB2O4:0.03La and ZnB2O4:0.04La) synthesized by nitric acid method have been calculated. Thermoluminescence (TL) glow curves of ZnB2O4:La phosphors after beta-irradiation showed a very well defined main peak having the maximum temperature at around 200°C and a shoulder peak at around 315°C with a constant heating rate of 5°C/s. The kinetic parameters of ZnB2O4:La phosphors TL glow peaks (i.e. order of kinetics (b), activation energies (Ea) and frequency factors (s)) have been determined and evaluated by Computerized Glow Curve Deconvolution (CGCD), and Peak Shape (PS) methods using the glow curve data. From the results, it can conclude that the values of Ea obtained with these methods for ZnB2O4:La phosphors are consistent with each other, but the s values differ considerably.

  19. Determination of thermoluminescence kinetic parameters of terbium-doped zirconium oxide

    NASA Astrophysics Data System (ADS)

    Rivera, T.; Azorín, J.; Falcony, C.; Martínez, E.; García, M.

    2001-06-01

    In recent years considerable importance has been attached to zirconium oxide doped with rare earth (ZrO 2 : RE) thin films due to their desirable characteristics for use in UV dosimetry. In our laboratories we have developed a method to prepare ZrO 2 : RE thin films. Dosimetric characteristics of these materials have been reported previously (Azorin et al., Radiat. Meas. 29 (1998) 315; Radiat. Prot. Dosim. 85 (1999) 317) and results of these have stimulated continued development and analysis of the thermoluminescence mechanism. Two important parameters to be determined in TL studies are the activation energy ( E) and the frequency factor ( s). This paper presents the results of determining kinetic parameters of terbium-doped zirconium oxide (ZrO 2 : Tb) thin films, exposed to 260 nm UV light, using the Lushchik (Sov. Phys. JETF 3 (1956) 390) and Chen (J. Appl. Phys. 40 (1969) 570; J. Electrochem. Soc. 166 (1969) 1254) methods. Kinetic analysis of the glow curve shows second order kinetics for both the first and second glow peaks.

  20. Evaluating kinetic models for preferential CO-oxidation catalysts using optimization-based parameter estimation

    NASA Astrophysics Data System (ADS)

    Baughman, Adam C.; Huang, Xinqun; Martin, Lealon L.

    2012-07-01

    We adapt a general-purpose optimization-based parameter estimation technique previously described in the literature [1] to evaluate the suitability of a number of common kinetic models for the representation of key performance characteristics (conversion and selectivity) of catalysts used for the preferential oxidation of CO in the presence of H2. We find that, for process engineering applications, there is no clear practical advantage to using mechanistically based kinetic models (e.g. Langmuir-Hinshelwood) unless the precise chemical mechanism is known. Empirical rate models are found generally to provide equivalent or better simulations of key performance variables for a diverse group of catalyst formulations. Furthermore, we demonstrate that the water-gas-shift (WGS) reaction is relevant within PROX reaction systems under conditons containing high fractions of CO2 and H2, confirming the expectations of Choi and Stenger (2004) [2]. Finally, we attempt to identify any emergent trends in kinetic parameters among catalysts sharing similar active metal or metal oxide components. Unfortunately, apart from confirming that the activation barrier for CO oxidation is generally less than the barrier for H2 oxidation (an expected relationship for PROX catalysts), no such trends are found.

  1. Enhanced heat stability and kinetic parameters of maize endosperm ADPglucose pyrophosphorylase by alteration of phylogenetically identified amino acids.

    PubMed

    Boehlein, Susan K; Shaw, Janine R; Georgelis, Nikolaos; Hannah, L Curtis

    2014-02-01

    ADP-glucose pyrophosphorylase (AGPase) controls the rate-limiting step in starch biosynthesis and is regulated at various levels. Cereal endosperm enzymes, in contrast to other plant AGPases, are particularly heat labile and transgenic studies highlight the importance of temperature for cereal yield. Previously, a phylogenetic approach identified Type II and positively selected amino acid positions in the large subunit of maize endosperm AGPase. Glycogen content, kinetic parameters and heat stability were measured in AGPases having mutations in these sites and interesting differences were observed. This study expands on our earlier evolutionary work by determining how all Type II and positively selected sites affect kinetic constants, heat stability and catalytic rates at increased temperatures. Variants with enhanced properties were identified and combined into one gene, designated Sh2-E. Enhanced properties include: heat stability, enhanced activity at 37 °C, activity at 55 °C, reduced Ka and activity in the absence of activator. The resulting enzyme exhibited all improved properties of the various individual changes. Additionally, Sh2-E was expressed with a small subunit variant with enhanced enzyme properties resulting in an enzyme that has exceptional heat stability, a high catalytic rate at increased temperatures and significantly decreased Km values for both substrates in the absence of the activator.

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

    PubMed

    Nakatani-Webster, Eri; Nath, Abhinav

    2017-03-14

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

  3. Kinetics, Mechanism and Product Yields in the Atmospheric Oxidation of Dimethylsulfide

    DTIC Science & Technology

    2016-06-14

    Rosenstiel School of Marine and Atmospheric Science University of Miami 4600 Rickenbacker Causeway Miami, Florida 33149-1098 ahynes...decomposition and reaction, b) direct confirmation of production, and quantitative product yields of potential reaction products and intermediates...School of Marine and Atmospheric Science ,4600 Rickenbacker Causeway,Miami,FL,33149 8. PERFORMING ORGANIZATION REPORT NUMBER 9. SPONSORING/MONITORING

  4. Alternative Bio-Based Solvents for Extraction of Fat and Oils: Solubility Prediction, Global Yield, Extraction Kinetics, Chemical Composition and Cost of Manufacturing

    PubMed Central

    Sicaire, Anne-Gaëlle; Vian, Maryline; Fine, Frédéric; Joffre, Florent; Carré, Patrick; Tostain, Sylvain; Chemat, Farid

    2015-01-01

    The present study was designed to evaluate the performance of alternative bio-based solvents, more especially 2-methyltetrahydrofuran, obtained from crop’s byproducts for the substitution of petroleum solvents such as hexane in the extraction of fat and oils for food (edible oil) and non-food (bio fuel) applications. First a solvent selection as well as an evaluation of the performance was made with Hansen Solubility Parameters and the COnductor-like Screening MOdel for Realistic Solvation (COSMO-RS) simulations. Experiments were performed on rapeseed oil extraction at laboratory and pilot plant scale for the determination of lipid yields, extraction kinetics, diffusion modeling, and complete lipid composition in term of fatty acids and micronutrients (sterols, tocopherols and tocotrienols). Finally, economic and energetic evaluations of the process were conducted to estimate the cost of manufacturing using 2-methyltetrahydrofuran (MeTHF) as alternative solvent compared to hexane as petroleum solvent. PMID:25884332

  5. Alternative bio-based solvents for extraction of fat and oils: solubility prediction, global yield, extraction kinetics, chemical composition and cost of manufacturing.

    PubMed

    Sicaire, Anne-Gaëlle; Vian, Maryline; Fine, Frédéric; Joffre, Florent; Carré, Patrick; Tostain, Sylvain; Chemat, Farid

    2015-04-15

    The present study was designed to evaluate the performance of alternative bio-based solvents, more especially 2-methyltetrahydrofuran, obtained from crop's byproducts for the substitution of petroleum solvents such as hexane in the extraction of fat and oils for food (edible oil) and non-food (bio fuel) applications. First a solvent selection as well as an evaluation of the performance was made with Hansen Solubility Parameters and the COnductor-like Screening MOdel for Realistic Solvation (COSMO-RS) simulations. Experiments were performed on rapeseed oil extraction at laboratory and pilot plant scale for the determination of lipid yields, extraction kinetics, diffusion modeling, and complete lipid composition in term of fatty acids and micronutrients (sterols, tocopherols and tocotrienols). Finally, economic and energetic evaluations of the process were conducted to estimate the cost of manufacturing using 2-methyltetrahydrofuran (MeTHF) as alternative solvent compared to hexane as petroleum solvent.

  6. The influence of energy migration on luminescence kinetics parameters in upconversion nanoparticles

    NASA Astrophysics Data System (ADS)

    Alyatkin, Sergey; Asharchuk, Ilya; Khaydukov, Kirill; Nechaev, Andrey; Lebedev, Oleg; Vainer, Yuri; Semchishen, Vladimir; Khaydukov, Evgeny

    2017-01-01

    The mechanism of upconversion at the nanoscale is still under discussion. In this paper, we report on the experimental results of anti-Stokes luminescence kinetics in the upconversion nanoparticles of β-NaYF4: 20%Yb3+; 0.6%Tm3+. The parameters of the luminescence kinetics were found to be unambiguously dependent on the number of excitation quanta n, which are necessary for certain transitions between the energy states of thulium ions. The observed correlation has been explained by means of the long-lasting energy migration between the ytterbium ions. The spread in time between the luminescent maxima of the corresponding thulium transitions not only shows the nonlinear character of upconversion, but also reveals the time scale of energy migration as well. From these, we derive that the conventional Förster formalism applied to the estimation of energy transfer efficiency in UCNP-fluorophore pairs can provide misleading results.

  7. Heterogeneous reactivity of pyrene and 1-nitropyrene with NO 2: Kinetics, product yields and mechanism

    NASA Astrophysics Data System (ADS)

    Miet, K.; Le Menach, K.; Flaud, P.-M.; Budzinski, H.; Villenave, E.

    The heterogeneous reactivity of nitrogen dioxide with pyrene and 1-nitropyrene (1NP) adsorbed on silica particles has been investigated using a fast-flow-tube in the absence of light. Reactants and products were extracted from particles using pressurised fluid extraction (PFE) and concentration measurements were performed using gas chromatography/mass spectrometry (GC/MS). The pseudo-first order rate constants were obtained from the fit of the experimental decay of particulate polycyclic compound concentrations versus reaction time. Experiments were performed at three different NO 2 concentrations and second order rate constants were calculated considering the oxidant concentration. The following rate constant values were obtained at room temperature: k(NO 2 + pyrene) = (9.3 ± 2.3) × 10 -17 cm 3 molecule -1 s -1 and k(NO 2 + 1NP) = (6.2 ± 1.5) × 10 -18 cm 3 molecule -1 s -1, showing that the reactivity of 1NP was slower by a factor of 15 than that of pyrene. 1NP was identified as the only NO 2-initiated oxidation product of pyrene and all the three dinitropyrenes were identified in the case of the 1NP reaction. The product quantification allowed showing that the kinetics of oxidation product formation was equal to that measured for parent compounds degradation, within uncertainties, confirming the validity of the reaction kinetics measurements.

  8. A Theoretical Analysis for Assessing the Variability of Secondary Model Thermal Inactivation Kinetic Parameters

    PubMed Central

    Giannakourou, Maria C.; Stoforos, Nikolaos G.

    2017-01-01

    Traditionally, for the determination of the kinetic parameters of thermal inactivation of a heat labile substance, an appropriate index is selected and its change is measured over time at a series of constant temperatures. The rate of this change is described through an appropriate primary model and a secondary model is applied to assess the impact of temperature. By this approach, the confidence intervals of the estimates of the rate constants are not taken into account. Consequently, the calculated variability of the secondary model parameters can be significantly lower than the actual variability. The aim of this study was to demonstrate the influence of the variability of the primary model parameters in establishing the confidence intervals of the secondary model parameters. Using a Monte Carlo technique and assuming normally distributed DT values (parameter associated with a primary inactivation model), the error propagating on the DTref and z-values (secondary model parameters) was assessed. When DT confidence intervals were broad, the secondary model’s parameter variability was appreciably high and could not be adequately estimated through the traditional deterministic approach that does not take into account the variation on the DT values. In such cases, the proposed methodology was essential for realistic estimations. PMID:28231086

  9. Quantitative genetic parameters for yield, plant growth and cone chemical traits in hop (Humulus lupulus L.)

    PubMed Central

    2014-01-01

    Background Most traits targeted in the genetic improvement of hop are quantitative in nature. Improvement based on selection of these traits requires a comprehensive understanding of their inheritance. This study estimated quantitative genetic parameters for 20 traits related to three key objectives for the genetic improvement of hop: cone chemistry, cone yield and agronomic characteristics. Results Significant heritable genetic variation was identified for α-acid and β-acid, as well as their components and relative proportions. Estimates of narrow-sense heritability for these traits (h 2  = 0.15 to 0.29) were lower than those reported in previous hop studies, but were based on a broader suite of families (108 from European, North American and hybrid origins). Narrow-sense heritabilities are reported for hop growth traits for the first time (h 2  = 0.04 to 0.20), relating to important agronomic characteristics such as emergence, height and lateral morphology. Cone chemistry and growth traits were significantly genetically correlated, such that families with more vigorous vegetative growth were associated with lower α-acid and β-acid levels. This trend may reflect the underlying population structure of founder genotypes (European and North American origins) as well as past selection in the Australian environment. Although male and female hop plants are thought to be indistinguishable until flowering, sex was found to influence variation in many growth traits, with male and female plants displaying differences in vegetative morphology from emergence to cone maturity. Conclusions This study reveals important insights into the genetic control of quantitative hop traits. The information gained will provide hop breeders with a greater understanding of the additive genetic factors which affect selection of cone chemistry, yield and agronomic characteristics in hop, aiding in the future development of improved cultivars. PMID:24524684

  10. Different singularities in the functions of extended kinetic theory at the origin of the yield stress in granular flows

    SciTech Connect

    Berzi, Diego; Vescovi, Dalila

    2015-01-15

    We use previous results from discrete element simulations of simple shear flows of rigid, identical spheres in the collisional regime to show that the volume fraction-dependence of the stresses is singular at the shear rigidity. Here, we identify the shear rigidity, which is a decreasing function of the interparticle friction, as the maximum volume fraction beyond which a random collisional assembly of grains cannot be sheared without developing force chains that span the entire domain. In the framework of extended kinetic theory, i.e., kinetic theory that accounts for the decreasing in the collisional dissipation due to the breaking of molecular chaos at volume fractions larger than 0.49, we also show that the volume fraction-dependence of the correlation length (measure of the velocity correlation) is singular at random close packing, independent of the interparticle friction. The difference in the singularities ensures that the ratio of the shear stress to the pressure at shear rigidity is different from zero even in the case of frictionless spheres: we identify that with the yield stress ratio of granular materials, and we show that the theoretical predictions, once the different singularities are inserted into the functions of extended kinetic theory, are in excellent agreement with the results of numerical simulations.

  11. 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.

  12. 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...

  13. Order Parameter and Kinetics of Non-Equilibrium Phase Transition Stimulated by the Impact of Volumetric Heat Source

    NASA Astrophysics Data System (ADS)

    Slyadnikov, E. E.; Turchanovskii, I. Yu.

    2017-01-01

    The authors formulated an understanding of the order parameter and built a kinetic model for the nonequilibrium first-order "solid body - liquid" phase transition stimulated by the impact of the volumetric heat source. Analytical solutions for kinetic equations were found, and it was demonstrated that depending on the phase transition rate "surface" and "bulk" melting mechanisms are implemented.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1984-04-01

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

  16. Rod outer segment structure influences the apparent kinetic parameters of cyclic GMP phosphodiesterase

    PubMed Central

    1994-01-01

    Cyclic GMP hydrolysis by the phosphodiesterase (PDE) of retinal rod outer segments (ROS) is a key amplification step in phototransduction. Definitive estimates of the turnover number, kcat, and of the Km are crucial to quantifying the amplification contributed by the PDE. Published estimates for these kinetic parameters vary widely; moreover, light-dependent changes in the Km of PDE have been reported. The experiments and analyses reported here account for most observed variations in apparent Km, and they lead to definitive estimates of the intrinsic kinetic parameters in amphibian rods. We first obtained a new and highly accurate estimate of the ratio of holo-PDE to rhodopsin in the amphibian ROS, 1:270. We then estimated the apparent kinetic parameters of light-activated PDE of suspensions of disrupted frog ROS whose structural integrity was systematically varied. In the most severely disrupted ROS preparation, we found Km = 95 microM and kcat = 4,400 cGMP.s-1. In suspensions of disc-stack fragments of greater integrity, the apparent Km increased to approximately 600 microM, though kcat remained unchanged. In contrast, the Km for cAMP was not shifted in the disc stack preparations. A theoretical analysis shows that the elevated apparent Km of suspensions of disc stacks can be explained as a consequence of diffusion with hydrolysis in the disc stack, which causes active PDEs nearer the center of the stack to be exposed to a lower concentration of cyclic GMP than PDEs at the disc stack rim. The analysis predicts our observation that the apparent Km for cGMP is elevated with no accompanying decrease in kcat. The analysis also predicts the lack of a Km shift for cAMP and the previously reported light dependence of the apparent Km for cGMP. We conclude that the intrinsic kinetic parameters of the PDE do not vary with light or structural integrity, and are those of the most severely disrupted disc stacks. PMID:7931138

  17. Formation of gas-phase peptide ions and their dissociation in MALDI: insights from kinetic and ion yield studies.

    PubMed

    Moon, Jeong Hee; Yoon, Sohee; Bae, Yong Jin; Kim, Myung Soo

    2015-01-01

    Insights on mechanisms for the generation of gas-phase peptide ions and their dissociation in matrix-assisted laser desorption ionization (MALDI) gained from the kinetic and ion yield studies are presented. Even though the time-resolved photodissociation technique was initially used to determine the dissociation kinetics of peptide ions and their effective temperature, it was replaced by a simpler method utilizing dissociation yields from in-source decay (ISD) and post-source decay (PSD). The ion yields for a matrix and a peptide were measured by repeatedly irradiating a region on a sample and collecting ion signals until the sample in the region was completely depleted. Matrix- and peptide-derived gas-phase cations were found to be generated by pre-formed ion emission or by ion-pair emission followed by anion loss, but not by laser-induced ionization. The total number of ions, that is, matrix plus peptide, was found to be equal to the number of ions emitted from a pure matrix. A matrix plume was found to cool as it expanded, from around 800-1,000 K to 400-500 K. Dissociation of peptide ions along b/y channels was found to occur statistically, that is, following RRKM behavior. Small critical energy (E0  = 0.6-0.7 eV) and highly negative critical entropy (ΔS(‡)  = -30 to -25 eu) suggested that the transition structure was stabilized by multiple intramolecular interactions.

  18. Parameter Identification and On-line Estimation of a Reduced Kinetic Model

    SciTech Connect

    Dellorco, P.C.; Flesner, R.L.; Le, L.A.; Littell, J.D.; Muske, K.R.

    1999-02-01

    In this work, we present the estimation techniques used to update the model parameters in a reduced kinetic model describing the oxidation-reduction re- actions in a hydrothermal oxidation reactor. The model is used in a nonlinear model-based controller that minimizes the total aqueous nitrogen in the reac- tor effluent. Model reduction is accomplished by com- bining similar reacting compounds into one of four component groups and considering the global reac- tion pathways for each of these groups. The reduced kinetic model developed for thk reaction system pro- vides a means to characterize the complex chemical reaction system without considering each chemicaJ species present and the reaction kinetics of every pos- sible reaction pathway. For the reaction system under study, model reduction is essential in order to reduce the computational requirement so that on-line imple- mentation of the nonlinear model-based controller is possible and also to reduce the amount of a priori information required for the model.

  19. Direct determination of enzyme kinetic parameters from single reactions using a new progress curve analysis tool.

    PubMed

    Bäuerle, Felix; Zotter, Agnes; Schreiber, Gideon

    2016-10-15

    With computer-based data-fitting methods becoming a standard tool in biochemistry, progress curve analysis of enzyme kinetics is a feasible, yet seldom used tool. Here we present a versatile Matlab-based tool (PCAT) to analyze catalysis progress curves with three complementary model approaches. The first two models are based on the known closed-form solution for this problem: the first describes the required Lambert W function with an analytical approximation and the second provides a numerical solution of the Lambert W function. The third model is a direct simulation of the enzyme kinetics. Depending on the chosen model, the tools excel in speed, accuracy or initial value requirements. Using simulated and experimental data, we show the strengths and pitfalls of the different fitting models. Direct simulation proves to have the highest level of accuracy, but it also requires reasonable initial values to converge. Finally, we propose a standard procedure to obtain optimized enzyme kinetic parameters from single progress curves.

  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. Nutrient Uptake by Microorganisms according to Kinetic Parameters from Theory as Related to Cytoarchitecture

    PubMed Central

    Button, D. K.

    1998-01-01

    The abilities of organisms to sequester substrate are described by the two kinetic constants specific affinity, a°, and maximal velocity Vmax. Specific affinity is derived from the frequency of substrate-molecule collisions with permease sites on the cell surface at subsaturating concentrations of substrates. Vmax is derived from the number of permeases and the effective residence time, τ, of the transported molecule on the permease. The results may be analyzed with affinity plots (v/S versus v, where v is the rate of substrate uptake), which extrapolate to the specific affinity and are usually concave up. A third derived parameter, the affinity constant KA, is similar to KM but is compared to the specific affinity rather than Vmax  and is defined as the concentration of substrate necessary to reduce the specific affinity by half. It can be determined in the absence of a maximal velocity measurement and is equal to the Michaelis constant for a system with hyperbolic kinetics. Both are taken as a measure of τ, with departure of KM from KA being affected by permease/enzyme ratios. Compilation of kinetic data indicates a 108-fold range in specific affinities and a smaller (103-fold) range in Vmax values. Data suggest that both specific affinities and maximal velocities can be underestimated by protocols which interrupt nutrient flow prior to kinetic analysis. A previously reported inverse relationship between specific affinity and saturation constants was confirmed. Comparisons of affinities with ambient concentrations of substrates indicated that only the largest a°S values are compatible with growth in natural systems. PMID:9729603

  2. Determination of the kinetic parameters of BeO using isothermal decay method.

    PubMed

    Azorin Nieto, Juan; Vega, Claudia Azorin; Montalvo, Teodoro Rivera; Cabrera, Eugenio Torijano

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

    Berezovska, Ganna; Prada-Gracia, Diego; Mostarda, Stefano; Rao, Francesco

    2012-11-01

    Molecular simulations as well as single molecule experiments have been widely analyzed in terms of order parameters, the latter representing candidate probes for the relevant degrees of freedom. Notwithstanding this approach is very intuitive, mounting evidence showed that such descriptions are inaccurate, leading to ambiguous definitions of states and wrong kinetics. To overcome these limitations a framework making use of order parameter fluctuations in conjunction with complex network analysis is investigated. Derived from recent advances in the analysis of single molecule time traces, this approach takes into account the fluctuations around each time point to distinguish between states that have similar values of the order parameter but different dynamics. Snapshots with similar fluctuations are used as nodes of a transition network, the clusterization of which into states provides accurate Markov-state-models of the system under study. Application of the methodology to theoretical models with a noisy order parameter as well as the dynamics of a disordered peptide illustrates the possibility to build accurate descriptions of molecular processes on the sole basis of order parameter time series without using any supplementary information.

  4. Local field potentials in primate motor cortex encode grasp kinetic parameters

    PubMed Central

    Milekovic, Tomislav; Truccolo, Wilson; Grün, Sonja; Riehle, Alexa; Brochier, Thomas

    2015-01-01

    Reach and grasp kinematics are known to be encoded in the spiking activity of neuronal ensembles and in local field potentials (LFPs) recorded from primate motor cortex during movement planning and execution. However, little is known, especially in LFPs, about the encoding of kinetic parameters, such as forces exerted on the object during the same actions. We implanted two monkeys with microelectrode arrays in the motor cortical areas MI and PMd to investigate encoding of grasp-related parameters in motor cortical LFPs during planning and execution of reach-and-grasp movements. We identified three components of the LFP that modulated during grasps corresponding to low (0.3 - 7Hz), intermediate (∼10 - ∼40Hz) and high (∼80 - 250Hz) frequency bands. We show that all three components can be used to classify not only grip types but also object loads during planning and execution of a grasping movement. In addition, we demonstrate that all three components recorded during planning or execution can be used to continuously decode finger pressure forces and hand position related to the grasping movement. Low and high frequency components provide similar classification and decoding accuracies, which were substantially higher than those obtained from the intermediate frequency component. Our results demonstrate that intended reach and grasp kinetic parameters are encoded in multiple LFP bands during both movement planning and execution. These findings also suggest that the LFP is a reliable signal for the control of parameters related to object load and applied pressure forces in brain-machine interfaces. PMID:25869861

  5. Kinetics of the reaction HO2 + NO2 + M yields HO2NO2 + M

    NASA Technical Reports Server (NTRS)

    Sander, S. P.; Peterson, M. E.

    1984-01-01

    The flash photolysis/ultraviolet absorption technique was used to measure the rate constants for the reaction HO2 + NO2 + M yields HO2NO2 + M over the pressure range 50-700 torr and temperature range 229-362 K using He, O2, and N2 as diluent gases. The data were fit to the expression derived by Troe (1979) and co-workers for describing the pressure and temperature dependence of reactions in the falloff region. By combining these data with recent measurements of the rate constant for HO2NO2 thermal decomposition values of 73.8 + or - 2 eu for the standard entropy and -12.6 + or - kcal/mol for the standard enthalpy of formation of HO2NO2 were obtained. A significant enhancement in the rate constant was observed when water vapor was added to the system.

  6. 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.

  7. Optimization of glycerol fed-batch fermentation in different reactor states: a variable kinetic parameter approach.

    PubMed

    Xie, Dongming; Liu, Dehua; Zhu, Haoli; Zhang, Jianan

    2002-05-01

    To optimize the fed-batch processes of glycerol fermentation in different reactor states, typical bioreactors including 500-mL shaking flask, 600-mL and 15-L airlift loop reactor, and 5-L stirred vessel were investigated. It was found that by reestimating the values of only two variable kinetic parameters associated with physical transport phenomena in a reactor, the macrokinetic model of glycerol fermentation proposed in previous work could describe well the batch processes in different reactor states. This variable kinetic parameter (VKP) approach was further applied to model-based optimization of discrete-pulse feed (DPF) strategies of both glucose and corn steep slurry for glycerol fed-batch fermentation. The experimental results showed that, compared with the feed strategies determined just by limited experimental optimization in previous work, the DPF strategies with VKPs adjusted could improve glycerol productivity at least by 27% in the scale-down and scale-up reactor states. The approach proposed appeared promising for further modeling and optimization of glycerol fermentation or the similar bioprocesses in larger scales.

  8. A computer program for enzyme kinetics that combines model discrimination, parameter refinement and sequential experimental design.

    PubMed Central

    Franco, R; Gavaldà, M T; Canela, E I

    1986-01-01

    A method of model discrimination and parameter estimation in enzyme kinetics is proposed. The experimental design and analysis of the model are carried out simultaneously and the stopping rule for experimentation is deduced by the experimenter when the probabilities a posteriori indicate that one model is clearly superior to the rest. A FORTRAN77 program specifically developed for joint designs is given. The method is very powerful, as indicated by its usefulness in the discrimination between models. For example, it has been successfully applied to three cases of enzyme kinetics (a single-substrate Michaelian reaction with product inhibition, a single-substrate complex reaction and a two-substrate reaction). By using this method the most probable model and the estimates of the parameters can be obtained in one experimental session. The FORTRAN77 program is deposited as Supplementary Publication SUP 50134 (19 pages) at the British Library (Lending Division), Boston Spa, Wetherby, West Yorkshire LS23 7BQ, U.K., from whom copies can be obtained on the terms indicated in Biochem. J. (1986) 233, 5. PMID:3800965

  9. Kinetically Stable Lanthanide Complexes Displaying Exceptionally High Quantum Yields upon Long-Wavelength Excitation: Synthesis, Photophysical Properties, and Solution Speciation.

    PubMed

    Routledge, Jack D; Jones, Michael W; Faulkner, Stephen; Tropiano, Manuel

    2015-04-06

    We demonstrate how highly emissive, kinetically stable complexes can be prepared using the macrocyclic scaffold of DO3A bearing coordinating aryl ketones as highly effective sensitizing chromophores. In the europium complexes, high quantum yields (up to 18% in water) can be combined with long-wavelength excitation (370 nm). The behavior in solution upon variation of pH, studied by means of UV-vis absorption, emission, and NMR spectroscopies, reveals that the nature of the chromophore can give rise to pH-dependent behavior as a consequence of deprotonation adjacent to the carbonyl group. Knowledge of the molecular speciation in solution is therefore critical when assessing the luminescence properties of such complexes.

  10. Kinetics and methane gas yields of selected C1 to C5 organic acids in anaerobic digestion.

    PubMed

    Yang, Yu; Chen, Qian; Guo, Jialiang; Hu, Zhiqiang

    2015-12-15

    Volatile fatty acids (VFAs) and other short-chain organic acids such as lactic and pyruvic acids are intermediates in anaerobic organic degradation. In this study, anaerobic degradation of seven organic acids in salt form was investigated, including formate (C1), acetate (C2), propionate (C3), pyruvate (C3), lactate (C3), butyrate (C4), and valerate (C5). Microbial growth kinetics on these organic acids were determined individually at 37 °C through batch anaerobic digestion tests by varying substrate concentrations from 250 to 4000 mg COD/L. The cumulative methane generation volume was determined real-time by respirometry coupled with gas chromatographic analysis while methane yield and related kinetics were calculated. The methane gas yields (fe, mg CH4 COD/mg substrate COD) from anaerobic degradation of formate, acetate, propionate, pyruvate, lactate, butyrate, and valerate were 0.44 ± 0.27, 0.58 ± 0.05, 0.53 ± 0.18, 0.24 ± 0.05, 0.17 ± 0.05, 0.43 ± 0.15, 0.49 ± 0.11, respectively. Anaerobic degradation of formate showed self-substrate inhibition at the concentrations above 3250 mg COD/L. Acetate, propionate, pyruvate, butyrate, lactate, and valerate did not inhibit methane production at the highest concentrations tested (i.e., 4000 mg COD/L). Microbes growing on acetate had the highest overall specific growth rate (0.30 d(-1)) in methane production. For comparison, the specific microbial growth rates on formate, propionate, pyruvate, butyrate, lactate, and valerate for methane production were 0.10, 0.06, 0.08, 0.07, 0.05, 0.15 d(-1), respectively.

  11. Growth kinetics and yield study on Chlorella pyrenoidosa in chemically defined media

    SciTech Connect

    Joung, J.J.; Akin, C.

    1983-01-01

    A Chlorella culture free from heterotrophic bacteria was obtained by eliminating the bacteria with successive use of antibiotics and agar plants. The purified Chlorella was cultured in chemically defined media. Under a photon flux (16.7 mw/cmS) similar to insolation, both heterotrophic and mixotrophic cultures were luxurious but the growth rates of autotrophic cultures were reduced substantially. The Chlorella culture grew most rapidly at 30 C in the absence of heterotrophic bacteria, and the highest specific growth rates were 1.43 x 10 h and 0.46 x 10 h for mixotrophic and autotrophic cultures, respectively. The highest photosynthetic efficiency over its growth period was 2.9% for autotrophic cultures. Elimination of heterotrophic bacteria from Chlorella cultures improved the algal growth rate as well as biomass yield significantly. A parasite of 0.1- m size was identified. The motile microorganism played an important role in the growth of the Chlorella and appeared to be common to green algae. 16 references, 2 tables.

  12. Decay kinetics of the excited S{sub 1} state of the cyanine dye Cy{sup +}I{sup -} (thiacarbocyanine iodide): The computation of quantum yields for different pathways

    SciTech Connect

    Odinokov, A. V.; Basilevsky, M. V.; Petrov, N. Kh.

    2011-10-14

    This work explains the unordinary solvent effect which was observed in the photochemical decay kinetics for the cyanine dye thiacarbocyanine iodide (Cy{sup +}I{sup -}) in binary solvent mixtures toluene/dimethylsulfoxide. The interpretation is formulated in terms of the probability density F(R) describing the distribution of interionic distances R in the ion pair Cy{sup +}I{sup -} and depending on the solvent composition. The proper normalization of this distribution is expressed via the degree of association {alpha} for the ion pair in a given solvent mixture. The {alpha} values are, in turn, extracted by means of the mass action law from the ionic association constants computed in a separate publication. The detailed kinetic scheme includes the empirical parametrization of the R-dependent kinetic constants for different decay channels. The multiparameter fitting procedure represents, with the reasonable parameter values, the dependence of the observed quantum yields on the solvent composition.

  13. Kinetics of the reaction OH + HO2 yields H2O + O2 at 296 K

    NASA Technical Reports Server (NTRS)

    Sridharan, U. C.; Kaufman, F.; Qiu, L. X.

    1981-01-01

    The rate constant of the title reaction was measured in a discharge-flow reactor by addition of excess HO2 from a movable double injector to a gas stream containing small concentrations of OH. The concentration of OH was measured by laser-induced fluorescence, HO2 by conversion to OH, and H and O by vacuum-UV resonance fluorescence. Five sets of experiments, each with different excess concentration of HO2, gave an average rate constant of (7.5 + or - 1.2) x 10 to the -11th cu cm/s where the error limits (single sigma) include uncertainties of all experimental parameters. This result is compared with other findings and is discussed in terms of its importance in stratospheric chemistry and in rate theory.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  15. Chemical kinetics parameters and model validation for the gasification of PCEA nuclear graphite

    NASA Astrophysics Data System (ADS)

    El-Genk, Mohamed S.; Tournier, Jean-Michel P.; Contescu, Cristian I.

    2014-01-01

    A series of gasification experiments, using two right cylinder specimens (∼12.7 × 25.4 mm and 25.4 × 25.4 mm) of PCEA nuclear graphite in ambient airflow, measured the total gasification flux at weight losses up to 41.5% and temperatures (893-1015 K) characteristics of those for in-pores gasification Mode (a) and in-pores diffusion-limited Mode (b). The chemical kinetics parameters for the gasification of PCEA graphite are determined using a multi-parameters optimization algorithm from the measurements of the total gasification rate and transient weight loss in experiments. These parameters are: (i) the pre-exponential rate coefficients and the Gaussian distributions and values of specific activation energies for adsorption of oxygen and desorption of CO gas; (ii) the specific activation energy and pre-exponential rate coefficient for the breakup of stable un-dissociated C(O2) oxygen radicals to form stable (CO) complexes; (iii) the specific activation energy and pre-exponential coefficient for desorption of CO2 gas and; (iv) the initial surface area of reactive free sites per unit mass. This area is consistently 13.5% higher than that for nuclear graphite grades of NBG-25 and IG-110 and decreases inversely proportional with the square root of the initial mass of the graphite specimens in the experiments. Experimental measurements successfully validate the chemical-reactions kinetics model that calculates continuous Arrhenius curves of the total gasification flux and the production rates of CO and CO2 gases. The model results at different total weight losses agree well with measurements and expand beyond the temperatures in the experiments to the diffusion-limited mode of gasification. Also calculated are the production rates of CO and CO2 gases and their relative contributions to the total gasification rate in the experiments as functions of temperature, for total weight losses of 5% and 10%.

  16. Chemical kinetics parameters and model validation for the gasification of PCEA nuclear graphite

    SciTech Connect

    El-Genk, Mohamed S; Tournier, Jean-Michel; Contescu, Cristian I

    2014-01-01

    A series of gasification experiments, using two right cylinder specimens (~ 12.7 x 25.4 mm and 25.4 x 25.4 mm) of PCEA nuclear graphite in ambient airflow, measured the total gasification flux at weight losses up to 41.5% and temperatures (893-1015 K) characteristics of those for in-pores gasification Mode (a) and in-pores diffusion-limited Mode (b). The chemical kinetics parameters for the gasification of PCEA graphite are determined using a multi-parameters optimization algorithm from the measurements of the total gasification rate and transient weight loss in experiments. These parameters are: (i) the pre-exponential rate coefficients and the Gaussian distributions and values of specific activation energies for adsorption of oxygen and desorption of CO gas; (ii) the specific activation energy and pre-exponential rate coefficient for the breakup of stable un-dissociated C(O2) oxygen radicals to form stable (CO) complexes; (iii) the specific activation energy and pre-exponential coefficient for desorption of CO2 gas and; (iv) the initial surface area of reactive free sites per unit mass. This area is consistently 13.5% higher than that for nuclear graphite grades of NBG-25 and IG-110 and decreases inversely proportional with the square root of the initial mass of the graphite specimens in the experiments. Experimental measurements successfully validate the chemical-reactions kinetics model that calculates continuous Arrhenius curves of the total gasification flux and the production rates of CO and CO2 gases. The model results at different total weight losses agree well with measurements and expand beyond the temperatures in the experiments to the diffusion-limited mode of gasification. Also calculated are the production rates of CO and CO2 gases and their relative contributions to the total gasification rate in the experiments as functions of temperature, for total weight losses of 5% and 10%.

  17. {sup 82}Rb kinetic parameter variability due to depth of anesthesia in the anesthetized canine

    SciTech Connect

    Coxson, P.G.; Brennan, K.M.; Yang, L.

    1995-05-01

    The effect of {open_quotes}depth of anesthesia{close_quotes} on {sup 82}Rb kinetic parameter estimates in the myocardium was tested in a series of replicated studies on six dogs using the Donner 600-Crystal Positron Tomograph. A single lateral slice through the myocardium was imaged following each of four successive injections of {sup 82}Rb. For three of the injections the animals were lightly anesthetized (mean blood pressure about 90 mmHg). For the second injection, the amount of anesthetic was increased until blood pressure dipped to about 70 mHg. The fourth injection was preceded by an infusion of dipyridamole to induce a stress-state. The entire sequence was repeated at least twice with each of the six animals. A two compartment model with parameters k{sub 1} (uptake rate), k{sub 2} (wash-out rate), and f{sub v} (vascular fraction) was fit to the data. There was a consistent finding of a 20% to 30% decrease in k{sub 1} during the deeply anesthetized state compared with the two lightly anesthetized rest states. Analysis of variance showed that the difference observed is significant, though small in comparison with the difference between the rest and stress states (60% to 160% increase). The difference between the two lightly anesthetized states was not significant. Kinetic PET studies using dogs are routinely carried out with the animal anesthetized. Depth of anesthesia has been suspected as as source of variability in parameter estimates, but this conjecture has not previously been systematically investigated. These studies at extremes in the depth of anesthesia show a small but predictable effect on the uptake k{sub 1} of {sup 82}Rb.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  19. Param-Medic: A Tool for Improving MS/MS Database Search Yield by Optimizing Parameter Settings.

    PubMed

    May, Damon H; Tamura, Kaipo; Noble, William S

    2017-03-13

    In shotgun proteomics analysis, user-specified parameters are critical to database search performance and therefore to the yield of confident peptide-spectrum matches (PSMs). Two of the most important parameters are related to the accuracy of the mass spectrometer. Precursor mass tolerance defines the peptide candidates considered for each spectrum. Fragment mass tolerance or bin size determines how close observed and theoretical fragments must be to be considered a match. For either of these two parameters, too wide a setting yields randomly high-scoring false PSMs, whereas too narrow a setting erroneously excludes true PSMs, in both cases, lowering the yield of peptides detected at a given false discovery rate. We describe a strategy for inferring optimal search parameters by assembling and analyzing pairs of spectra that are likely to have been generated by the same peptide ion to infer precursor and fragment mass error. This strategy does not rely on a database search, making it usable in a wide variety of settings. In our experiments on data from a variety of instruments including Orbitrap and Q-TOF acquisitions, this strategy yields more high-confidence PSMs than using settings based on instrument defaults or determined by experts. Param-Medic is open-source and cross-platform. It is available as a standalone tool ( http://noble.gs.washington.edu/proj/param-medic/ ) and has been integrated into the Crux proteomics toolkit ( http://crux.ms ), providing automatic parameter selection for the Comet and Tide search engines.

  20. Steady-state and transient Zener parameters in viscoplasticity: Drag strength versus yield strength

    NASA Technical Reports Server (NTRS)

    Freed, A. D.; Walker, K. P.

    1990-01-01

    A hypothesis is put forth which enables the viscoplastician to formulate a theory of viscoplasticity that reduces, in closed form, to the classical theory of creep. This hypothesis is applied to a variety of drag and yield strength models. Because of two theoretical restrictions that are a consequence of this hypothesis, three different yield strength models and one drag strength model are shown to be theoretically admissible. One of these yield strength models is selected as being the most appropriate representation for isotropic hardening.

  1. Mass Yields and Average Total Kinetic Energy Release in Fission for 235U, 238U, and 239Pu

    NASA Astrophysics Data System (ADS)

    Duke, Dana

    2015-10-01

    Mass yield distributions and average total kinetic energy (TKE) in neutron induced fission of 235U, 238U, and 239Pu targets were measured with a gridded ionization chamber. Despite decades of fission research, our understanding of how fragment mass yields and TKE depend on incident neutron energy is limited, especially at higher energies (above 5-10 MeV). Improved accuracy in these quantities is important for nuclear technology as it enhances our simulation capabilities and increases the confidence in diagnostic tools. The data can also guide and validate theoretical fission models where the correlation between the fragment mass and TKE is of particular value for constraining models. The Los Alamos Neutron Science Center - Weapons Neutron Research (LANSCE - WNR) provides a neutron beam with energies from thermal to hundreds of MeV, well-suited for filling in the gaps in existing data and exploring fission behavior in the fast neutron region. The results of the studies on target nuclei 235U, 238U, and 239Pu will be presented with a focus on exploring data trends as a function of neutron energy from thermal through 30 MeV. Results indicate clear evidence of structure due to multi-chance fission in the TKE . LA-UR-15-24761.

  2. Bioenergy conversion studies of organic fraction of MSW: kinetic studies and gas yield--organic loading relationships for process optimisation.

    PubMed

    Rao, M S; Singh, S P

    2004-11-01

    Batch digestion of municipal garbage was carried out for 100 days at room temperature (26+/-4 degrees C; average temperature 25 degrees C) and at ambient temperature (32+/-10 degrees C; average temperature 29 degrees C) conditions for total solids concentrations varying between 45 and 135 g/l. A first order model based on the availability of substrate as the limiting factor was used to perform the kinetic studies of batch anaerobic digestion system. Effect of organic solids concentration and digestion time on biogas yield was studied and mass and energy balance analysis was conducted for batch digestion. The net bioenergy yield from municipal garbage and corresponding bioprocess conversion efficiency over the length of the digestion time were observed to be 12,528 kJ/kg volatile solids and 84.51% respectively. The methane content of the biogas generated from the reactors was in the range of 62-72% with the overall average methane content of the biogas, computed over the total digestion period was 65 vol%.

  3. 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.

  4. Kinetic parameters of lithium and aluminium doped quartz from thermoluminescence glow curves.

    PubMed

    Gómez-Ros, J M; Correcher, V; García-Guinea, J; Delgado, A

    2002-01-01

    The thermoluminescence (TL) glow curves of irradiated annealed and non-annealed synthetic beta-quartz (Li0.73Al0.73Si1.27O4) synthesised using the ceramic method have been studied. Annealed samples (1200 degrees C for 12 h) exhibit some changes of shape and intensity in the TL glow curves when compared to non-annealed samples in the range of 0.1-5 Gy. These changes can be attributed mainly to thermal alkali self-diffusion through the lattice interfaces involving modifications in the components of the luminescent traps. In non-annealed samples six groups of components at about 100 degrees C, 130 degrees C, 160 degrees C, 210 degrees C, 330 degrees C and 450 degrees C can be found, whereas annealed samples only display one very intense peak at a lower temperature (deconvoluted into three peaks at 90 degrees C, 105 degrees C and 130 degrees C) and a lower intensity second wide broad emission at approximately 240 degrees C. In this paper, a computerised curve-fitting based on general order kinetics has been used to characterise the glow curve structure resolving trapping parameters for each glow peak: trap depth (E), frequency factor (s) and the order of the kinetics (b). The dose dependence of the individual components of the glow curve has been also studied. These data allow us to select the most stable component for use in dosimetric purposes.

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

    PubMed

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

    2015-11-01

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

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

    PubMed

    Zhao, He; Sokhansanj, Bahrad A

    2007-10-01

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

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

    PubMed

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

    2010-09-01

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

  8. 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.

  9. Kinetics of surface segregation in metallic alloys with first-principles interaction parameters

    SciTech Connect

    Wille, L.T. |; Ouannasser, S.; Dreysse, H.

    1996-12-31

    The authors report the results of Monte Carlo simulations of the kinetics of surface segregation at the (001) face of CuNi and MoW alloys. These two systems were selected because they are based on different lattice structures and show contrasting segregation behavior: CuNi exhibits a monotonic profile, while that of MoW is oscillatory. To describe the energetics they have determined a set of effective cluster interactions (ECI) which govern the ordering or clustering tendencies of these alloys. The ECI were obtained by means of tight-binding electronic structure calculations in which no adjustable or experimentally determined parameters were used. Equilibrium segregation profiles are calculated and a series of quenches are performed. The layer concentrations are studied as a function of time and the existence of metastable phases in the surface region is investigated.

  10. Parameter identification and on-line estimation for reduced kinetic model

    SciTech Connect

    Littel, J.D.; Muske, K.R.; Del`Orco, P.C.; Le, L.A.; Flesner, R.L.

    1998-08-07

    The base hydrolysis process for the destruction of energetic or explosive materials results is a high pH hydrolysate solution with reaction products that include a series of carboxylic acid salts, glycolates, amines, and nitrates. The hydrolysate solutions obtained from this process contain from two to ten wt% of organic carbon and nitrogen compounds that must be further treated before disposal. Hydrothermal oxidation at elevated temperatures (450 C) and pressure (14,000 psi) was selected as the treatment process for the hydrolysate solutions obtained from hydrolysis of the high explosive PBX 9404 at the Department of Energy Pantex facility in Amarillo, Texas. In this work, the authors describe the use of receding horizon identification and estimation techniques to determine the model parameters for a reduced kinetic model describing the oxidation-reduction reactions in a hydrothermal oxidation reactor. This model is used in a model predictive controller that minimizes the total aqueous nitrogen in the hydrothermal oxidation reactor effluent.

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

    PubMed

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

    2015-03-10

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

  12. [Flag leaf photosynthetic characteristics, change in chlorophyll fluorescence parameters, and their relationships with yield of winter wheat sowed in spring].

    PubMed

    Xu, Lan; Gao, Zhi-qang; An, Wei; Li, Yan-liang; Jiao, Xiong-fei; Wang, Chuang-yun

    2016-01-01

    With five good winter wheat cultivars selected from the middle and lower reaches of Yangtze River and Southwest China as test materials, a field experiment in Xinding basin area of Shanxi Province was conducted to study the photosynthetic characteristics, chlorophyll content, and chlorophyll fluorescence parameters of flag leaf at different sowing dates, as well as the correlations between these indices and yield for two years (2013-2014). The results showed that the difference in most fluorescence parameters except chlorophyll content among cultivars was significant. The correlations between these fluorescence parameters and yield were significant. The variation coefficient of chlorophyll (Chl) content was low (0.12-0.17), and that of performance index based on absorption (PIabs) was high (0.32-0.39), with the partial correlation coefficients of them with grain yield from 2013 to 2014 ranged in 0.70-0.81. Under the early sowing condition, the grain yield positively correlated with PIabs at flowering and filling stages and chlorophyll content at grain filling stage, but negatively correlated with the relative variable fluorescence at I point (Vi) at grain filling stage. About 81.1%-82.8% of grain yield were determined by the variations of PIabs, Chl, and Vi. Wheat cultivars had various performances in the treatments with different sowing dates and a consistent trend was observed in the two experimental years. Among these 5 cultivars, Yangmai 13 was suitable for early sowing, with the flag leaf photosynthetic rate (Pn), Chl, most fluorescence parame-ters, and grain yield showed obviously high levels. In conclusion, under early sowing condition chlorophyll content at grain filling stages, PIabs at flowering and filling stages, and Pn were important indices for selecting wheat cultivars with high photosynthetic efficiency.

  13. 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

  14. 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.

  15. Methane from cattle waste: effects of temperature, hydraulic retention time, and influent substrate concentration on kinetic parameter (k)

    SciTech Connect

    Hashimoto, A.G.

    1982-09-01

    The effects of temperature (35 and 55 degrees C), influent volatile solids (VS) concentration (So equal to 43, 64, 82, 100, 128 kg VS/cu.m) and hydraulic retention time (HRT equal to 4, 5, 8, 10, 15, and 25 days) on methane (CH/sub 4/) production from cattle waste were evaluated using 3-d cu.m laboratory scale fermentors. The highest CH/sub 4/ production rate achieved was 6.11 cu.m CH/sub 4//cu.m fermentor/day at 55 degrees C, four days HRT, and So equal to 100 kg VS/cu.m. Batch fermentations showed an ultimate CH/sub 4/ yield (Bo) of 0.42 cu.m CH/sub 4//kg VS fed. The maximum loading rates for unstressed fermentation were 7 kg VS/cu.m/day at 35 degrees C and 20 kg VS/cu.m/day at 55 degrees C. The kinetic parameter (K, an increasing K indicates inhibition of fermentation) increased exponentially as So increased, and was described by : K equal to 0.8 plus 0.0016e 0.06So. Temperature had no significant effect on K for So between 40 and 100 kg VS/cu.m. The above equation predicted published K values for cattle waste within a mean standard error of 7%. (Refs. 11).

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

    PubMed

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

    2016-03-10

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

  17. Kinetic parameters for the oxidation of pulverised coal as measured from drop tube tests

    SciTech Connect

    Ballester, J.; Jimenez, S.

    2005-08-01

    The methodology for measuring the oxidation parameters for pulverised coal combustion from drop-tube tests is reviewed, and some modifications to the traditional procedure (based on Arrhenius plots) are proposed. The work includes the experimental characterisation of an anthracite's combustion in a drop-tube furnace, which will be used as the reference data. One of the main points in the discussion is the consideration of a particle-size distribution instead of a single representative diameter. Since a true monosized sample cannot be obtained by sieving, the particles injected always display a size distribution and, therefore, the experimental results are the outcome of a range of oxidation rates. As a result, the assumption of a single particle size cannot explain some aspects of the experimental results (e.g., the 'curvature' of the burnoff curve) and may lead to significant deviations in the calculated parameters. On the other hand, an alternative method for deriving the parameters, based on calculating the particle's full combustion history, is proposed. The analysis presented here enables a more systematic and unambiguous approach for deriving the kinetic parameters for oxidation from experimental measurements. If the actual particle-size distribution is taken into account, the calculations are in good agreement with the experimental results and, in particular, reproduce the progressive decay in apparent oxidation rate while the fuel burns. Even though the deviations might still be reduced by using a more sophisticated model (e.g., accounting for heterogeneity in the particles' properties, or deactivation phenomena), the results obtained suggest that such corrections should be relatively small, the correct treatment of the size distribution of the particles being more important in this case.

  18. Mainz Organics Mechanism (MOM): description and sensitivity to some estimated kinetic parameters

    NASA Astrophysics Data System (ADS)

    Taraborrelli, Domenico; Cabrera Perez, David; Sander, Rolf; Pozzer, Andrea

    2015-04-01

    Despite decades of reasearch, global atmospheric chemistry models still have significant biases compared to the estimated distribution and evolution of tropospheric ozone and hydroxyl radical. The gas-phase oxidation of volatile organic compounds (VOC) is acknowledged to play an important role among the processes affecting tropospheric ozone, methane lifetime and aerosol evolution. Thus, chemical mechanisms of very diverse complexity have been developed for the major VOCs. However, all mechanisms present shortcomings such as neglection or lumping of intermediates and estimate of many rate constants and product distributions. Here, we present a VOC oxidation mechanism of intermediate complexity called the Mainz Organics Mechanism (MOM). With about 400 species and 1500 reactions, it represents the oxidation of about 20 primarily emitted VOCs comprising small alkanes and alkenes, isoprene, pinenes and monocyclic aromatic compounds. The development protocol significantly borrows from the Master Chemical Mechanism (MCM). However, MOM distinguishes itself for a number of features. First, the structure activity relationship for estimating the rate constants involving hydroxyl radical is site-specific and dependent on temperature. Second, the alkyl nitrate yields are considered to be dependent on temperature, pressure and molecular structure. RO2 + HO2 reaction kinetics is consistent with the recent direct studies of \\chem{OH}-reformation. Isoprene chemistry includes the latest experimental advancements with respect to OH-recycling and alkyl nitrate chemistry. Pinenes chemistry is largely the one by the MCM but with some modifications according to the work of the Leuven's group. Finally, the chemistry of the aromatics is also borrowed from the MCM but with additional photolysis of ortho-nitrophenols leading to \\chem{HONO} formation. The sensitivity of the model to the temperature and pressure dependence of estimated \\chem{OH} rate constants and alkyl nitrate yields will

  19. 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.

  20. Estimation of the growth kinetic parameters of Bacillus cereus spores as affected by pulsed light treatment.

    PubMed

    Aguirre, Juan S; de Fernando, Gonzalo García; Hierro, Eva; Hospital, Xavier F; Ordóñez, Juan A; Fernández, Manuela

    2015-06-02

    Quantitative microbial risk assessment requires the knowledge of the effect of food preservation technologies on the growth parameters of the survivors of the treatment. This is of special interest in the case of the new non-thermal technologies that are being investigated for minimal processing of foods. This is a study on the effect of pulsed light technology (PL) on the lag phase of Bacillus cereus spores surviving the treatment and the maximum growth rate (μmax) of the survivors after germination. The D value was estimated as 0.35 J/cm(2) and our findings showed that PL affected the kinetic parameters of the microorganism. A log linear relationship was observed between the lag phase and the intensity of the treatment. Increasing the lethality lengthened the mean lag phase and proportionally increased its variability. A polynomial regression was fitted between the μmax of the survivors and the inactivation achieved. The μmax decreased as intensity increased. From these data, and their comparison to published results on the effect of heat and e-beam irradiation on B. cereus spores, it was observed that the shelf-life of PL treated foods would be longer than those treated with heat and similar to irradiated ones. These findings offer information of interest for the implementation of PL for microbial decontamination in the food industry.

  1. Functional imaging of kinetic parameters from the time dependent linear response function by dynamic scintigraphy

    SciTech Connect

    Stritzke, P.; Knop, J.; Spielmann, R.P.; Montz, R.; Schneider, C.

    1984-01-01

    A new method is proposed to determine the locally differing time dependent linear response function h(r,t) of a radioactive tracer injected into a patients blood pool B(t) by mathematical analysis of a dynamic scintigraphic study A(r,t). Transit times, uptake rates and clearance rates of different tracers are calculated from the linear response function at every matrix point by one computer program. The parameters are presented in functional images on a standard computer display. Thus the whole information from a dynamic study can be condensed within a few images. The integral equation A=h+B +c(r)*B (+ means convolution, c(r)*B(t)=nontarget activity) derived from tracer theory is deconvoluted by mathematical methods, which are unsensitive against noise contamination of the input data. The numerical technique is successfully applied in Iodide-123-Hippuran and Tc-99m-DMSA kidney studies, in Tc-99m-MDP and -DPD bone studies, in Tl-201 myocardial studies and in Iodide-123 thyroid studies. Because the regional blood pool-or nontarget activity is calculated and subtracted, the kinetic parameters are considered to be free from nontarget contributions in all dynamic scintigraphic studies. Examples are demonstrated and the usefulness for clinical application is discussed.

  2. Improvement of kinetics, yield, and colloidal stability of biogenic gold nanoparticles using living cells of Euglena gracilis microalga

    NASA Astrophysics Data System (ADS)

    Dahoumane, Si Amar; Yéprémian, Claude; Djédiat, Chakib; Couté, Alain; Fiévet, Fernand; Coradin, Thibaud; Brayner, Roberta

    2016-03-01

    Recent years have witnessed a boom in the biosynthesis of a large variety of nanomaterials using different biological resources among which algae-based entities have been gaining much more attention within the community of material scientists worldwide. In our previously published findings, we explored some factors that governed the biofabrication of gold nanoparticles using living cultures of microalgae, such as the utilized microalgal genera, the phylum they belong to, and the impact of tetrachloroauric acid concentrations on the ability of these strains to perform the biosynthesis of gold nanoparticles once in contact with these cations. As a follow-up, we present in this paper an improvement of the features of bioproduced gold colloids using living cells of Euglena gracilis microalga when this species is grown under either mixotrophic or autotrophic conditions, i.e., exposed to light and grown in an organic carbon-enriched culture medium versus under autotrophic conditions. As an outcome to this alteration, the growth rate of this photosynthetic microorganism is multiplied 7-8 times when grown under mixotrophic conditions compared to autotrophic ones. Therefore, the yield, the kinetics, and the colloidal stability of the biosynthesized gold nanoparticles are dramatically enhanced. Moreover, the shape and the size of the as-produced nano-objects via this biological method are affected. In addition to round-shaped gold nanoparticles, particular shapes, such as triangles and hexagons, appear. These findings add up to the amassed knowledge toward the design of photobioreactors for the scalable and sustainable production of interesting nanomaterials.

  3. 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 (K2) for Pb was observed, indicating that the interaction between lead cations and alginate beads was faster than for cadmium. Similarly, isotherm data were fitted to different models reported in literature and it was found that the Langmuir-Freundlich (L-F) and Dubinin-Radushkevich (D-R) models describe the isotherms in all cases. CAB sorption capacity for cadmium was 27.4 mg/g and 150.4 mg/g for lead, at 25°C. Sorption capacities of Cd and Pb increase as temperature rises. According to the thermodynamic parameters, the cadmium and lead adsorption process was spontaneous and endothermic. It was also found that pH has an important effect on the adsorption of these metals by CAB, as more were removed at pH values between 6 and 7. PMID:24587740

  4. Determination of design and operation parameters for upper atmospheric research instrumentation to yield optimum resolution with deconvolution

    NASA Technical Reports Server (NTRS)

    Ioup, George E.; Ioup, Juliette W.

    1991-01-01

    The final report for work on the determination of design and operation parameters for upper atmospheric research instrumentation to yield optimum resolution with deconvolution is presented. Papers and theses prepared during the research report period are included. Among all the research results reported, note should be made of the specific investigation of the determination of design and operation parameters for upper atmospheric research instrumentation to yield optimum resolution with deconvolution. A methodology was developed to determine design and operation parameters for error minimization when deconvolution is included in data analysis. An error surface is plotted versus the signal-to-noise ratio (SNR) and all parameters of interest. Instrumental characteristics will determine a curve in this space. The SNR and parameter values which give the projection from the curve to the surface, corresponding to the smallest value for the error, are the optimum values. These values are constrained by the curve and so will not necessarily correspond to an absolute minimum in the error surface.

  5. Cerium oxide nanoparticles impact yield and modify nutritional parameters in wheat (Triticum aestivum L.).

    PubMed

    Rico, Cyren M; Lee, Sang Chul; Rubenecia, Rosnah; Mukherjee, Arnab; Hong, Jie; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

    2014-10-08

    The implications of engineered nanomaterials on crop productivity and food quality are not yet well understood. The impact of cerium oxide nanoparticles (nCeO2) on growth and yield attributes and nutritional composition in wheat (Triticum aestivum L.) was examined. Wheat was cultivated to grain production in soil amended with 0, 125, 250, and 500 mg of nCeO2/kg (control, nCeO2-L, nCeO2-M, and nCeO2-H, respectively). At harvest, grains and tissues were analyzed for mineral, fatty acid, and amino acid content. Results showed that, relative to the control, nCeO2-H improved plant growth, shoot biomass, and grain yield by 9.0%, 12.7%, and 36.6%, respectively. Ce accumulation in roots increased at increased nCeO2 concentration but did not change across treatments in leaves, hull, and grains, indicating a lack of Ce transport to the above-ground tissues. nCeO2 modified S and Mn storage in grains. nCeO2-L modified the amino acid composition and increased linolenic acid by up to 6.17% but decreased linoleic acid by up to 1.63%, compared to the other treatments. The findings suggest the potential of nanoceria to modify crop physiology and food quality with unknown consequences for living organisms.

  6. Yield of Ozone, Nitrite Nitrogen and Hydrogen Peroxide Versus Discharge Parameter Using APPJ Under Water

    NASA Astrophysics Data System (ADS)

    Chen, Bingyan; Zhu, Changping; Fei, Juntao; He, Xiang; Yin, Cheng; Wang, Yuan; Gao, Ying; Jiang, Yongfeng; Wen, Wen; Chen, Longwei

    2016-03-01

    Discharge plasma in and in contact with water can be accompanied with ultraviolet radiation and electron impact, thus can generate hydroxyl radicals, ozone, nitrite nitrogen and hydrogen peroxide. In this paper, a non-equilibrium plasma processing system was established by means of an atmospheric pressure plasma jet immersed in water. The hydroxyl intensities and discharge energy waveforms were tested. The results show that the positive and negative discharge energy peaks were asymmetric, where the positive discharge energy peak was greater than the negative one. Meanwhile, the yield of ozone and nitrite nitrogen was enhanced with the increase of both the treatment time and the discharge energy. Moreover, the pH value of treated water was reduced rapidly and maintained at a lower level. The residual concentration of hydrogen peroxide in APPJ treated water was kept at a low level. Additionally, both the efficiency energy ratio of the yield of ozone and nitrite nitrogen and that of the removal of p-nitrophenol increased as a function of discharge energy and discharge voltage. The experimental results were fully analyzed and the chemical reaction equations and the physical processes of discharges in water were given. supported by National Natural Science Foundation of China (Nos. 11274092, 11404092, 61401146), the Nantong Science and Technology Project, Nantong, China (No. BK2014024), the Open Project of Jiangsu Province Key Laboratory of Environmental Engineering, Nanjing, China (No. KF2014001), and the Fundamental Research Funds for the Central Universities of China (No. 2014B11414)

  7. 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.

  8. Re-examination of safety parameters using kinetic theory of nano-granular flows

    NASA Astrophysics Data System (ADS)

    Bouillard, Jacques Xavier; Marchal, Philippe; Henry, François; Vignes, Alexis; Dufaud, Olivier; Perrin, Laurent; Plasari, Edouard

    2011-07-01

    The origin of the kinetic theory of granular flow was originally credited to Bagnold [1]. By using a very primitive expression of the particle collision frequency, he derived an expression for the repulsive pressure of the particles in uniform shear flows. His repulsive pressure was proportional to the square of the velocity gradient and the particle diameter and directly proportional to the particle density. This theory was later extended by Savage [2] and Gidaspow [3]. Such theories provide insight on the dependence of the viscosity, and various moduli (elastic, non elastic, viscous...) in terms of the granular temperature and the associated shear-rates. Until recently, such parameters were difficult to measure because of the lack of specifically designed equipment. This challenge was successfully taken up and resolved by P. Marchal of ENSIC who designed a new rheometer for powders (figure 1). This equipment can put in evidence the importance of the granular temperature on the elastic and viscous behaviors of the granular flows. Such rheological behavior is important in risk analysis for nanopowders, because as the nanopowder may be subjected to process shear rates and stresses, its structural and topological changes, in terms of the transformation of agglomerates into primary nanoparticles, have strong impacts on emission factors of nanosized particles that can be released in the environment or into a workplace from such dense-phase nanopowder processes. Such transformation can be analyzed by studying the nano-granular rheological signature of the system. Such risk assessment approach using these new fundamental rheological safety parameters is described in this paper.

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

  10. Purification of lactoperoxidase from bovine whey and investigation of kinetic parameters

    PubMed Central

    Borzouee, Fatemeh; Mofid, Mohammad Reza; Varshosaz, Jaleh; Samsam Shariat, Seyed Ziyae Aldin

    2016-01-01

    Background: Lactoperoxidase (LPO) is related to mammalian peroxidase family which contains a wide spectrum of biological activities. Despite the wide studies on the LPO, there is little study has been performed to simplify and shorten the procedure of enzyme purification. The aim of this project was to purify the enzyme through a simple method, and investigating enzyme kinetic parameters. Materials and Methods: LPO was purified from bovine whey through modified method of Yoshida (1990) using two steps of ammonium sulfate precipitation and ion-exchange chromatography. The purity of isolated enzyme was monitored by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). Results: The enzyme was purified 59.13-fold with a recovery of 10.26 having a specific activity of 5.78 U/mg protein and an Rz value of 0.8. The enzyme activity was measured using guaiacol as a chromogenic substrate in phosphate buffer pH 6. SDS-PAGE showed a single bond with molecular weight of 78 kDa. The purified enzyme displayed optimum activity at pH 6 in 30 mM phosphate buffer and at a temperature of 50°C, with a Km value of 178 mM and Vmax 0.63 U/ml.min for guaiacol. Conclusion: Using only one step ion-exchange chromatography, LPO was isolated from bovine whey in high purity. PMID:28028529

  11. Quantification of morphologic, cytologic, and kinetic parameters of unirradiated swine skin: a histologic model

    SciTech Connect

    Archambeau, J.O.; Bennett, G.W.

    1984-05-01

    This study determines multiple histologic and cell kinetic parameters of unirradiated swine skin. The prickle cell layer exists as a shell three to six cells thick. The proliferative basal layer exists as a confluent monolayer with 2031 +/- 48 cells/cm; it has delta growth fraction of 1, an average cell generation time of 12 days, a T/sub s/ of 9 hr, and a T/sub s/ + T/sub G2/ + T/sub 1/2M/ of 17 to 19 hr. The labeling index is 3.9% with a diurnal variation having a 5% peak at 1800 hr and a 2.5% nadir at 0900-1100 hr. The mitotic index varies from 1.7 to 3.2% and has no clear-cut diurnal variation. These values are similar to those available for man. These data and those published previously are utilized to define a histologic model of the irradiated epidermal cell renewal system. These measured values are compared with those derived from analysis of available time-dose isoeffect data using a single-hit multitarget and a linear-quadratic model.

  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. The Impact of Multi-Sensor Data Assimilation on Plant Parameter Retrieval and Yield Estimation for Sugar Beet

    NASA Astrophysics Data System (ADS)

    Hodrius, M.; Migdall, S.; Bach, H.; Hank, T.

    2015-04-01

    Yield Maps are a basic information source for site-specific farming. For sugar beet they are not available as in-situ measurements. This gap of information can be filled with Earth Observation (EO) data in combination with a plant growth model (PROMET) to improve farming and harvest management. The estimation of yield based on optical satellite imagery and crop growth modelling is more challenging for sugar beet than for other crop types since the plants' roots are harvested. These are not directly visible from EO. In this study, the impact of multi-sensor data assimilation on the yield estimation for sugar beet is evaluated. Yield and plant growth are modelled with PROMET. This multi-physics, raster-based model calculates photosynthesis and crop growth based on the physiological processes in the plant, including the distribution of biomass into the different plant organs (roots, stem, leaves and fruit) at different phenological stages. The crop variable used in the assimilation is the green (photosynthetically active) leaf area, which is derived as spatially heterogeneous input from optical satellite imagery with the radiative transfer model SLC (Soil-Leaf-Canopy). Leaf area index was retrieved from RapidEye, Landsat 8 OLI and Landsat 7 ETM+ data. It could be shown that the used methods are very suitable to derive plant parameters time-series with different sensors. The LAI retrievals from different sensors are quantitatively compared to each other. Results for sugar beet yield estimation are shown for a test-site in Southern Germany. The validation of the yield estimation for the years 2012 to 2014 shows that the approach reproduced the measured yield on field level with high accuracy. Finally, it is demonstrated through comparison of different spatial resolutions that small-scale in-field variety is modelled with adequate results at 20 m raster size, but the results could be improved by recalculating the assimilation at a finer spatial resolution of 5 m.

  14. 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)

  15. Respirometric kinetic parameter calculations of a batch jet loop bioreactor treating leachate and oxygen uptake rate estimation by DTM.

    PubMed

    Ince, M; Yildiz, F; Engin, G Onkal; Engin, S N; Keskinler, B

    2008-05-30

    A novel circulating jet loop bioreactor adapted for organic matter oxidation has been designed and constructed. In this study, the input was leachate samples collected from Kemerburgaz Odayeri waste landfill site located on the European side of Istanbul. Controlling the jet loop bioreactor to realize high rates of purification depends on maintaining the appropriate loadings and operating conditions. This requires collecting various system data to estimate the dynamics of the system satisfactorily with the aim of keeping certain parameters within the specified range. The differential transform method (DTM) based solution of the state equations reveals the current state of the process so that any deviation in the system parameters can be immediately detected and regulated accordingly. The respirometric method for kinetic parameter calculations for biodegradation has been used for some time. In many studies, the respirometer was designed separately, usually in bench-scale. However, when a separate respirometer is used, the scale effect and parameters that affect the hydrodynamic structure of the system should be taken into consideration. In this study, therefore, the jet loop reactor itself was used as a respirometer. Thus, the kinetic parameters found reflecting the characteristics of microorganisms used for biodegradation would be more realistic. If the main reactor, here the jet loop reactor, would be used as the respirometer, the kinetic parameter changes can easily be monitored in the long run. Using the bioreactor as a respirometer, the most important kinetic parameters, Ks, kd and micromax were found to be 11,000 mg L(-1), 0.019 day(-1), and 0.21 day(-1), respectively. The stoichiometric coefficient, Y, was found to be 0.28 gr gr(-1) for the present system.

  16. Silica coating and photocatalytic activities of ZnO nanoparticles: effect of operational parameters and kinetic study.

    PubMed

    Ismail, L F M; Emara, M M; El-Moselhy, M M; Maziad, N A; Hussein, O K

    2014-10-15

    Silica-coating ZnO nanoparticles were prepared using the hydrothermal method. The prepared nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive X-ray Spectroscopy (EDX). It was found that ultrafine core/shell structured silica-coating ZnO nanoparticles were successfully obtained. TEM analysis revealed a continuous and uniform silica coating layer of about 8nm in thickness on the surface of ZnO nanoparticles. The photocatalytic performance of silica-coating ZnO core/shell nanoparticles in methylene blue aqueous solution was investigated. The effects of some operational parameters such as pH value, nanocatalyst loading and initial MB concentration on the degradation efficiency were discussed. Kinetic parameters were experimentally determined and a pseudo-first-order kinetic was observed. Thus, the main advantage of the coating is the stability of the photocatalysts and the better performance in acidic or alkaline solutions. Compared to ZnO the maximum apparent rate constant is obtained at pH 8.5 (pH 11.5 in case of bare ZnO). Moreover, the Langmuir adsorption model was applied to describe the equilibrium isotherm at different MB concentration. The applicability of the Langmuir isotherm suggests monolayer coverage of the MB onto surface of silica-coating ZnO nanoparticles. The kinetics of the adsorption with respect to the initial dye concentration, were also investigated. The pseudo-first-order and second-order kinetic models were used and the rate constants were evaluated. The kinetic studies revealed that the pseudo-second-order kinetic model better represented the adsorption kinetics, suggesting that the adsorption process may be chemisorption.

  17. Genetic parameters of health disorders, and relationships with 305-day milk yield and conformation traits of registered Holstein cows.

    PubMed

    Van Dorp, T E; Dekkers, J C; Martin, S W; Noordhuizen, J P

    1998-08-01

    A total of 4368 first lactation records for Holstein cows from 30 herds was used to estimate genetic parameters for yield, conformation traits, and the binary coded disease traits of udder edema, milk fever, retained placenta, metritis, displaced abomasum, ketosis, cystic ovary, mastitis, and lameness. Data on health, parentage, and yield came from an on-farm program for record keeping and management. Test day production data were obtained from British Columbia DHI. Type classification data were received from the Holstein Association of Canada. Heritabilities of disease traits were low ranging from 0 to 0.05. Exceptions were lameness (0.16) and ketosis (0.39). Correlations of disease traits with 305-d milk yield and of selected type traits with retained placenta, displaced abomasum, mastitis, and lameness were estimated. Phenotypic correlations did not substantially differ from 0 except for the correlation between lameness and rear leg set (0.37). Genetic correlations between disease traits and milk yield were mostly positive (0.02 to 0.44). Only retained placenta had a negative genetic correlation with milk yield (-0.28). Genetic correlations ranged from 0 to 0.37 between udder conformation traits and mastitis, from -0.38 to 0.09 between leg conformation traits and lameness, and from -0.11 to 0.38 between rump conformation and retained placenta. The results suggest that selection based solely on yield may increase the incidence of disease. Selection on conformation traits can help reduce the incidence of disease, although genetic correlations are low.

  18. The influence of tomograph sensitivity on kinetic parameter estimation in positron emission tomography imaging studies of the rat brain.

    PubMed

    Meikle, S R; Eberl, S; Fulton, R R; Kassiou, M; Fulham, M J

    2000-08-01

    We investigated the influence of tomograph sensitivity on reliability of parameter estimation in positron emission tomography studies of the rat brain. The kinetics of two tracers in rat striatum and cerebellum were simulated. A typical injected dose of 10 MBq and a reduced dose of 1 MBq were assumed. Kinetic parameters were estimated using a region of interest (ROI) analysis and two pixel-by-pixel analyses. Striatal binding potential was estimated as a function of effective tomograph sensitivity (S(eff)) using a simplified reference tissue model. A S(eff) value of > or =1% was required to ensure reliable parameter estimation for ROI analysis and a S(eff) of 3-6% was required for pixel-by-pixel analysis. We conclude that effective tomograph sensitivity of 3% may be an appropriate design goal for rat brain imaging.

  19. Nonlinear electrophoretic response yields a unique parameter for separation of biomolecules

    PubMed Central

    Pel, Joel; Broemeling, David; Mai, Laura; Poon, Hau-Ling; Tropini, Giorgia; Warren, René L.; Holt, Robert A.; Marziali, Andre

    2009-01-01

    We demonstrate a unique parameter for biomolecule separation that results from the nonlinear response of long, charged polymers to electrophoretic fields and apply it to extraction and concentration of nucleic acids from samples that perform poorly under conventional methods. Our method is based on superposition of synchronous, time-varying electrophoretic fields, which can generate net drift of charged molecules even when the time-averaged molecule displacement generated by each field individually is zero. Such drift can only occur for molecules, such as DNA, whose motive response to electrophoretic fields is nonlinear. Consequently, we are able to concentrate DNA while rejecting high concentrations of contaminants. We demonstrate one application of this method by extracting DNA from challenging samples originating in the Athabasca oil sands. PMID:19706437

  20. 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

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

    PubMed

    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

  2. Interaction between chitosan and uranyl ions. Role of physical and physicochemical parameters on the kinetics of sorption

    SciTech Connect

    Piron, E. |; Accominotti, M.; Domard, A.

    1997-03-19

    This work corresponds to the first part of our studies on the interactions between chitosan particles dispersed in water and uranyl ions. The measurements were obtained by ICP, and we considered the role of various physical and physicochemical parameters related to chitosan. We showed that the crystallinity, the particle dimensions, and the swelling in water of chitosan are parameters which are connected together and govern the kinetic laws of metal diffusion and sorption. The molecular mobility of the polymer chains is then essential parameter. 31 refs., 5 figs., 3 tabs.

  3. Kinetic parameter estimation in N. europaea biofilms using a 2-D reactive transport model.

    PubMed

    Lauchnor, Ellen G; Semprini, Lewis; Wood, Brian D

    2015-06-01

    Biofilms of the ammonia oxidizing bacterium Nitrosomonas europaea were cultivated to study microbial processes associated with ammonia oxidation in pure culture. We explored the hypothesis that the kinetic parameters of ammonia oxidation in N. europaea biofilms were in the range of those determined with batch suspended cells. Oxygen and pH microelectrodes were used to measure dissolved oxygen (DO) concentrations and pH above and inside biofilms and reactive transport modeling was performed to simulate the measured DO and pH profiles. A two dimensional (2-D) model was used to simulate advection parallel to the biofilm surface and diffusion through the overlying fluid while reaction and diffusion were simulated in the biofilm. Three experimental studies of microsensor measurements were performed with biofilms: i) NH3 concentrations near the Ksn value of 40 μM determined in suspended cell tests ii) Limited buffering capacity which resulted in a pH gradient within the biofilms and iii) NH3 concentrations well below the Ksn value. Very good fits to the DO concentration profiles both in the fluid above and in the biofilms were achieved using the 2-D model. The modeling study revealed that the half-saturation coefficient for NH3 in N. europaea biofilms was close to the value measured in suspended cells. However, the third study of biofilms with low availability of NH3 deviated from the model prediction. The model also predicted shifts in the DO profiles and the gradient in pH that resulted for the case of limited buffering capacity. The results illustrate the importance of incorporating both key transport and chemical processes in a biofilm reactive transport model.

  4. A compilation of rate parameters of water-mineral interaction kinetics for application to geochemical modeling

    USGS Publications Warehouse

    Palandri, James L.; Kharaka, Yousif K.

    2004-01-01

    Geochemical reaction path modeling is useful for rapidly assessing the extent of water-aqueous-gas interactions both in natural systems and in industrial processes. Modeling of some systems, such as those at low temperature with relatively high hydrologic flow rates, or those perturbed by the subsurface injection of industrial waste such as CO2 or H2S, must account for the relatively slow kinetics of mineral-gas-water interactions. We have therefore compiled parameters conforming to a general Arrhenius-type rate equation, for over 70 minerals, including phases from all the major classes of silicates, most carbonates, and many other non-silicates. The compiled dissolution rate constants range from -0.21 log moles m-2 s-1 for halite, to -17.44 log moles m-2 s-1 for kyanite, for conditions far from equilibrium, at 25 ?C, and pH near neutral. These data have been added to a computer code that simulates an infinitely well-stirred batch reactor, allowing computation of mass transfer as a function of time. Actual equilibration rates are expected to be much slower than those predicted by the selected computer code, primarily because actual geochemical processes commonly involve flow through porous or fractured media, wherein the development of concentration gradients in the aqueous phase near mineral surfaces, which results in decreased absolute chemical affinity and slower reaction rates. Further differences between observed and computed reaction rates may occur because of variables beyond the scope of most geochemical simulators, such as variation in grain size, aquifer heterogeneity, preferred fluid flow paths, primary and secondary mineral coatings, and secondary minerals that may lead to decreased porosity and clogged pore throats.

  5. The effects of process parameters on yield and properties of iron nanoparticles from ferrocene in a low-pressure plasma

    NASA Astrophysics Data System (ADS)

    Panchal, V.; Lahoti, G.; Bhandarkar, U.; Neergat, M.

    2011-08-01

    The effects of process parameters on iron nanoparticle formation and properties while using ferrocene as a precursor in a low-pressure capacitively coupled plasma are investigated. The L18 array of the Taguchi method, followed by the L4 array, is used with the notional objective of increasing the yield of nanoparticles. A study of the size, shape and composition of the particles (using transmission electron microscopy, high-resolution transmission electron microscopy, Raman spectroscopy, x-ray diffraction, CHON and inductively coupled plasma-atomic emission spectroscopy analysis) gives an insight into the role played by various process parameters. Pressure is the most critical parameter in increasing nanoparticle yield, whereas hydrogen flow plays a key role in determining the nanoparticle size and composition. Atomic hydrogen helps in removing amorphous carbon and reducing the nanoparticle size. RF power plays an important role in the dissociation of ferrocene thus also affecting the composition. Nanoparticles obtained using optimized conditions are a mixture of Fe3O4 and Fe2O3 with cluster size 25-40 nm in diameter that are further made up of 2-4 nm crystallites. Magnetic property measurements indicate that the nanoparticles are super-paramagnetic in nature.

  6. Feed intake, milk yield, and metabolic parameters prior to left displaced abomasum in dairy cows.

    PubMed

    Van Winden, S C L; Jorritsma, R; Müller, K E; Noordhuizen, J P T M

    2003-04-01

    As left-displaced abomasum (LDA) often occurs in cows with high contents of fat in the liver (fatty liver), a postpartum fatty liver-inducing regimen was applied to 16 cows. The main interest of the study was whether there were productive or metabolic changes in cows prior to LDA. Therefore, feed intake and milk production were monitored and blood samples were collected from the cows. The LDA occurred in 4 out of 16 dairy cows that were included in the feeding regimen. Compared to cows not developing LDA, LDA-cows had a significantly lower feed intake, 6.5 kg/d less, and milk production, 8 kg/d less, prior to clinical diagnosis of LDA. In the 10-d period preceding clinical diagnosis of LDA, blood concentrations of calcium, glucose, and insulin were significantly lower, whereas blood concentrations of nonesterified fatty acids and beta-hydroxybutyrate, as well as aspartate aminotransferase activities were significantly elevated compared to cows not developing LDA. These preclinical changes may play an important role in the pathogenesis of LDA. It is not certain, however, whether there is a causal association between these parameters and LDA.

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

    PubMed

    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.

  8. 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.

  9. Genetic parameters for milk fatty acids, milk yield and quality traits of a Holstein cattle population reared under tropical conditions.

    PubMed

    Petrini, J; Iung, L H S; Rodriguez, M A P; Salvian, M; Pértille, F; Rovadoscki, G A; Cassoli, L D; Coutinho, L L; Machado, P F; Wiggans, G R; Mourão, G B

    2016-10-01

    Information about genetic parameters is essential for selection decisions and genetic evaluation. These estimates are population specific; however, there are few studies with dairy cattle populations reared under tropical and sub-tropical conditions. Thus, the aim was to obtain estimates of heritability and genetic correlations for milk yield and quality traits using pedigree and genomic information from a Holstein population maintained in a tropical environment. Phenotypic records (n = 36 457) of 4203 cows as well as the genotypes for 57 368 single nucleotide polymorphisms from 755 of these cows were used. Covariance components were estimated using the restricted maximum likelihood method under a mixed animal model, considering a pedigree-based relationship matrix or a combined pedigree-genomic matrix. High heritabilities (around 0.30) were estimated for lactose and protein content in milk whereas moderate values (between 0.19 and 0.26) were obtained for percentages of fat, saturated fatty acids and palmitic acid in milk. Genetic correlations ranging from -0.38 to -0.13 were determined between milk yield and composition traits. The smaller estimates compared to other similar studies can be due to poor environmental conditions, which may reduce genetic variability. These results highlight the importance in using genetic parameters estimated in the population under evaluation for selection decisions.

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

    SciTech Connect

    Geslot, Benoit; Gruel, Adrien; Pepino, Alexandra; Di Salvo, Jacques; Izarra, Gregoire de; Jammes, Christian; Destouches, Christophe; Blaise, Patrick

    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 two 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)

  11. Monoculture parameters successfully predict coculture growth kinetics of Bacteroides thetaiotaomicron and two Bifidobacterium strains.

    PubMed

    Van Wey, A S; Cookson, A L; Roy, N C; McNabb, W C; Soboleva, T K; Shorten, P R

    2014-11-17

    Microorganisms rarely live in isolation but are most often found in a consortium. This provides the potential for cross-feeding and nutrient competition among the microbial species, which make it challenging to predict the growth kinetics in coculture. In this paper we developed a mathematical model to describe substrate consumption and subsequent microbial growth and metabolite production for bacteria grown in monoculture. The model characterized substrate utilization kinetics of 18 Bifidobacterium strains. Some bifidobacterial strains demonstrated preferential degradation of oligofructose in that sugars with low degree of polymerization (DP) (DP≤3 or 4) were metabolized before sugars of higher DP, or vice versa. Thus, we expanded the model to describe the preferential degradation of oligofructose. In addition, we adapted the model to describe the competition between human colonic bacteria Bacteroides thetaiotaomicron LMG 11262 and Bifidobacterium longum LMG 11047 or Bifidobacterium breve Yakult for inulin as well as cross-feeding of breakdown products from the extracellular hydrolysis of inulin by B. thetaiotaomicron LMG 11262. We found that the coculture growth kinetics could be predicted based on the respective monoculture growth kinetics. Using growth kinetics from monoculture experiments to predict coculture dynamics will reduce the number of in vitro experiments required to parameterize multi-culture models.

  12. Optimization of process parameters by response surface methodology and kinetic modeling for batch production of canthaxanthin by Dietzia maris NIT-D (accession number: HM151403).

    PubMed

    Goswami, Gargi; Chakraborty, Samarprit; Chaudhuri, Surabhi; Dutta, Debjani

    2012-10-01

    Dietzia maris NIT-D, a canthaxanthin producer, was isolated during routine screening of pigment-producing bacteria. Response surface methodology was applied for statistical designing of process parameters for biomass and canthaxanthin production. The effects of four process parameters (considered as independent variables), namely temperature (10-30 °C), pH (4.75-5.75), shaker speed (75-135 rpm) and percentage inoculum (0.5-2.5 %) on the biomass and canthaxanthin yield (considered as dependent variables) were studied. As much as 122 mg L(-1) of canthaxanthin was obtained when Dietzia maris NIT-D was incubated for 120 h at 25 °C and 120 rpm, initial pH and percentage inoculum being 5.5 and 2 % respectively. The pigment yield is the highest reported till date, with Dietzia maris as the test organism. The maximum biomass yield was 7.39 g L(-1) under optimized process parameters. The predicted values were also verified by validation experiments in 5-day fermentation. Different mathematical models were used to describe growth and production, considering the effect of glucose in batch mode. The kinetic constants were calculated by fitting the experimental data to the models. Cell growth was inhibited beyond a glucose concentration of 15 g L(-1). Andrews' model gave the best fit with a R (2) value of 0.9993. During the exponential growth phase, the specific growth rate was found to remain fairly constant with respect to time. There was no inhibitory effect due to intracellular product accumulation for all concentrations of glucose. This observation is the first of its kind, as previous studies have reported that increasing accumulation of intracellular carotenoid exerts greater degree of inhibition on growth.

  13. Genetic parameters of different measures of cheese yield and milk nutrient recovery from an individual model cheese-manufacturing process.

    PubMed

    Bittante, G; Cipolat-Gotet, C; Cecchinato, A

    2013-01-01

    Cheese yield (CY) is an important technological trait in the dairy industry, and the objective of this study was to estimate the genetic parameters of cheese yield in a dairy cattle population using an individual model-cheese production procedure. A total of 1,167 Brown Swiss cows belonging to 85 herds were sampled once (a maximum of 15 cows were sampled per herd on a single test day, 1 or 2 herds per week). From each cow, 1,500 mL of milk was processed according to the following steps: milk sampling and heating, culture addition, rennet addition, gelation-time recording, curd cutting, whey draining and sampling, wheel formation, pressing, salting in brine, weighing, and cheese sampling. The compositions of individual milk, whey, and curd samples were determined. Three measures of percentage cheese yield (%CY) were calculated: %CY(CURD), %CY(SOLIDS), and %CY(WATER), which represented the ratios between the weight of fresh curd, the total solids of the curd, and the water content of the curd, respectively, and the weight of the milk processed. In addition, 3 measures of daily cheese yield (dCY, kg/d) were defined, considering the daily milk yield. Three measures of nutrient recovery (REC) were computed: REC(FAT), REC(PROTEIN), and REC(SOLIDS), which represented the ratio between the weights of the fat, protein, and total solids in the curd, respectively, and the corresponding nutrient in the milk. Energy recovery, REC(ENERGY), represented the energy content of the cheese versus that in the milk. For statistical analysis, a Bayesian animal model was implemented via Gibbs sampling. The effects of parity (1 to ≥4), days in milk (6 classes), and laboratory vat (15 vats) were assigned flat priors; those of herd-test-date, animal, and residual were given Gaussian prior distributions. Intra-herd heritability estimates of %CY(CURD), %CY(SOLIDS), and %CY(WATER) ranged from 0.224 to 0.267; these were larger than the estimates obtained for milk yield (0.182) and milk fat

  14. Study of Monotonic Properties' Relevance for Estimation of Cyclic Yield Stress and Ramberg-Osgood Parameters of Steels

    NASA Astrophysics Data System (ADS)

    Marohnić, Tea; Basan, Robert

    2016-11-01

    Most of existing methods for estimation of cyclic stress-strain parameters have been developed for steels in general with no regard to the peculiarities of individual steel subgroups. Also, proposed models were commonly developed and evaluated without systematically determining if, and to what extent, individual monotonic properties contribute to their accuracy. In this work, a thorough statistical analysis of experimental datasets of 116 different steels obtained from literature was performed in order to determine which monotonic properties might be relevant for the estimation of cyclic yield stress and cyclic Ramberg-Osgood parameters of unalloyed, low-alloy and high-alloy steels. Only certain monotonic properties used in existing methods were found to be suitable for estimation purposes, while for a number of monotonic properties used in those references no such conclusion can be given. Furthermore, obtained results indicate that steels should not be treated as a single group since different sets of monotonic properties proved to be relevant for unalloyed, low- and high-alloy steel subgroups. Provided list of specific monotonic properties relevant for estimation of individual cyclic parameters of particular steel subgroups can be used for improving the accuracy of existing or development of new estimation methods.

  15. Aminolysis of acyl-chymotrypsins by amino acids. Kinetic appearance of concentration effect in peptide yield enhancement by freezing.

    PubMed

    Töugu, V; Talts, P; Meos, H; Haga, M; Aaviksaar, A

    1995-03-15

    The effects of reagent concentrations, various added substances, pH and temperature on the yield of peptide synthesis by chymotrypsin in frozen and liquid solutions at subzero temperatures have been studied. Increased nucleophile concentration in the liquid microinclusions of ice has been shown to be sufficient for explaining the peptide yield improvement found at freezing conditions.

  16. Effects of the Lycopersicon chmielewskii sucrose accumulator gene (sucr) on fruit yield and quality parameters following introgression into tomato.

    PubMed

    Chetelat, R T; Deverna, J W; Bennett, A B

    1995-07-01

    A gene controlling fruit sucrose accumulation, sucr, was introgressed from the wild tomato species Lycopersicon chmielewskii into the genetic background of a hexose-accumulating cultivated tomato, L. esculentum. During introgression, the size of the L. chmielewskii chromosomal segment containing sucr was reduced by selection for recombination between RFLP markers for the sucr gene and flanking loci. The effects of sucr on soluble solids content, fruit size, yield and other fruit parameters were studied in the genetic background of the processing tomato cultivar 'Huntl00'. In a segregating BC5F2 generation, the smallest introgression containing sucr-associated markers was necessary and sufficient to confer high-level sucrose accumulation, the effects of which were completely recessive. Fruit of sucr/sucr genotypes were smaller than those of +/sucr or +/+ genotypes at all stages of development. The timing of sugar accumulation and total sugar concentration were unaffected by sugar composition. No differences in total fruit biomass (fresh weight of red and green fruit) at harvest were observed between the genotypes, and sucrose accumulators produced greater numbers of fruit than hexose accumulators in one family. However, the proportion of ripe fruit at harvest, and hence yield of ripe fruit, as well as average ripe fruit weight and seed set were reduced in sucr/sucr genotypes. Sucrose accumulation was also associated with increased soluble solids content, consistency, serum viscosity, predicted paste yield and acidity, and decreased color rating. In the first backcross to L. chmielewskii, hexose accumulators (+/sucr) had larger fruit than sucrose accumulators (sucr/sucr), while no difference in soluble solids was detected.

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

    PubMed

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

    2005-01-31

    The estimation of enzyme kinetic parameters by nonlinear fitting reaction curve to the integrated Michaelis-Menten rate equation ln(S(0)/S)+(S(0)-S)/K(m)=(V(m)/K(m))xt was investigated and compared to that by fitting to (S(0)-S)/t=V(m)-K(m)x[ln(S(0)/S)/t] (Atkins GL, Nimmo IA. The reliability of Michaelis-Menten constants and maximum velocities estimated by using the integrated Michaelis-Menten equation. Biochem J 1973;135:779-84) with uricase as the model. Uricase reaction curve was simulated with random absorbance error of 0.001 at 0.075 mmol/l uric acid. Experimental reaction curve was monitored by absorbance at 293 nm. For both CV and deviation <20% by simulation, K(m) from 5 to 100 micromol/l was estimated with Eq. (1) while K(m) from 5 to 50 micromol/l was estimated with Eq. (2). The background absorbance and the error in the lag time of steady-state reaction resulted in negative K(m) with Eq. (2), but did not affect K(m) estimated with Eq. (1). Both equations gave better estimation of V(m). The computation time and the goodness of fit with Eq. (1) were 40-fold greater than those with Eq. (2). By experimentation, Eq. (1) yielded K(m) consistent with the Lineweaver-Burk plot analysis, but Eq. (2) gave many negative parameters. Apparent K(m) by Eq. (1) linearly increased, while V(m) were constant, vs. xanthine concentrations, and the inhibition constant was consistent with the Lineweaver-Burk plot analysis. These results suggested that the integrated rate equation that uses the predictor variable of reaction time was reliable for the estimation of enzyme kinetic parameters and applicable for the characterization of enzyme inhibitors.

  18. A Sensitivity Test of the Ozone Solar Cycle Response with Respect to Chemical Kinetics and Model Parameters

    NASA Astrophysics Data System (ADS)

    Zhang, Q.; Li, K.; Li, C.; Liang, M.; Yung, Y. L.

    2012-12-01

    Previous studies have shown that the observed O3 solar cycle (SC) responses in upper and middle stratosphere are very different from those predicted by models. It is argued whether the differences are within the uncertainties of measurements and chemical kinetic rates. To answer this question, a simple one-dimensional (1-D) Caltech/JPL photochemical model is employed to study the discrepancies between observed and model O3 solar cycle responses. A simplified list of reactions is developed including Chapman, HOx, NOx and ClOx chemistry. We perform sensitivity tests on a significant portion of the kinetic rates to investigate whether the observed O3 SC response can be modeled using standard chemistry. Other model parameters such as eddy diffusivity are included in the tests. Finally, the optimal estimation method (OEM) is employed to derive a set of kinetic rate coefficients and model parameters that would minimize the difference between the observed and the model SC responses in O3. The outcome of retrieval represents the best-fit O3 response under the constraints of standard chemistry and measurement uncertainties.

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

    PubMed

    Remane, Y; Leopold, C S

    2006-01-01

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

  20. Identification of quantitative trait loci for resistance to Verticillium wilt and yield parameters in hop (Humulus lupulus L.).

    PubMed

    Jakse, Jernej; Cerenak, Andreja; Radisek, Sebastjan; Satovic, Zlatko; Luthar, Zlata; Javornik, Branka

    2013-06-01

    Verticillium wilt (VW) can cause substantial yield loss in hop particularly with the outbreaks of the lethal strain of Verticillium albo-atrum. To elucidate genetic control of VW resistance in hop, an F1 mapping population derived from a cross of cultivar Wye Target, with the predicted genetic basis of resistance, and susceptible male breeding line BL2/1 was developed to assess wilting symptoms and to perform QTL mapping. The genetic linkage map, constructed with 203 markers of various types using a pseudo-testcross strategy, formed ten major linkage groups (LG) of the maternal and paternal maps, covering 552.98 and 441.1 cM, respectively. A significant QTL for VW resistance was detected at LOD 7 on a single chromosomal region on LG03 of both parental maps, accounting for 24.2-26.0 % of the phenotypic variance. QTL analysis for alpha-acid content and yield parameters was also performed on this map. QTLs for these traits were also detected and confirmed our previously detected QTLs in a different pedigree and environment. The work provides the basis for exploration of QTL flanking markers for possible use in marker-assisted selection.

  1. 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.

  2. On the protein residues that control the yield and kinetics of O(630) in the photocycle of bacteriorhodopsin.

    PubMed Central

    Li, Q; Bressler, S; Ovrutsky, D; Ottolenghi, M; Friedman, N; Sheves, M

    2000-01-01

    The effects of pH on the yield (phi(r)), and on the apparent rise and decay constants (k(r), k(d)), of the O(630) intermediate are important features of the bacteriorhodopsin (bR) photocycle. The effects are associated with three titration-like transitions: 1) A drop in k(r), k(d), and phi(r) at high pH [pK(a)(1) approximately 8]; 2) A rise in phi(r) at low pH [pK(a)(2) approximately 4.5]; and 3) A drop in k(r) and k(d) at low pH [pK(a)(3) approximately 4. 5]. (pK(a) values are for native bR in 100 mM NaCl). Clarification of these effects is approached by studying the pH dependence of phi(r), k(r), and k(d) in native and acetylated bR, and in its D96N and R82Q mutants. The D96N experiments were carried out in the presence of small amounts of the weak acids, azide, nitrite, and thiocyanate. Analysis of the mutant's data leads to the identification of the protein residue (R(1)) whose state of protonation controls the magnitude of phi(r), k(r), and k(d) at high pH, as Asp-96. Acetylation of bR modifies the Lys-129 residue, which is known to affect the pK(a) of the group (XH), which releases the proton to the membrane exterior during the photocycle. The effects of acetylation on the O(630) parameters reveal that the low-pH titrations should be ascribed to two additional protein residues R(2) and R(3). R(2) affects the rise of phi(r) at low pH, whereas the state of protonation of R(3) affects both k(r) and k(d). Our data confirm a previous suggestion that R(3) should be identified as the proton release moiety (XH). A clear identification of R(2), including its possible identity with R(3), remains open. PMID:10620299

  3. 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.

  4. Estimation of kinetic parameters for enzyme-inhibition reaction models using direct time-dependent equations for reactant concentrations.

    PubMed

    Goličnik, Marko

    2012-03-01

    To facilitate the determination of a reaction type and its kinetics constants for reversible inhibitors of Michaelis-Menten-type enzymes using progress-curve analysis, I present here an explicit equation for direct curve fitting to full time-course data of inhibited enzyme-catalyzed reactions. This algebraic expression involves certain elementary functions where their values are readily available using any standard nonlinear regression program. Hence this allows easy analysis of experimentally observed kinetics without any data conversion prior to fitting. Its implementation gives correct parameter estimates that are in very good agreement with results obtained using both the numerically integrated Michaelis-Menten rate equation or its exact closed-form solution which is expressed in terms of the Lambert W function.

  5. Enzymatic kinetic parameters for polyfluorinated alkyl phosphate hydrolysis by alkaline phosphatase.

    PubMed

    Jackson, Derek A; Mabury, Scott A

    2012-09-01

    The hydrolysis kinetics of three polyfluorinated alkyl phosphate monoesters (monoPAPs), differing in fluorinated chain length, were measured using bovine intestinal alkaline phosphatase to catalyze the reaction. Kinetic values were also measured for analogous hydrogenated phosphate monoesters to elucidate the effects of the fluorinated chain on the rate of enzymatic hydrolysis. Michaelis constants (K(m)) were obtained by a competition kinetics technique in the presence of p-nitrophenyl phosphate (PNPP) using UV-vis spectroscopy. Compared with K(m) (PNPP), Michaelis constants for monoPAPs ranged from 0.9 to 2.1 compared with hydrogenated phosphates, which ranged from 4.0 to 13.0. Apparent bimolecular rate constants (k(cat)/K(m)) were determined by monitoring rates of product alcohol formation at low substrate concentrations using gas chromatography-mass spectrometry. The experimental values for k(cat)/K(m) averaged as 1.1 × 10(7) M(-1) s(-1) for monoPAPs compared with 3.8 × 10(5) M(-1) s(-1) for hexyl phosphate. This suggests that the electron-withdrawing nature of the fluorinated chain enhanced the alcohol leaving group ability. The results were used in a simple model to suggest that monoPAPs in a typical mammalian digestive tract would hydrolyze in approximately 100 s, supporting a previous study that showed its absence after a dosing study in rats.

  6. MECS-VINE®: A New Proximal Sensor for Segmented Mapping of Vigor and Yield Parameters on Vineyard Rows

    PubMed Central

    Gatti, Matteo; Dosso, Paolo; Maurino, Marco; Merli, Maria Clara; Bernizzoni, Fabio; José Pirez, Facundo; Platè, Bonfiglio; Bertuzzi, Gian Carlo; Poni, Stefano

    2016-01-01

    Ground-based proximal sensing of vineyard features is gaining interest due to its ability to serve in even quite small plots with the advantage of being conducted concurrently with normal vineyard practices (i.e., spraying, pruning or soil tilling) with no dependence upon weather conditions, external services or law-imposed limitations. The purpose of the present work was to test performance of the new terrestrial multi-sensor MECS-VINE® in terms of reliability and degree of correlation with several canopy growth and yield parameters in the grapevine. MECS-VINE®, once conveniently positioned in front of the tractor, can provide simultaneous assessment of growth features and microclimate of specific canopy sections of the two adjacent row sides. MECS-VINE® integrates a series of microclimate sensors (air relative humidity, air and surface temperature) with two (left and right) matrix-based optical RGB imaging sensors and a related algorithm, termed Canoyct). MECS-VINE® was run five times along the season in a mature cv. Barbera vineyard and a Canopy Index (CI, pure number varying from 0 to 1000), calculated through its built-in algorithm, validated vs. canopy structure parameters (i.e., leaf layer number, fractions of canopy gaps and interior leaves) derived from point quadrat analysis. Results showed that CI was highly correlated vs. any canopy parameter at any date, although the closest relationships were found for CI vs. fraction of canopy gaps (R2 = 0.97) and leaf layer number (R2 = 0.97) for data pooled over 24 test vines. While correlations against canopy light interception and total lateral leaf area were still unsatisfactory, a good correlation was found vs. cluster and berry weight (R2 = 0.76 and 0.71, respectively) suggesting a good potential also for yield estimates. Besides the quite satisfactory calibration provided, main improvements of MECS-VINE® usage versus other current equipment are: (i) MECS-VINE® delivers a segmented evaluation of the

  7. MECS-VINE(®): A New Proximal Sensor for Segmented Mapping of Vigor and Yield Parameters on Vineyard Rows.

    PubMed

    Gatti, Matteo; Dosso, Paolo; Maurino, Marco; Merli, Maria Clara; Bernizzoni, Fabio; José Pirez, Facundo; Platè, Bonfiglio; Bertuzzi, Gian Carlo; Poni, Stefano

    2016-11-27

    Ground-based proximal sensing of vineyard features is gaining interest due to its ability to serve in even quite small plots with the advantage of being conducted concurrently with normal vineyard practices (i.e., spraying, pruning or soil tilling) with no dependence upon weather conditions, external services or law-imposed limitations. The purpose of the present work was to test performance of the new terrestrial multi-sensor MECS-VINE(®) in terms of reliability and degree of correlation with several canopy growth and yield parameters in the grapevine. MECS-VINE(®), once conveniently positioned in front of the tractor, can provide simultaneous assessment of growth features and microclimate of specific canopy sections of the two adjacent row sides. MECS-VINE(®) integrates a series of microclimate sensors (air relative humidity, air and surface temperature) with two (left and right) matrix-based optical RGB imaging sensors and a related algorithm, termed Canoyct). MECS-VINE(®) was run five times along the season in a mature cv. Barbera vineyard and a Canopy Index (CI, pure number varying from 0 to 1000), calculated through its built-in algorithm, validated vs. canopy structure parameters (i.e., leaf layer number, fractions of canopy gaps and interior leaves) derived from point quadrat analysis. Results showed that CI was highly correlated vs. any canopy parameter at any date, although the closest relationships were found for CI vs. fraction of canopy gaps (R² = 0.97) and leaf layer number (R² = 0.97) for data pooled over 24 test vines. While correlations against canopy light interception and total lateral leaf area were still unsatisfactory, a good correlation was found vs. cluster and berry weight (R² = 0.76 and 0.71, respectively) suggesting a good potential also for yield estimates. Besides the quite satisfactory calibration provided, main improvements of MECS-VINE(®) usage versus other current equipment are: (i) MECS-VINE(®) delivers a segmented

  8. The anomalous expansion of lattice parameter as a function of temperature for an Fe-24Mn alloy during {gamma}{yields}{epsilon} martensitic transformation

    SciTech Connect

    Lu, X.; Qin, Z.; Zhang, Y.; Ding, B.; Hu, Z.

    2000-02-14

    In the present letter, the authors will report their experiment on an Fe-24Mn alloy using high temperature XRD and dilation. A relation between the lattice parameter of austenite and temperature during {gamma}{yields}{epsilon} martensitic transformation was determined. It is expected to be helpful in the understanding of {gamma}{yields}{epsilon} martensitic transformation in Fe-Mn based alloys.

  9. 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.

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

    PubMed

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

    2017-01-13

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

  11. Effect of the label of oligosaccharide acceptors on the kinetic parameters of nasturtium seed xyloglucan endotransglycosylase (XET).

    PubMed

    Kosík, Ondřej; Garajová, Soňa; Matulová, Mária; Rehulka, Pavel; Stratilová, Eva; Farkaš, Vladimír

    2011-02-01

    Fluorescently labeled derivatives of a xyloglucan (XG) nonasaccharide Glc(4)Xyl(3)Gal(2) (XLLG) were used as glycosyl acceptors in assays of xyloglucan endotransglycosylase (XET) from germinated nasturtium (Tropaeolum majus) seeds. We have investigated how the type of the oligosaccharide label influences the kinetic parameters of the reaction. The fluorescent probes used to label XLLG were anthranilic acid (AA), 8-aminonaphtalene-1,3,6-trisulfonic acid (ANTS), fluorescein isothiocyanate (FITC), and sulforhodamine (SR), respectively. The obtained data were compared with those of the reactions where aldose and/or alditol forms of tritium-labeled xyloglucan-derived nonasaccharide served as the respective acceptors. Modification at C-1 of the reducing-end glucose in XLLG by substitution with the fluorophore markedly affected the kinetic parameters of the reaction. The Michaelis constants K(m) for individual acceptors increased in the order [1-(3)H]XLLGXLLG-SR>XLLG-ANTS>[1-(3)H]XLLGol>[1-(3)H]XLLG>XLLG-AA. Catalytic efficiency (expressed as k(cat)/K(m)) with XLLG labeled with SR or FITC was 15 and 28 times, respectively, higher than with the tritium-labeled natural substrate [1-(3)H]XLLG. Comparison of the kinetic parameters found with acceptors labeled with different types of labels enables to select the most effective substrates for the high-throughput assays of XET.

  12. Fast pyrolysis of palm kernel shells: influence of operation parameters on the bio-oil yield and the yield of phenol and phenolic compounds.

    PubMed

    Kim, Seon-Jin; Jung, Su-Hwa; Kim, Joo-Sik

    2010-12-01

    Palm kernel shells were pyrolyzed in a pyrolysis plant equipped with a fluidized-bed reactor and a char-separation system. The influence of reaction temperature, feed size and feed rate on the product spectrum was also investigated. In addition, the effect of reaction temperature on the yields of phenol and phenolic compounds in the bio-oil was examined. The maximum bio-oil yield was 48.7 wt.% of the product at 490 degrees C. The maximum yield of phenol plus phenolic compounds amounted to about 70 area percentage at 475 degrees C. The yield of pyrolytic lignin after its isolation from the bio-oil was approximately 46 wt.% based on the water and ash free oil. The pyrolytic lignin was mainly composed of phenol, phenolic compounds and oligomers of coniferyl, sinapyl and p-coumaryl alcohols. From the result of a GPC analysis, the number average molecular weight and the weight average molecular weight were 325 and 463 g/mol, respectively.

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

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

    PubMed

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

    2007-01-01

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

  15. Effect of malathion on kinetic parameters of acetylcholinesterase (EC 3.1.1.7) in vitro.

    PubMed

    Kamal, M A

    1997-09-01

    Kinetic analysis of the interaction of malathion with camel erythrocyte acetylcholinesterase was investigated in the present study. The Michaelis-Menten constant (K(m)) for the hydrolysis of acetylthiocholine iodide (ASCh) was found to be 53.15 microM and the Vmax was 0.287 mumol/min/mg protein. The Kmapp and Vmaxapp were both decreased by increased malathion concentration. Dixon as well as Lineweaver-Burk plots and their secondary replots indicated that the nature of the inhibition was of the pure uncompetitive type with Ki value estimated as 102.1 ppm. The Kiapp decreased while Vmaxiapp increased by an increased concentration in ASCh.

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

    PubMed

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

    2013-12-01

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

  17. Non-isothermal kinetic parameters and models of crystallization for amorphous Fe-Co-Nb-Cu-B alloys

    NASA Astrophysics Data System (ADS)

    Wang, Xin; Deng, Longjiang; Xie, Jianliang; Liang, Difei

    2013-02-01

    The non-isothermal differential scanning calorimetry (DSC) measurements are often used to study kinetics of amorphous alloys. However non-isothermal kinetic parameters and models of amorphous alloy crystallization process were unclear. In our research, amorphous (FexCo1-x)NbCuB (x=0.33, 0.5 and 0.75) alloys were produced in the form of ribbon by a single roller melt-spinning method. DSC curves at heating rate 5, 10, 15, 20 and 25 K/min were obtained. Kissinger, Ozawa and model-free methods obtain identical activation energies at each exothermic peak of all compositions. We conclude that first exothermic reaction is determined by the migration activation energy of Fe or Co atom; second reaction determined by the energy between parent and product boride phases; and the third reaction determined by the energy between parent α-FeCo phase and product bcc-Fe/fcc-Co phases. We hypothesized a non-isothermal kinetic modelf(α)=α(1, which fit our experiment results well. In this model, m depends on nucleus shape and growth dimension, and n are determined by lattice positions participated in new phase formation.

  18. Model of 2,3-bisphosphoglycerate metabolism in the human erythrocyte based on detailed enzyme kinetic equations: equations and parameter refinement.

    PubMed Central

    Mulquiney, P J; Kuchel, P W

    1999-01-01

    Over the last 25 years, several mathematical models of erythrocyte metabolism have been developed. Although these models have identified the key features in the regulation and control of erythrocyte metabolism, many important aspects remain unexplained. In particular, none of these models have satisfactorily accounted for 2,3-bisphosphoglycerate (2,3-BPG) metabolism. 2,3-BPG is an important modulator of haemoglobin oxygen affinity, and hence an understanding of the regulation of 2,3-BPG concentration is important for understanding blood oxygen transport. A detailed, comprehensive, and hence realistic mathematical model of erythrocyte metabolism is presented that can explain the regulation and control of 2,3-BPG concentration and turnover. The model is restricted to the core metabolic pathways, namely glycolysis, the 2,3-BPG shunt and the pentose phosphate pathway (PPP), and includes membrane transport of metabolites, the binding of metabolites to haemoglobin and Mg(2+), as well as pH effects on key enzymic reactions and binding processes. The model is necessarily complex, since it is intended to describe the regulation and control of 2,3-BPG metabolism under a wide variety of physiological and experimental conditions. In addition, since H(+) and blood oxygen tension are important external effectors of 2,3-BPG concentration, it was important that the model take into account the large array of kinetic and binding phenomena that result from changes in these effectors. Through an iterative loop of experimental and simulation analysis many values of enzyme-kinetic parameters of the model were refined to yield close conformity between model simulations and 'real' experimental data. This iterative process enabled a single set of parameters to be found which described well the metabolic behaviour of the erythrocyte under a wide variety of conditions. PMID:10477269

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

    PubMed

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

    2014-01-03

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

  20. Enzyme immobilization in porous silicon: quantitative analysis of the kinetic parameters for glutathione-S-transferases.

    PubMed

    Delouise, Lisa A; Miller, Benjamin L

    2005-04-01

    Porous silicon matrixes are attractive materials for the construction of biosensors and may also have utility for the production of immobilized enzyme bioreactors. In an effort to gain a quantitative understanding of the effects of immobilization on enzyme activity, we compared the activity of glutathione-S-transferase immobilized in electrochemically etched porous silicon films (approximately 6.5 microm thick) with the enzyme in solution. Kinetic measurements were made by varying the glutathione concentration while maintaining a fixed saturating concentration of 1-chloro-2,4-dinitrobenzene. The reaction kinetics follow steady-state equilibrium behavior. The specific activity of the free enzyme in solution is approximately 4x higher than the immobilized enzyme, for which we measured an apparent K'(m)(GSH) value of 1.0 +/- 0.3. The maximum velocity, V'(max), is linearly proportional to immobilized enzyme concentration, but the magnitude is approximately 20 times lower than that in solution. Results suggest approximately 25% of the enzyme is bound with the catalytic site in an inactive conformation or in a hindered orientation. Finally, the effects of hydration and exposure to denaturants on the immobilized enzyme activity are presented.

  1. A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Semmes, D. H.; Ravishankara, A. R.

    1981-01-01

    Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

  2. Yields of clustered DNA damage induced by charged-particle radiations of similar kinetic energy per nucleon: LET dependence in different DNA microenvironments

    SciTech Connect

    Keszenman, D.J.; Sutherland, B. M.

    2010-08-01

    To determine the linear energy transfer (LET) dependence of the biological effects of densely ionizing radiation in relation to changes in the ionization density along the track, we measured the yields and spectrum of clustered DNA damages induced by charged particles of different atomic number but similar kinetic energy per nucleon in different DNA microenvironments. Yeast DNA embedded in agarose in solutions of different free radical scavenging capacity was irradiated with 1 GeV protons, 1 GeV/nucleon oxygen ions, 980 MeV/nucleon titanium ions or 968 MeV/nucleon iron ions. The frequencies of double-strand breaks (DSBs), abasic sites and oxypurine clusters were quantified. The total DNA damage yields per absorbed dose induced in non-radioquenching solution decreased with LET, with minor variations in radioquenching conditions being detected. However, the total damage yields per particle fluence increased with LET in both conditions, indicating a higher efficiency per particle to induce clustered DNA damages. The yields of DSBs and non-DSB clusters as well as the damage spectra varied with LET and DNA milieu, suggesting the involvement of more than one mechanism in the formation of the different types of clustered damages.

  3. Isotherm parameters and intraparticle mass transfer kinetics on molecularly imprinted polymers in acetonitrile/buffer mobile phases

    SciTech Connect

    Kim, Hyunjung; Kaczmarski, Krzysztof; Guiochon, Georges A

    2006-03-01

    The equilibrium isotherm and the intraparticle mass transfer kinetics of the enantiomers of the template were investigated on an Fmoc-L-tryptophan (Fmoc-L-Trp) imprinted polymer at different pHs and water concentrations in acetonitrile/aqueous buffer mobile phases. The equilibrium isotherm data were measured using frontal analysis at 25 {+-} 2 C. The adsorption energy distribution was found to be trimodal, with narrow modes. Consistent with this distribution, the adsorption data were modeled using a tri-Langmuir isotherm equation and the best estimates of the isotherm parameters were determined. The intraparticle mass transfer parameters were derived by comparing the profiles of experimental overloaded bands and the profiles calculated using the isotherm model and the lumped pore diffusion (POR) model of chromatography. These results showed that different adsorption and mass transfer mechanisms exist in mobile phases made of acetonitrile/aqueous buffer and of acetonitrile/acetic acid solutions.

  4. Yield and kinetic constants estimation in the production of hydroxy fatty acids from oleic acid in a bioreactor by Pseudomonas aeruginosa 42A2.

    PubMed

    Martin-Arjol, Ignacio; Llacuna, Joan Llorens; Manresa, Angeles

    2014-12-01

    We modelled the production of hydroxy fatty acids from oleic acid by Pseudomonas aeruginosa 42A2 in a bioreactor with a non-dispersive aeration system. First, we designed an adapted wetted-wall gas-absorption column, offering a k La value of 39.9 h(-1), to enhance oxygen absorption in the culture media and prevent foam formation. Then, we analysed different kinetic models to simulate the yield coefficients and the kinetic constants in this bacterial transformation. Monod model fitting (μ max1 = 0.51 h(-1), K S1 = 1.60 C-mol l(-1), μ max2 = 0.12 h(-1), K S2 = 0.035 C-mol l(-1), and k 2 = 0.033 h(-1)) showed a good accuracy with the experimental data sets and was chosen for its simplicity. Lastly, mass balances were carried out to establish the stoichiometry of this biotransformation with the following yield coefficients, Υ X/OA, Υ X/(10S)-HPOME and Υ (10S)-HPOME/(7S10S)-HPOME of 0.172, 0.347 and 2.388 C-mol C-mol(-1), respectively.

  5. Degradation of ciprofloxacin in water by advanced oxidation process: kinetics study, influencing parameters and degradation pathways.

    PubMed

    Sayed, Murtaza; Ismail, M; Khan, Sanaullah; Tabassum, Safia; Khan, Hasan M

    2016-01-01

    Gamma-radiation-induced degradation of ciprofloxacin (CIP) in aqueous solution and the factors affecting the degradation process have been investigated. The results showed that CIP (4.6 mg/L) was almost completely degraded at an absorbed dose of 870 Gy. The kinetic studies of aqueous solutions containing 4.6, 10, 15 and 17.9 mg/L indicated that the decomposition of CIP by gamma irradiation followed pseudo-first-order kinetics and the decay constant (k) decreased from 5.9  ×  10(-3) to 1.6  ×  10(-3) Gy(-1) with an increase in CIP initial concentration from 4.6 to 17.9 mg/L. The effect of saturation of CIP solution with N2, N2O or air on radiation-induced degradation of CIP was also investigated. The effects of radical scavengers, such as t-BuOH and i-PrOH, showed the role of reactive radicals towards degradation of CIP in the order of OH > e(aq)- . H. The apparent second-order rate constant of [Formula: see text] with CIP was calculated to be 2.64 × 10(9) M(-1) s(-1). The effects of solution pH as well as natural water contaminants, such as [HCO3-, CO3(2-), and NO2-, on CIP degradation by gamma-irradiation were also investigated. Major degradation products, including organic acids, were identified using UPLC-MS/MS and IC, and degradation pathways have been proposed.

  6. A Compilation of Rate Parameters of Water-Mineral Interaction Kinetics for Application to Geochemical Modeling

    DTIC Science & Technology

    2004-03-01

    35 3.3.1 Cordierite and Tourmaline ...Cyclosilicates 3.3.1 Cordierite and Tourmaline Rate parameters for the acidic and neutral mechanisms (data are absent for the basic mechanism) for cordierite...and tourmaline were compiled from Sverdrup (1990; Table 24), with activation energies calculated herein from reported rate constants at 8 and 25 °C

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

    SciTech Connect

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

    2012-04-19

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

  8. Kinetic modeling and parameter estimation in a tower bioreactor for bioethanol production.

    PubMed

    Ccopa Rivera, Elmer; da Costa, Aline Carvalho; Lunelli, Betânia Hoss; Maciel, Maria Regina Wolf; Maciel Filho, Rubens

    2008-03-01

    In this work, a systematic method to support the building of bioprocess models through the use of different optimization techniques is presented. The method was applied to a tower bioreactor for bioethanol production with immobilized cells of Saccharomyces cerevisiae. Specifically, a step-by-step procedure to the estimation problem is proposed. As the first step, the potential of global searching of real-coded genetic algorithm (RGA) was applied for simultaneous estimation of the parameters. Subsequently, the most significant parameters were identified using the Placket-Burman (PB) design. Finally, the quasi-Newton algorithm (QN) was used for optimization of the most significant parameters, near the global optimum region, as the initial values were already determined by the RGA global-searching algorithm. The results have shown that the performance of the estimation procedure applied in a deterministic detailed model to describe the experimental data is improved using the proposed method (RGA-PB-QN) in comparison with a model whose parameters were only optimized by RGA.

  9. Decay kinetics and quantum yields of fluorescence in photosystem I from Synechococcus elongatus with P700 in the reduced and oxidized state: are the kinetics of excited state decay trap-limited or transfer-limited?

    PubMed Central

    Byrdin, M; Rimke, I; Schlodder, E; Stehlik, D; Roelofs, T A

    2000-01-01

    Transfer and trapping of excitation energy in photosystem I (PS I) trimers isolated from Synechococcus elongatus have been studied by an approach combining fluorescence induction experiments with picosecond time-resolved fluorescence measurements, both at room temperature (RT) and at low temperature (5 K). Special attention was paid to the influence of the oxidation state of the primary electron donor P700. A fluorescence induction effect has been observed, showing a approximately 12% increase in fluorescence quantum yield upon P700 oxidation at RT, whereas at temperatures below 160 K oxidation of P700 leads to a decrease in fluorescence quantum yield ( approximately 50% at 5 K). The fluorescence quantum yield for open PS I (with P700 reduced) at 5 K is increased by approximately 20-fold and that for closed PS I (with P700 oxidized) is increased by approximately 10-fold, as compared to RT. Picosecond fluorescence decay kinetics at RT reveal a difference in lifetime of the main decay component: 34 +/- 1 ps for open PS I and 37 +/- 1 ps for closed PS I. At 5 K the fluorescence yield is mainly associated with long-lived components (lifetimes of 401 ps and 1.5 ns in closed PS I and of 377 ps, 1.3 ns, and 4.1 ns in samples containing approximately 50% open and 50% closed PS I). The spectra associated with energy transfer and the steady-state emission spectra suggest that the excitation energy is not completely thermally equilibrated over the core-antenna-RC complex before being trapped. Structure-based modeling indicates that the so-called red antenna pigments (A708 and A720, i.e., those with absorption maxima at 708 nm and 720 nm, respectively) play a decisive role in the observed fluorescence kinetics. The A720 are preferentially located at the periphery of the PS I core-antenna-RC complex; the A708 must essentially connect the A720 to the reaction center. The excited-state decay kinetics turn out to be neither purely trap limited nor purely transfer (to the trap

  10. Optimization of urease immobilization onto non-porous HEMA incorporated poly(EGDMA) microbeads and estimation of kinetic parameters.

    PubMed

    Ayhan, F; Ayhan, H; Pişkin, E; Tanyolaç, A

    2002-01-01

    Jack bean urease (urea aminohydrolase, EC 3.5.1.5) was immobilized onto modified non-porous poly(ethylene glycol dimethacrylate/2-hydroxy ethylene methacrylate), (poly(EGDMA/HEMA)), microbeads prepared by suspension copolymerization for the potential use in hemoperfusion columns, not previously reported. The conditions of immobilization; enzyme concentration, medium pH, substrate and ethylene diamine tetra acetic acid (EDTA) presence in the immobilization medium in different concentrations, enzyme loading ratio, processing time and immobilization temperature were investigated for highest apparent activity. Immobilized enzyme retained 73% of its original activity for 75 days of repeated use with a deactivation constant kd = 3.72 x 10(-3) day(-1). A canned non-linear regression program was used to estimate the intrinsic kinetic parameters of immobilized enzyme with a low value of observable Thiele modulus (phi < 0.3) and these parameters were compared with those of free urease. The best-fit kinetic parameters of a Michaelis-Menten model were estimated as Vm = 3.318 x 10(-4) micromol/s mg bound enzyme protein, Km = 15.94 mM for immobilized, and Vm = 1.074 micromol NH3/s mg enzyme protein, Km = 14.49 mM for free urease. The drastic decrease in Vm value was attributed to steric effects, conformational changes in enzyme structure or denaturation of the enzyme during immobilization. Nevertheless, the change in Km value was insignificant for the unchanged affinity of the substrate with immobilization. For higher immobilized urease activity, smaller particle size and concentrated urease with higher specific activity could be used in the immobilization process.

  11. 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

  12. Kinetics Parameters of VVER-1000 Core with 3 MOX Lead Test Assemblies To Be Used for Accident Analysis Codes

    SciTech Connect

    Pavlovitchev, A.M.

    2000-03-08

    The present work is a part of Joint U.S./Russian Project with Weapons-Grade Plutonium Disposition in VVER Reactor and presents the neutronics calculations of kinetics parameters of VVER-1000 core with 3 introduced MOX LTAs. MOX LTA design has been studied in [1] for two options of MOX LTA: 100% plutonium and of ''island'' type. As a result, zoning i.e. fissile plutonium enrichments in different plutonium zones, has been defined. VVER-1000 core with 3 introduced MOX LTAs of chosen design has been calculated in [2]. In present work, the neutronics data for transient analysis codes (RELAP [3]) has been obtained using the codes chain of RRC ''Kurchatov Institute'' [5] that is to be used for exploitation neutronics calculations of VVER. Nowadays the 3D assembly-by-assembly code BIPR-7A and 2D pin-by-pin code PERMAK-A, both with the neutronics constants prepared by the cell code TVS-M, are the base elements of this chain. It should be reminded that in [6] TVS-M was used only for the constants calculations of MOX FAs. In current calculations the code TVS-M has been used both for UOX and MOX fuel constants. Besides, the volume of presented information has been increased and additional explications have been included. The results for the reference uranium core [4] are presented in Chapter 2. The results for the core with 3 MOX LTAs are presented in Chapter 3. The conservatism that is connected with neutronics parameters and that must be taken into account during transient analysis calculations, is discussed in Chapter 4. The conservative parameters values are considered to be used in 1-point core kinetics models of accident analysis codes.

  13. Respirometric measurement of kinetic parameters: effect of activated sludge floc size.

    PubMed

    Chu, K H; van Veldhuizen, H M; van Loosdrecht, M C M

    2003-01-01

    The variation of activated sludge floc size with the mixing intensity of a mechanically stirred respirometer, expressed in terms of the mean energy dissipation rate, was characterized using a photometric dispersion analyzer. The floc size decreased rapidly when the energy dissipation rate was increased from 1.33 x 10(-3) to 2.68 x 10(-3) W/kg. Experiments were performed to investigate the effect of floc size on the oxygen saturation coefficient measured under the condition of acetate oxidation. The respirometric data were interpreted by considering only the kinetics of biochemical reactions. The variation of the oxygen saturation coefficient with mixing intensity was found to correlate with the variation of floc size with mixing intensity. The oxygen saturation coefficient was found to decrease from 0.23 to 0.08 mg/L when the mean energy dissipation rate was increased from 1.33 x 10(-3) to 2.68 x 10(-3) W/kg. The dependence of the oxygen saturation coefficient on floc size or mixing intensity suggests the presence of mass transfer resistances in large flocs.

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

    PubMed

    Bünemann, H

    1982-11-25

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

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

    PubMed Central

    Bünemann, H

    1982-01-01

    The accessibility of immobilized DNA has been shown to depend more crucially on the method of immobilization than on the type of support used for fixation. When sonicated denatured DNA is coupled via diazotization or via cyanogen bromide reaction to solid Sephadex G-25 and Cellex 410 or to macroporous Sephacryl S-500 and Sepharose C1-6B its accessibility varies from 100 to 24 percent. Generally the loss of accessibility is linked to a depression of the melting temperature of DNA helices formed on the support. This correlation shows a characteristic course for a particular coupling method. DNA coupled under denaturing conditions may become totally inaccessible when only 3 percent of its bases are involved in the covalent linkage. Kinetic experiments with sonicated E.coli DNA have shown that the rate constants for renaturation or hybridization reactions are very similar for DNA immobilized by different methods to solid or macroporous supports. Generally the second order rate constant for a heterogeneous reaction (between mobile and immobilized DNA) is about one order of magnitude smaller than that of the analogous homogeneous reaction (in solution). PMID:6185922

  16. Temperature Effects on Kinetic Parameters and Substrate Affinity of Cel7A Cellobiohydrolases*

    PubMed Central

    Sørensen, Trine Holst; Cruys-Bagger, Nicolaj; Windahl, Michael Skovbo; Badino, Silke Flindt; Borch, Kim; Westh, Peter

    2015-01-01

    We measured hydrolytic rates of four purified cellulases in small increments of temperature (10–50 °C) and substrate loads (0–100 g/liter) and analyzed the data by a steady state kinetic model that accounts for the processive mechanism. We used wild type cellobiohydrolases (Cel7A) from mesophilic Hypocrea jecorina and thermophilic Rasamsonia emersonii and two variants of these enzymes designed to elucidate the role of the carbohydrate binding module (CBM). We consistently found that the maximal rate increased strongly with temperature, whereas the affinity for the insoluble substrate decreased, and as a result, the effect of temperature depended strongly on the substrate load. Thus, temperature had little or no effect on the hydrolytic rate in dilute substrate suspensions, whereas strong temperature activation (Q10 values up to 2.6) was observed at saturating substrate loads. The CBM had a dual effect on the activity. On one hand, it diminished the tendency of heat-induced desorption, but on the other hand, it had a pronounced negative effect on the maximal rate, which was 2-fold larger in variants without CBM throughout the investigated temperature range. We conclude that although the CBM is beneficial for affinity it slows down the catalytic process. Cel7A from the thermophilic organism was moderately more activated by temperature than the mesophilic analog. This is in accord with general theories on enzyme temperature adaptation and possibly relevant information for the selection of technical cellulases. PMID:26183777

  17. Chemical mechanism of lysophosphatidylcholine: lysophosphatidylcholine acyltransferase from rabbit lung. pH-dependence of kinetic parameters.

    PubMed Central

    Pérez-Gil, J; Martín, J; Acebal, C; Arche, R

    1990-01-01

    Lysophosphatidylcholine: lysophosphatidylcholine acyltransferase is an enzyme that catalyses two reactions: hydrolysis of lysophosphatidylcholine and transacylation between two molecules of lysophosphatidylcholine to give disaturated phosphatidylcholine. Following the kinetic model previously proposed for this enzyme [Martín, Pérez-Gil, Acebal & Arche (1990) Biochem. J. 266, 47-53], the values of essential pK values in free enzyme and substrate-enzyme complexes have now been determined. The chemical mechanism of catalysis was dependent on the deprotonation of a histidine residue with pK about 5.7. This result was supported by the perturbation of pK values by addition of organic solvent. Very high and exothermic enthalpy of ionization was measured, indicating that a conformational re-arrangement in the enzyme accompanies the ionization of the essential histidine residue. These results, as well as the results from previous studies, enabled the proposal of a chemical mechanism for the enzymic reactions catalysed by lysophosphatidylcholine: lysophosphatidylcholine acyltransferase from rabbit lung. PMID:2241908

  18. Electrochemical oxidation of an azo dye in aqueous media investigation of operational parameters and kinetics.

    PubMed

    Parsa, J Basiri; Rezaei, M; Soleymani, A R

    2009-09-15

    In this research two types of electrochemical reactors for the treatment of simulated wastewaters containing Direct blue 71 azo dye (DB71) were used: (1) Laboratory scale undivided electrolysis cell system (450 mL volume) with one 2 cm x 2 cm platinum plate as the anode placed in the middle of the cell and two 2 cm x 8 cm steel plates (SS-304) as cathodes placed in the sides of the cell 2 cm from the central anode. (2) Pilot scale reactor (9L volume), equipped with two 3 cm x 23 cm stainless steel plates as anode and cathode, with distance of 3 cm apart. The influence of supporting electrolyte, applied voltage and pH were studied. The UV-vis spectra of samples during the electrochemical oxidation showed the rapid decolorization of the dye solution. During the process, the COD and current were measured in order to evaluate the degree of mineralization, energy consumption, current and anode efficiencies. The optimum supporting electrolyte and applied voltage were NaCl (5 g L(-1)) and 15 V. Using the lab scale reactor resulted in complete decolorization and mineralization of the dye solutions after ca. 90 and 120 min, respectively. Similar results were obtained using the pilot plant reactor under the same conditions. The good fit of the data to pseudo-first-order kinetics for COD removal at all applied voltages (except 20 V) was taken as proof of the involvement of indirect oxidation pathways in the process.

  19. Estimates of genetic parameters for total milk yield over multiple ages in Brazilian Murrah buffaloes using different models.

    PubMed

    Sesana, R C; Baldi, F; Borquis, R R A; Bignardi, A B; Hurtado-Lugo, N A; El Faro, L; Albuquerque, L G; Tonhati, H

    2014-04-14

    The objective of this study was to estimate variance components and genetic parameters for accumulated 305-day milk yield (MY305) over multiple ages, from 24 to 120 months of age, applying random regression (RRM), repeatability (REP) and multi-trait (MT) models. A total of 4472 lactation records from 1882 buffaloes of the Murrah breed were utilized. The contemporary group (herd-year-calving season) and number of milkings (two levels) were considered as fixed effects in all models. For REP and RRM, additive genetic, permanent environmental and residual effects were included as random effects. MT considered the same random effects as did REP and RRM with the exception of permanent environmental effect. Residual variances were modeled by a step function with 1, 4, and 6 classes. The heritabilities estimated with RRM increased with age, ranging from 0.19 to 0.34, and were slightly higher than that obtained with the REP model. For the MT model, heritability estimates ranged from 0.20 (37 months of age) to 0.32 (94 months of age). The genetic correlation estimates for MY305 obtained by RRM (L23.res4) and MT models were very similar, and varied from 0.77 to 0.99 and from 0.77 to 0.99, respectively. The rank correlation between breeding values for MY305 at different ages predicted by REP, MT, and RRM were high. It seems that a linear and quadratic Legendre polynomial to model the additive genetic and animal permanent environmental effects, respectively, may be sufficient to explain more parsimoniously the changes in MY305 genetic variation with age.

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

    PubMed Central

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

    2012-01-01

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

  1. Deciphering the impact of parameters influencing transgene expression kinetics after repeated cell transduction with integration-deficient retroviral vectors.

    PubMed

    Schott, Juliane W; Jaeschke, Nico M; Hoffmann, Dirk; Maetzig, Tobias; Ballmaier, Matthias; Godinho, Tamaryin; Cathomen, Toni; Schambach, Axel

    2015-05-01

    Lentiviral and gammaretroviral vectors are state-of-the-art tools for transgene expression within target cells. The integration of these vectors can be deliberately suppressed to derive a transient gene expression system based on extrachromosomal circular episomes with intact coding regions. These episomes can be used to deliver DNA templates and to express RNA or protein. Importantly, transient gene transfer avoids the genotoxic side effects of integrating vectors. Restricting their applicability, episomes are rapidly lost upon dilution in dividing target cells. Addressing this limitation, we could establish comparably stable percentages of transgene-positive cells over prolonged time periods in proliferating cells by repeated transductions. Flow cytometry was applied for kinetic analyses to decipher the impact of individual parameters on the kinetics of fluoroprotein expression after episomal retransduction and to visualize sequential and simultaneous transfer of heterologous fluoroproteins. Expression windows could be exactly timed by the number of transduction steps. The kinetics of signal loss was affected by the cell proliferation rate. The transfer of genes encoding fluoroproteins with different half-lives revealed a major impact of protein stability on temporal signal distribution and accumulation, determining optimal retransduction intervals. In addition, sequential transductions proved broad applicability in different cell types and using different envelope pseudotypes without receptor overload. Stable percentages of cells coexpressing multiple transgenes could be generated upon repeated coadministration of different episomal vectors. Alternatively, defined patterns of transgene expression could be recapitulated by sequential transductions. Altogether, we established a methodology to control and adjust a temporally defined window of transgene expression using retroviral episomal vectors. Combined with the highly efficient cell entry of these vectors while

  2. 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.

  3. 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.

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

    PubMed

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

    2004-03-01

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

  5. A stochastic formulation of the gompertzian growth model for in vitro bactericidal kinetics: parameter estimation and extinction probability.

    PubMed

    Ferrante, L; Bompadre, S; Leone, L; Montanari, M P

    2005-06-01

    Time-kill curves have frequently been employed to study the antimicrobial effects of antibiotics. The relevance of pharmacodynamic modeling to these investigations has been emphasized in many studies of bactericidal kinetics. Stochastic models are needed that take into account the randomness of the mechanisms of both bacterial growth and bacteria-drug interactions. However, most of the models currently used to describe antibiotic activity against microorganisms are deterministic. In this paper we examine a stochastic differential equation representing a stochastic version of a pharmacodynamic model of bacterial growth undergoing random fluctuations, and derive its solution, mean value and covariance structure. An explicit likelihood function is obtained both when the process is observed continuously over a period of time and when data is sampled at time points, as is the custom in these experimental conditions. Some asymptotic properties of the maximum likelihood estimators for the model parameters are discussed. The model is applied to analyze in vitro time-kill data and to estimate model parameters; the probability of the bacterial population size dropping below some critical threshold is also evaluated. Finally, the relationship between bacterial extinction probability and the pharmacodynamic parameters estimated is discussed.

  6. Estimation of transport and degradation parameters for naphthalene and anthracene: influence of mass transfer on kinetics.

    PubMed

    Owabor, Chiedu N; Ogbeide, Samuel E; Susu, Alfred A

    2010-10-01

    The method of temporal moment solutions (MOM) for one-dimensional convective-dispersive solute transport involving linear equilibrium sorption and first-order degradation for time pulse sources has been applied to analyze experimental data from a soil microcosm reactor. Estimation of the pore water velocity V for a nonreactive solute was aided by the use of only the first normalized moment while the dispersion coefficient D, first-order degradation rate constant lambda, and the retardation factor R were estimated using both first and second normalized moments. These transport and degradation parameters were compared to those obtained by a transport model using a nonlinear least square curve-fitting program CXTFIT (version 2.0). Results obtained showed that the MOM fits the breakthrough curve with tailing better than the CXTFIT. The initial estimates of these parameters aided the reduction of the dimensionality of the search process of the non- steady-state model. A residual concentration of 1.12E-5 and 1.48 mg/l for naphthalene and 7.67E-4 and 1.61 mg/l for anthracene, in the axial and radial directions, respectively, suggests the preference of naphthalene during the biodegradation process. The surface concentration as depicted using three-dimensional plots showed that there is occlusion of the aromatics (naphthalene and anthracene) within the soil micropores, thereby limiting their bioavailability and in the long run increasing their toxicity.

  7. Determination of kinetic parameters of crystal growth rate of borax in aqueous solution by using the rotating disc technique

    NASA Astrophysics Data System (ADS)

    Sahin, Omer; Aslan, Fevzi; Ozdemir, Mustafa; Durgun, Mustafa

    2004-10-01

    Growth rate of polycrystalline disc of borax compressed at different pressure and rotated at various speed has been measured in a rotating disc crystallizer under well-defined conditions of supersaturation. It was found that the mass transfer coefficient, K, increased while overall growth rate constant, Kg, and surface reaction constant, kr, decreased with increasing smoothness of the disc. It was also determined that kinetic parameters (kr , r , K , g) of crystal growth rate of borax decreased with increasing rotating speed of the polycrystalline disc. The effectiveness factor was calculated from the growth rate data to evaluate the relative magnitude of the steps in series bulk diffusion through the mass transfer boundary layer and the surface integration. At low rotating speed of disc, the crystal growth rate of borax is mainly controlled by integration. However, both diffusion and integration steps affect the growth rate of borax at higher rotating speed of polycrystalline disc.

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

    NASA Astrophysics Data System (ADS)

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

    2006-03-01

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

  9. Thermoluminescence dosimetry properties and kinetic parameters of lithium potassium borate glass co-doped with titanium and magnesium oxides.

    PubMed

    Hashim, S; Alajerami, Y S M; Ramli, A T; Ghoshal, S K; Saleh, M A; Abdul Kadir, A B; Saripan, M I; Alzimami, K; Bradley, D A; Mhareb, M H A

    2014-09-01

    Lithium potassium borate (LKB) glasses co-doped with TiO2 and MgO were prepared using the melt quenching technique. The glasses were cut into transparent chips and exposed to gamma rays of (60)Co to study their thermoluminescence (TL) properties. The TL glow curve of the Ti-doped material featured a single prominent peak at 230 °C. Additional incorporation of MgO as a co-activator enhanced the TL intensity threefold. LKB:Ti,Mg is a low-Z material (Z(eff)=8.89) with slow signal fading. Its radiation sensitivity is 12 times lower that the sensitivity of TLD-100. The dose response is linear at doses up to 10(3) Gy. The trap parameters, such as the kinetics order, activation energy, and frequency factor, which are related to the glow peak, were determined using TolAnal software.

  10. Dynamic determination of kinetic parameters, computer simulation, and probabilistic analysis of growth of Clostridium perfringens in cooked beef during cooling.

    PubMed

    Huang, Lihan

    2015-02-16

    The objective of this research was to develop a new one-step methodology that uses a dynamic approach to directly construct a tertiary model for prediction of the growth of Clostridium perfringens in cooked beef. This methodology was based on simultaneous numerical analysis and optimization of both primary and secondary models using multiple dynamic growth curves obtained under different conditions. Once the models were constructed, the bootstrap method was used to calculate the 95% confidence intervals of kinetic parameters, and a Monte Carlo simulation method was developed to validate the models using the growth curves not previously used in model development. The results showed that the kinetic parameters obtained from this study accurately matched the common characteristics of C. perfringens, with the optimum temperature being 45.3°C. The results also showed that the predicted growth curves matched accurately with experimental observations used in validation. The mean of residuals of the predictions is -0.02logCFU/g, with a standard deviation of only 0.23logCFU/g. For relative growths <1logCFU/g, the residuals of predictions are <0.4logCFU/g. Overall, 74% of the residuals of predictions are <0.2logCFU/g, 7.7% are >0.4logCFU/g, while only 1.5% are >0.8logCFU/g. In addition, the dynamic model also accurately predicted four isothermal growth curves arbitrarily chosen from the literature. Finally, the Monte Carlo simulation was used to provide the probability of >1 and 2logCFU/g relative growths at the end of cooling. The results of this study will provide a new and accurate tool to the food industry and regulatory agencies to assess the safety of cooked beef in the event of cooling deviation.

  11. Chlorophyll fluorescence induction kinetics and yield responses in rainfed crops with variable potassium nutrition in K deficient semi-arid alfisols.

    PubMed

    Srinivasarao, Ch; Shanker, Arun K; Kundu, Sumanta; Reddy, Sharanbhoopal

    2016-07-01

    Optimum potassium (K) nutrition in semi-arid regions may help crop plants to overcome constraints in their growth and development such as moisture stress, leading to higher productivity of rainfed crops, thus judicious K management is essential. A study was conducted to evaluate the importance of K nutrition on physiological processes like photosynthesis through chlorophyll a fluorescence and chlorophyll fluorescence induction kinetics (OJIP) of rainfed crops viz., maize (Zea mays L.), pearl millet (Pennisetum glaucum), groundnut (Arachis hypogaea), sunflower (Helianthus annuus), castor (Ricinus communis L.) and cotton (Gossypium hirsutum) under water stress conditions by studying their growth attributes, water relations, yield, K uptake and use efficiency under varied K levels. Highest chlorophyll content was observed under K60 in maize and pearl millet. Narrow and wide Chl a:b ratio was observed in castor and groundnut respectively. The fluorescence yield decreased in the crops as K dosage increased, evidenced by increasing of all points (O, J, I and P) of the OJIP curves. The fluorescence transient curve for K60 was lower than K0 and K40 for all the crops. Potassium levels altered the fluorescence induction and impaired photosynthetic systems in all the crops studied. There was no distinct trend observed in leaf water potential of crops under study. Uptake of K was high in sunflower with increased rate of K application. Quantitatively, K uptake by castor crop was lesser compared to all other crops. Our results indicate that the yield reduction under low K was due to the low capacity of the crops to translocate K from non-photosynthetic organs such as stems and petioles to upper leaves and harvested organs and this in turn influenced the capacity of the crops to produce a high economic yield per unit of K taken up thus reducing utilization efficiency of K.

  12. On the design of optimal dynamic experiments for parameter estimation of a Ratkowsky-type growth kinetics at suboptimal temperatures.

    PubMed

    Bernaerts, K; Versyck, K J; Van Impe, J F

    2000-03-10

    It is generally known that accurate model building, i.e., proper model structure selection and reliable parameter estimation, constitutes an essential matter in the field of predictive microbiology, in particular, when integrating these predictive models in food safety systems. In this context, Versyck et al. (1999) have introduced the methodology of optimal experimental design techniques for parameter estimation within the field. Optimal experimental design focuses on the development of optimal input profiles such that the resulting rich (i.e., highly informative) experimental data enable unique model parameter estimation. As a case study, Versyck et al. (1999) [Versyck, K., Bernaerts, K., Geeraerd, A.H., Van Impe, J.F., 1999. Introducing optimal experimental design in predictive modeling: a motivating example. Int. J. Food Microbiol., 51(1), 39-51] have elaborated the estimation of Bigelow inactivation kinetics parameters (in a numerical way). Opposed to the classic (static) experimental approach in predictive modelling, an optimal dynamic experimental setup is presented. In this paper, the methodology of optimal experimental design or parameter estimation is applied to obtain uncorrelated estimates of the square root model parameters [Ratkowsky, D.A., Olley, J., McMeekin, T.A., Ball, A., 1982. Relationship between temperature and growth rate of bacterial cultures. J. Bacteriol. 149, 1-5] describing the effect of suboptimal growth temperatures on the maximum specific growth rate of microorganisms. These estimates are the direct result of fitting a primary growth model to cell density measurements as a function of time. Apart from the design of an optimal time-varying temperature profile based on a sensitivity study of the model output, an important contribution of this publication is a first experimental validation of this innovative dynamic experimental approach for uncorrelated parameter identification. An optimal step temperature profile, within the range of

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

    PubMed Central

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

    2013-01-01

    The steady-state kinetic parameters of pyridoxal 5’-phosphate-dependent recombinant methionine γ -lyase from three pathogenic bacteria, Clostridium tetani, Clostridium sporogenes, and Porphyromonas gingivalis, were determined in β- and γ-elimination reactions. The enzyme from C. sporogenes is characterized by the highest catalytic efficiency in the γ-elimination reaction of L-methionine. It was demonstrated that the enzyme from these three sources exists as a tetramer. The N-terminal poly-histidine fragment of three recombinant enzymes influences their catalytic activity and facilitates the aggregation of monomers to yield dimeric forms under denaturing conditions. The cytotoxicity of methionine γ-lyase from C. sporogenes and C. tetani in comparison with Citrobacter freundii was evaluated using K562, PC-3, LnCap, MCF7, SKOV-3, and L5178y tumor cell lines. K562 (IC50=0.4–1.3 U/ml), PC-3 (IC50=0.1–0.4 U/ml), and MCF7 (IC50=0.04–3.2 U/ml) turned out to be the most sensitive cell lines. PMID:24303205

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

    PubMed

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

    2013-07-01

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

  15. Kinetics and product yields of the acetyl peroxy + HO2 radical reaction studied by photoionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Dodson, L. G.; Shen, L.; Savee, J. D.; Eddingsaas, N. C.; Welz, O.; Taatjes, C. A.; Osborn, D. L.; Sander, S. P.; Okumura, M.

    2013-12-01

    The acetyl peroxy radical (CH3C(O)O2) is a key intermediate in the oxidation of carbonyl-containing hydrocarbons in the troposphere. Reaction of acetyl peroxy radicals with HO2 has been suggested as a source of OH radicals in low-NOx environments. Previous work on this reaction observed only two product channels forming (1) peracetic acid and (2) acetic acid. Recent experiments have shown that there is a third channel that generates the radicals OH and acetoxy: CH3C(O)O2 + HO2 → (1) CH3C(O)OOH + O2 (2) CH3C(O)OH + O3 (3) CH3C(O)O + O2 + OH This last pathway to OH formation would then contribute to the apparent isoprene OH recycling suggested by discrepancies between atmospheric models and field observations of OH. There have, however, been significant disagreements among experiments on the yield of OH from reaction of acetyl peroxy radicals with HO2. We report our preliminary studies of acetyl peroxy self-reaction and its reaction with HO2 at 298 K and 8 Torr. Experiments were conducted at the Advanced Light Source synchrotron at the Lawerence Berkeley National Laboratory using tunable VUV ionizing radiation coupled to the Sandia National Laboratory pulsed-laser-photolysis multiplexed photoionization mass spectrometer to detect the time- and isomer-resolved formation of radical intermediates and products. From these results, we report new branching fractions of the three product channels in the acetyl peroxy + HO2 radical reaction.

  16. The effect of sustained static kneeling on kinetic and kinematic knee joint gait parameters.

    PubMed

    Kajaks, Tara; Costigan, Patrick

    2015-01-01

    Despite epidemiological evidence for kneeling as an occupational risk factor for knee osteoarthritis, biomechanical evidence is lacking. Gait knee joint mechanics, a common measure used to study knee osteoarthritis initiation, were used in the present study to investigate the effect of sustained static kneeling on the knee. Ten healthy male subjects (24.1 years ± 3.5) performed ten baseline walking trials, followed by a 30-min kneeling protocol and a second set of walking trials. Knee joint moments and angles were calculated during the stance phase. Within-subject root mean squared differences were compared within and between the pre- and post-kneeling gait trials. Differences were observed between the pre-kneeling and post-kneeling walking trails for flexion and adduction knee moments (0.12 Nm/kg ± 0.03, 0.07 Nm/kg ± 0.02) and angles (3.18° ± 1.22 and 1.64° ± 1.15), indicating that sustained static deep-knee flexion kneeling does acutely alter knee joint gait parameters.

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

    PubMed

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

    2013-11-01

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

  18. Efficient method for calculating kinetic parameters using T1-weighted dynamic contrast-enhanced magnetic resonance imaging.

    PubMed

    Murase, Kenya

    2004-04-01

    It has become increasingly important to quantitatively estimate tissue physiological parameters such as perfusion, capillary permeability, and the volume of extravascular-extracellular space (EES) using T(1)-weighted dynamic contrast-enhanced MRI (DCE-MRI). A linear equation was derived by integrating the differential equation describing the kinetic behavior of contrast agent (CA) in tissue, from which K(1) (rate constant for the transfer of CA from plasma to EES), k(2) (rate constant for the transfer from EES to plasma), and V(p) (plasma volume) can be easily obtained by the linear least-squares (LLSQ) method. The usefulness of this method was investigated by means of computer simulations, in comparison with the nonlinear least-squares (NLSQ) method. The new method calculated the above parameters faster than the NLSQ method by a factor of approximately 6, and estimated them more accurately than the NLSQ method at a signal-to-noise ratio (SNR) of < approximately 10. This method will be useful for generating functional images of K(1), k(2), and V(p) from DCE-MRI data.

  19. Pyrolysis of safflower (Charthamus tinctorius L.) seed press cake: part 1. The effects of pyrolysis parameters on the product yields.

    PubMed

    Sensöz, Sevgi; Angin, Dilek

    2008-09-01

    Safflower (Charthamus tinctorius L.) seed press cake was pyrolysed in a fixed-bed reactor. The effects of pyrolysis temperature, heating rate and sweep gas flow rates on the yields of the products were investigated. Pyrolysis runs were performed using pyrolysis temperatures between 400 and 600 degrees C with heating rates of 10, 30 and 50 degrees C min(-1). The obtained bio-char, gas and bio-oil yields ranged between 25 and 34 wt%, 19 and 25 wt%, and 28 and 36 wt%, respectively, at different pyrolysis conditions. The highest liquid yield was obtained at 500 degrees C pyrolysis temperature with a heating rate of 50 degrees C min(-1) under the sweep gas of N(2) with a flow rate of 100 cm(3)min(-1). Employing the higher heating rate of 50 degrees C min(-1) results in maximum bio-oil yield, probably due to the decrease in mass transfer limitations. According to the results obtained under the conditions of this study, the effects of pyrolysis temperature and sweep gas flow rate are more significant than the effect of heating rate on the yields.

  20. Chitosan-tripolyphosphate nanoparticles: Optimization of formulation parameters for improving process yield at a novel pH using artificial neural networks.

    PubMed

    Hashad, Rania A; Ishak, Rania A H; Fahmy, Sherif; Mansour, Samar; Geneidi, Ahmed S

    2016-05-01

    At a novel pH value of the polymeric solution (6.2), variable chitosan (Cs) and sodium tripolyphosphate (TPP) concentrations and mass ratios were optimized to improve the process yield without undesirable particle flocculation. Prepared formulations were characterized in terms of particle size (PS), zeta potential (ZP) and percentage yield (% yield). Artificial neural networks (ANN) were built up and used to identify the parameters that control nanoparticle (NP) size and yield, in addition to being tested for their ability to predict these two experimental outputs. Using these networks, it was found that TPP concentration has the greatest effect on PS and% yield. The most optimum formulation was characterized by a notable process yield reaching 91.5%, a mean hydrodynamic PS 227 nm, ZP+24.13 mv and spherical compact morphology. Successful Cs-TPP interaction in NP formation was confirmed by both Fourier transform-infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC). This study demonstrated the ability of ANN to predict not only PS of the formed particles but also NP% yield. This may have a great impact on Cs-TPP NPs preparation and can be used to customize the required target formulations.

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

    SciTech Connect

    Bunting, Bruce G

    2012-10-01

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

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

    SciTech Connect

    Raposo, Maria Monteiro Timóteo, Ana Rita; Ribeiro, Paulo A.; Ferreira, Quirina; Botelho do Rego, Ana Maria

    2015-09-21

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

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

    NASA Astrophysics Data System (ADS)

    Raposo, Maria; Ferreira, Quirina; Monteiro Timóteo, Ana Rita; Ribeiro, Paulo A.; do Rego, Ana Maria Botelho

    2015-09-01

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

  4. Fractionation and physicochemical characterization of lignin from waste jute bags: Effect of process parameters on yield and thermal degradation.

    PubMed

    Ahuja, Dheeraj; Kaushik, Anupama; Chauhan, Ghanshyam S

    2017-04-01

    In this work lignin was extracted from waste jute bags using soda cooking method and effect of varying alkali concentration and pH on yield, purity, structure and thermal degradation of lignin were studied. The Lignin yield, chemical composition and purity were assessed using TAPPI method and UV-vis spectroscopy. Yield and purity of lignin ranged from 27 to 58% and 50-94%, respectively for all the samples and was maximum for 8% alkali concentration and at pH 2 giving higher thermal stability. Chemical structure, thermal stability and elementary analysis of lignin were studied using FTIR, (H)NMR, thermo gravimetric analysis (TGA) and Elemental analyzer. FTIR and (H)NMR results showed that core structure of lignin starts breaking beyond 10% alkali concentration. S/G ratio shows the dominance of Syringyl unit over guaiacyl unit.

  5. Olive oil pilot-production assisted by pulsed electric field: impact on extraction yield, chemical parameters and sensory properties.

    PubMed

    Puértolas, Eduardo; Martínez de Marañón, Iñigo

    2015-01-15

    The impact of the use of pulsed electric field (PEF) technology on Arroniz olive oil production in terms of extraction yield and chemical and sensory quality has been studied at pilot scale in an industrial oil mill. The application of a PEF treatment (2 kV/cm; 11.25 kJ/kg) to the olive paste significantly increased the extraction yield by 13.3%, with respect to a control. Furthermore, olive oil obtained by PEF showed total phenolic content, total phytosterols and total tocopherols significantly higher than control (11.5%, 9.9% and 15.0%, respectively). The use of PEF had no negative effects on general chemical and sensory characteristics of the olive oil, maintaining the highest quality according to EU legal standards (EVOO; extra virgin olive oil). Therefore, PEF could be an appropriate technology to improve olive oil yield and produce EVOO enriched in human-health-related compounds, such as polyphenols, phytosterols and tocopherols.

  6. NIRS-aided monitoring and prediction of biogas yields from maize silage at a full-scale biogas plant applying lumped kinetics.

    PubMed

    Jacobi, H Fabian; Ohl, Susanne; Thiessen, Eiko; Hartung, Eberhard

    2012-01-01

    The aim of this study was to apply near-infrared spectroscopy (NIRS), available biogas plant data and lumped degradation kinetics to predict biogas production (BPr) of maize silage. A full-scale agricultural biogas plant was equipped with NIRS-metrology at the feeding station. Continuously NIR-spectra were collected for 520 d. Substrate samples were analyzed by means of feedstuff analysis. Biogas potential of the samples was calculated from the laboratory analysis results and for a sample-subset practically assessed by "Hohenheim biogas tests". NIRS-regression-models for all mentioned parameters were calibrated. Continuously gathered spectra, NIRS-models, actual plant-feeding data and degradation kinetics were used to calculate time-series of theoretically expectable BPr. Results were validated against measured gas quantity. Determination coefficients between calculated and measured BPr were up to 58.2%. This outcome was mainly due to the positive correlation between BPr and input amount since the substrate was very homogeneous. The use of NIRS seems more promising for plants with stronger substrate heterogeneity.

  7. Determination of bacterial and viral transport parameters in a gravel aquifer assuming linear kinetic sorption and desorption

    NASA Astrophysics Data System (ADS)

    Mallén, G.; Maloszewski, P.; Flynn, R.; Rossi, P.; Engel, M.; Seiler, K.-P.

    2005-05-01

    The bacteria Escherichia coli and Pseudomonas putida, and the bacteriophage virus H40/1 are examined both for their transport behaviour relative to inert solute tracers and for their modelability under natural flow conditions in a gravel aquifer. The microbes are attenuated in the following sequence: H40/1≥ P. putida≫ E. coli. The latter is desorbed almost completely within a few days. Breakthrough and recovery curves of the simultaneously injected non-reactive tracers are simulated with the 2D and 1D dispersion equation, in order to ascertain longitudinal dispersivity ( αL) and mean flow time ( T0). Mathematical modelling is difficult due to the aquifer heterogeneity, which results in preferential flow paths between injection and observation wells. Therefore, any attempt of fitting the dispersion model (DM) to the entire inert-tracer breakthrough curve (BTC) fails. Adequate fitting of the model to measured data only succeeds using a DM consisting of a superposition of several BTCs, each representing another set of flow paths. This gives rise to a multimodal, rather than a Gaussian groundwater velocity distribution. Only hydraulic parameters derived from the fastest partial curve, which is fitted to the rising part of the Uranine BTC, are suitable to model microbial breakthroughs. The hydraulic parameters found using 2D and 1D models were nearly identical. Their values were put into an analytical solution of 1D advective-dispersive transport combined with two-site reaction model introduced by Cameron and Klute [Cameron, D.R., Klute, A., 1977. Convective-dispersive solute transport with a combined equilibrium and kinetic adsorption model. Water Resour. Res. 13, 183-189], in order to identify reactive transport parameters (sorption/desorption) and attenuation mechanisms for the microbes migration. This shows that the microbes are almost entirely transported through preferential flow paths, which are represented by the first partial curve. Inert tracers, however

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

    SciTech Connect

    La Fontaine, M; Bradshaw, T; Kubicek, L; Forrest, L; Jeraj, R

    2014-06-15

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

  9. Estimation of regional genetic parameters for mortality and 305-d milk yield of US Holsteins in the first 3 parities.

    PubMed

    Tokuhisa, K; Tsuruta, S; De Vries, A; Bertrand, J K; Misztal, I

    2014-07-01

    Several research reports have indicated increasing dairy cow mortality in recent years. The objectives of this research were to characterize the phenotypic differences in mortality in the first 3 parities across 3 regions of the United States to estimate the heritability of mortality of Holstein cows across regions and parities, and to estimate genetic and environmental correlations between milk yield and mortality across parities and regions. Dairy Herd Information (DHI) milk yield and mortality data were obtained from 3 different US regions: the Southeast (SE), Southwest (SW), and Northeast (NE). A total of 3,522,824 records for the first 3 parities were used: 732,009 (SE), 656,768 (SW), and 2,134,047 (NE) from 1999 to 2008. Cows that received a termination code of 6--"Cow died on the dairy; downer cows that were euthanized should be included here"--were given a mortality score of 2 (dead), whereas all other codes were assigned a mortality score of 1 (alive). Average annual mortalities in the first 3 parities across regions ranged from 2.2 to 7.2%, with mortality frequency increasing with increasing parity across all regions and with the SE having the highest mortality frequency. For genetic analysis, a 2-trait (305-d milk yield and mortality) linear-threshold animal model that fitted fixed effects of herd-year (for 305-d milk yield), cow age, days in milk (in month classes), month-of-termination, and random effects of herd-year (for mortality), animal, and residual was implemented. The model was used to estimate variance components separately for each region and parity. Heritability estimates for mortality were similar for all regions and parities, ranging from 0.04 to 0.07. Genetic correlations between mortality and 305-d milk yield across the first 3 parities were 0.14, 0.20, and 0.29 in SE; -0.01, 0.01, and 0.31 in SW; and 0.28, 0.33, and 0.19 in NE. We detected an adverse genetic relationship between milk production and mortality; however, the moderate

  10. Effects of growth parameters on the yield and morphology of Si{sub 3}N{sub 4} microcoils prepared by chemical vapor deposition

    SciTech Connect

    Du, Hongli; Zhang, Wei; Li, Yan

    2014-02-01

    Highlights: • CVD method was successfully applied to obtain Si{sub 3}N{sub 4} microcoils in high yield without the presence of catalyst. • The process was systematically investigated through a series of control experiments. • The effects of synthesis parameters on the yield and morphology of Si{sub 3}N{sub 4} microcoils were found. • The growth mechanism of the Si{sub 3}N{sub 4} microcoils could be explained by the different growth rates between the amorphous layer and the crystalline layer. - Abstract: In this study, we provided a reliable chemical vapor deposition (CVD) method to synthesize high-purity Si{sub 3}N{sub 4} microcoils in high yield without the presence of catalyst. The achieved products were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscope. The results indicated that the yield and morphology of Si{sub 3}N{sub 4} products were influenced by the synthesis parameters such as reaction temperature, reaction time and gas flow rate. The particular conditions favorable to high yield synthesis of Si{sub 3}N{sub 4} microcoils were obtained through a series of control experiments. Furthermore, the growth of Si{sub 3}N{sub 4} microcoils was supposed to be in accord with vapor-solid (VS) growth process and the different growth rates between the amorphous layer and the crystalline layer were used to explain the formation of the coil geometry.

  11. Carbon reaction and diffusion on Ni(111), Ni(100), and Fe(110): Kinetic parameters from x-ray photoelectron spectroscopy and density functional theory analysis

    SciTech Connect

    Wiltner, A.; Linsmeier, Ch.; Jacob, T.

    2008-08-28

    This paper investigates the reactivity of elemental carbon films deposited from the vapor phase with Fe and Ni substrates at room temperature. X-ray photoelectron spectroscopy (XPS) measurements are presented as a method for evaluating kinetic reaction data. Carbon films are deposited on different surface orientations representing geometries from a dense atom packing as in fcc (111) to an open surface structure as in fcc (100). During annealing experiments several reactions are observed (carbon subsurface diffusion, carbide formation, carbide decomposition, and graphite ordering). These reactions and the respective kinetic parameters are analyzed and quantified by XPS measurements performed while annealing at elevated temperatures (620-820 K). The resulting activation barriers for carbon subsurface diffusion are compared with calculated values using the density functional theory. The determined kinetic parameters are used to reproduce the thermal behavior of carbon films on nickel surfaces.

  12. Torrefaction of invasive alien plants: Influence of heating rate and other conversion parameters on mass yield and higher heating value.

    PubMed

    Mundike, Jhonnah; Collard, François-Xavier; Görgens, Johann F

    2016-06-01

    With the aim of controlling their proliferation, two invasive alien plants, Lantana camara (LC) and Mimosa pigra (MP), both widespread in Africa, were considered for torrefaction for renewable energy applications. Using thermogravimetric analysis, the influence of heating rate (HR: 2.18-19.82°Cmin(-1)) together with variable temperature and hold time on char yield and HHV (in a bomb calorimeter) were determined. Statistically significant effects of HR on HHV with optima at 10.5°Cmin(-1) for LC and 20°Cmin(-1) for MP were obtained. Increases of HHV up to 0.8MJkg(-1) or energy yield greater than 10%, together with a 3-fold reduction in torrefaction conversion time could be achieved by optimisation of HR. Analysis of the torrefaction volatiles by TG-MS showed that not only hemicelluloses, but also lignin conversion, could influence the optimum HR value.

  13. Infrared warming reduced winter wheat yields and some physiological parameters, which were mitigated by irrigation and worsened by delayed sowing.

    PubMed

    Fang, Shibo; Su, Hua; Liu, Wei; Tan, Kaiyan; Ren, Sanxue

    2013-01-01

    Winter wheat has a central role in ensuring the food security and welfare of 1.3 billion people in China. Extensive previous studies have concluded that winter wheat yields would decrease with higher temperatures, owing to warming-induced soil drying or shortening of phenophase. Temperature in China is predicted to increase by 1-5°C by 2100, which may greatly impact plant production and cause other negative effects. We performed a manipulative field experiment, creating diverse growth regimes for wheat by infrared radiation (IR) warming day and night, including IR warming only (DW), IR warming + delayed sowing dates (DS), IR warming + increased irrigation (IW), and a control (CK). The results show that IR warming increased daily average wheat canopy and soil temperatures by 2.0°C and 2.3°C, respectively. DW was associated with an advanced maturity of 10 days and yield reduction of 8.2%. IR-warming effects on the photosynthetic apparatus of wheat varied with season as well as significant differences were found in the booting stage. DS represented a worsened situation, lowering yield per plant by 16.4%, with a significant decline in aboveground biomass and functional leaf area. Wheat under DS showed double-peak patterns of diurnal gas exchange during booting stages and, consequently, lower photosynthetic capacity with high transpiration for cooling. Significantly lower actual water use efficiency and intrinsic water use efficiency from jointing to anthesis stages were also found under DS. However, IW had no significant difference from CK, irrespective of yield and photosynthesis. Therefore, we concluded that delayed sowing date may not be a good choice for winter wheat, whereas a thoroughly-watered wheat agroecosystem should be promoted in the context of global warming.

  14. Infrared Warming Reduced Winter Wheat Yields and Some Physiological Parameters, Which Were Mitigated by Irrigation and Worsened by Delayed Sowing

    PubMed Central

    Fang, Shibo; Su, Hua; Liu, Wei; Tan, Kaiyan; Ren, Sanxue

    2013-01-01

    Winter wheat has a central role in ensuring the food security and welfare of 1.3 billion people in China. Extensive previous studies have concluded that winter wheat yields would decrease with higher temperatures, owing to warming-induced soil drying or shortening of phenophase. Temperature in China is predicted to increase by 1–5°C by 2100, which may greatly impact plant production and cause other negative effects. We performed a manipulative field experiment, creating diverse growth regimes for wheat by infrared radiation (IR) warming day and night, including IR warming only (DW), IR warming + delayed sowing dates (DS), IR warming + increased irrigation (IW), and a control (CK). The results show that IR warming increased daily average wheat canopy and soil temperatures by 2.0°C and 2.3°C, respectively. DW was associated with an advanced maturity of 10 days and yield reduction of 8.2%. IR-warming effects on the photosynthetic apparatus of wheat varied with season as well as significant differences were found in the booting stage. DS represented a worsened situation, lowering yield per plant by 16.4%, with a significant decline in aboveground biomass and functional leaf area. Wheat under DS showed double-peak patterns of diurnal gas exchange during booting stages and, consequently, lower photosynthetic capacity with high transpiration for cooling. Significantly lower actual water use efficiency and intrinsic water use efficiency from jointing to anthesis stages were also found under DS. However, IW had no significant difference from CK, irrespective of yield and photosynthesis. Therefore, we concluded that delayed sowing date may not be a good choice for winter wheat, whereas a thoroughly-watered wheat agroecosystem should be promoted in the context of global warming. PMID:23874424

  15. Genetic parameters and correlations of collar rot resistance with important biochemical and yield traits in opium poppy (Papaver somniferum L.).

    PubMed

    Trivedi, Mala; Tiwari, Rajesh K; Dhawan, Om P

    2006-01-01

    Collar rot, caused by Rhizoctonia solani Kühn, is one of the most severe fungal diseases of opium poppy. In this study, heritability, genetic advance and correlation for 10 agronomic, 1 physiological, 3 biochemical and 1 chemical traits with disease severity index (DSI) for collar rot were assessed in 35 accessions of opium poppy. Most of the economically important characters, like seed and capsule straw yield per plant, oil and protein content of seeds, peroxidase activity in leaves, morphine content of capsule straw and DSI for collar rot showed high heritability as well as genetic advance. Highly significant negative correlation between DSI and seed yield clearly shows that as the disease progresses in plants, seed yield declines, chiefly due to premature death of infected plants as well as low seed and capsule setting in the survived population of susceptible plants. Similarly, a highly significant negative correlation between peroxidase activity and DSI indicated that marker-assisted selection of disease-resistant plants based on high peroxidase activity would be effective and survived susceptible plants could be removed from the population to stop further spread.

  16. Genetic parameters for body weight, carcass chemical composition and yield in a broiler-layer cross developed for QTL mapping

    PubMed Central

    Nunes, Beatriz do Nascimento; Ramos, Salvador Boccaletti; Savegnago, Rodrigo Pelicioni; Ledur, Mônica Corrêa; Nones, Kátia; Klein, Claudete Hara; Munari, Danísio Prado

    2011-01-01

    The objective of this study was to estimate genetic and phenotypic correlations of body weight at 6 weeks of age (BW6), as well as final carcass yield, and moisture, protein, fat and ash contents, using data from 3,422 F2 chickens originated from reciprocal cross between a broiler and a layer line. Variance components were estimated by the REML method, using animal models for evaluating random additive genetic and fixed contemporary group (sex, hatch and genetic group) effects. The heritability estimates (h2) for BW6, carcass yield and percentage of carcass moisture were 0.31 ± 0.07, 0.20 ± 0.05 and 0.33 ± 0.07, respectively. The h2 for the percentages of protein, fat and ash on a dry matter basis were 0.48 ± 0.09, 0.55 ± 0.10 and 0.36 ± 0.08, respectively. BW6 had a positive genetic correlation with fat percentage in the carcass, but a negative one with protein and ash contents. Carcass yield, thus, appears to have only low genetic association with carcass composition traits. The genetic correlations observed between traits, measured on a dry matter basis, indicated that selection for carcass protein content may favor higher ash content and a lower percentage of carcass fat. PMID:21931515

  17. Effects of pressed beet pulp silage inclusion in maize-based rations on performance of high-yielding dairy cows and parameters of rumen fermentation.

    PubMed

    Boguhn, J; Kluth, H; Bulang, M; Engelhard, T; Rodehutscord, M

    2010-01-01

    Beet pulp contains high amounts of pectins that can reduce the risk of rumen disorders compared to using feedstuffs high in starch. The objective was to study the effects of inclusion of ensiled pressed beet pulp in total mixed rations (TMR) for high-yielding dairy cows. Two TMR containing no or about 20% (on dry matter (DM) basis) beet pulp silage were used. The beet pulp silage mainly replaced maize silage and corn cob silage. The TMR were intentionally equal in the concentrations of energy and utilisable crude protein (CP) at the duodenum. TMR were fed to 39 and 40 dairy cows, respectively, for 118 days. The average daily milk yield was about 43 kg/day. No significant differences in milk yield and milk fat or milk protein content were detected. DM intake of cows was significantly reduced by the inclusion of beet pulp silage (23.0 v. 24.5 kg/day). However, a digestibility study, separately conducted with sheep, showed a significantly higher organic matter digestibility and metabolisable energy concentration for the TMR that contained beet pulp silage. In vitro gas production kinetics indicated that the intensity of fermentation was lower in the TMR that contained beet pulp silage. In vitro production of short-chain fatty acids, studied using a Rusitec, did not differ between the TMR. However, the inclusion of beet pulp silage in the ration caused a significant reduction in the efficiency of microbial CP synthesis in vitro. The amino acid profile of microbial protein remained unchanged. It was concluded that beet pulp silage has specific effects on ruminal fermentation that may depress feed intake of cows but improve digestibility. An inclusion of beet pulp silage of up to 20% of DM in rations for high-yielding dairy cows is possible without significant effects on milk yield and milk protein or milk fat.

  18. Effect of Simultaneous Inoculation with Yeast and Bacteria on Fermentation Kinetics and Key Wine Parameters of Cool-Climate Chardonnay

    PubMed Central

    Jussier, Delphine; Dubé Morneau, Amélie; Mira de Orduña, Ramón

    2006-01-01

    Inoculating grape musts with wine yeast and lactic acid bacteria (LAB) concurrently in order to induce simultaneous alcoholic fermentation (AF) and malolactic fermentation (MLF) can be an efficient alternative to overcome potential inhibition of LAB in wines because of high ethanol concentrations and reduced nutrient content. In this study, the simultaneous inoculation of yeast and LAB into must was compared with a traditional vinification protocol, where MLF was induced after completion of AF. For this, two suitable commercial yeast-bacterium combinations were tested in cool-climate Chardonnay must. The time courses of glucose and fructose, acetaldehyde, several organic acids, and nitrogenous compounds were measured along with the final values of other key wine parameters. Sensory evaluation was done after 12 months of storage. The current study could not confirm a negative impact of simultaneous AF/MLF on fermentation success and kinetics or on final wine parameters. While acetic acid concentrations were slightly increased in wines after simultaneous AF/MLF, the differences were of neither practical nor legal significance. No statistically significant differences were found with regard to the final values of pH or total acidity and the concentrations of ethanol, acetaldehyde, glycerol, citric and lactic acids, and the nitrogen compounds arginine, ammonia, urea, citrulline, and ornithine. Sensory evaluation by a semiexpert panel confirmed the similarity of the wines. However, simultaneous inoculation led to considerable reductions in overall fermentation durations. Furthermore, differences of physiological and microbiological relevance were found. Specifically, we report the vinification of “super-dry” wines devoid of glucose and fructose after simultaneous inoculation of yeast and bacteria. PMID:16391046

  19. Effect of simultaneous inoculation with yeast and bacteria on fermentation kinetics and key wine parameters of cool-climate chardonnay.

    PubMed

    Jussier, Delphine; Dubé Morneau, Amélie; Mira de Orduña, Ramón

    2006-01-01

    Inoculating grape musts with wine yeast and lactic acid bacteria (LAB) concurrently in order to induce simultaneous alcoholic fermentation (AF) and malolactic fermentation (MLF) can be an efficient alternative to overcome potential inhibition of LAB in wines because of high ethanol concentrations and reduced nutrient content. In this study, the simultaneous inoculation of yeast and LAB into must was compared with a traditional vinification protocol, where MLF was induced after completion of AF. For this, two suitable commercial yeast-bacterium combinations were tested in cool-climate Chardonnay must. The time courses of glucose and fructose, acetaldehyde, several organic acids, and nitrogenous compounds were measured along with the final values of other key wine parameters. Sensory evaluation was done after 12 months of storage. The current study could not confirm a negative impact of simultaneous AF/MLF on fermentation success and kinetics or on final wine parameters. While acetic acid concentrations were slightly increased in wines after simultaneous AF/MLF, the differences were of neither practical nor legal significance. No statistically significant differences were found with regard to the final values of pH or total acidity and the concentrations of ethanol, acetaldehyde, glycerol, citric and lactic acids, and the nitrogen compounds arginine, ammonia, urea, citrulline, and ornithine. Sensory evaluation by a semiexpert panel confirmed the similarity of the wines. However, simultaneous inoculation led to considerable reductions in overall fermentation durations. Furthermore, differences of physiological and microbiological relevance were found. Specifically, we report the vinification of "super-dry" wines devoid of glucose and fructose after simultaneous inoculation of yeast and bacteria.

  20. Theoretical estimation of kinetic parameters for nucleophilic substitution reactions in solution: an application of a solution translational entropy model.

    PubMed

    Han, Ling-Li; Li, Shi-Jun; Fang, De-Cai

    2016-02-17

    The kinetic parameters, such as activation entropy, activation enthalpy, activation free-energy, and reaction rate constant, for a series of nucleophilic substitution (SN) reactions in solution, are investigated using both a solution-phase translational entropy model and an ideal gas-phase translational entropy model. The results obtained from the solution translational entropy model are in excellent agreement with the experimental values, while the overestimation of activation free-energy from the ideal gas-phase translational entropy model is as large as 6.9 kcal mol(-1). For some of the reactions studied, such as and in methanol, and and in aqueous solution, the explicit + implicit model, namely, a cluster-continuum type model, should be employed to account for the strong solvent-solute interactions. In addition, the explicit + implicit models have also been applied to the DMSO-H2O mixtures, which would open up a door to investigate the reactions in a mixed solvent using density functional theory (DFT) methods.

  1. Optimization of laccase fermentation and evaluation of kinetic and thermodynamic parameters of a partially purified laccase produced by Daedalea flavida.

    PubMed

    Singha, Siddhartha; Panda, Tapobrata

    2015-01-01

    Studies on laccase production by Daedalea flavida were carried out in static and low-speed shake cultures. The enzyme production was reduced drastically at a high speed of shaking. Optimal production conditions are necessary to assess the quality of laccase suitable for a specific application. Thus, the production of laccase was optimized by the application of response surface methodology. Laccase production was 8-fold and 7.5-fold more in static and low-speed shake conditions, respectively, in an optimal medium composition than in an unoptimized medium. Laccase obtained using the optimal culture medium of D. flavida was tested for its stability at different temperatures and pH conditions. The partially purified enzyme was most stable at 30°C and pH 5. The half-life of laccase is 87 min at 60°C and at pH 6. The kinetic and thermodynamic parameters were evaluated for the inactivation of the partially purified laccase. The entropy change of inactivation of the enzyme is least at pH 4.

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

    PubMed

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

    2012-09-01

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

  3. Estimation of kinetic parameters of anthocyanins and color degradation in vitamin C fortified cranberry juice during storage.

    PubMed

    Roidoung, Sunisa; Dolan, Kirk D; Siddiq, Muhammad

    2017-04-01

    Color degradation in cranberry juice during storage is the most common consumer complaint. To enhance nutritional quality, juice is typically fortified with vitamin C. This study determined effect of gallic acid, a natural antioxidant, for the preservation of anthocyanins (ACYs) and color, and estimated kinetics of ACYs and color degradation. Juice, fortified with 40-80mg/100mL vitamin C and 0-320mg/100mL gallic acid, was pasteurized at 85°C for 1min and stored at 23°C for 16days. Total monomeric anthocyanins and red color intensity were evaluated spectrophotometrically and data were used to determine degradation rate constants (k values) and order of reaction (n) of ACYs and color. Due to high correlation, k and n could not be estimated simultaneously. To overcome this difficulty, both n and k were held at different constant values in separate analyses to allow accurate estimation of each. Parameters n and k were modeled empirically as functions of vitamin C, and of vitamin C and gallic acid, respectively. Reaction order n ranged from 1.2 to 4.4, and decreased with increasing vitamin C concentration. The final model offers an effective tool that could be used for predicting ACYs and color retention in cranberry juice during storage.

  4. Studies on fission with ALADIN. Precise and simultaneous measurement of fission yields, total kinetic energy and total prompt neutron multiplicity at GSI

    NASA Astrophysics Data System (ADS)

    Martin, Julie-Fiona; Taieb, Julien; Chatillon, Audrey; Bélier, Gilbert; Boutoux, Guillaume; Ebran, Adeline; Gorbinet, Thomas; Grente, Lucie; Laurent, Benoit; Pellereau, Eric; Alvarez-Pol, Héctor; Audouin, Laurent; Aumann, Thomas; Ayyad, Yassid; Benlliure, Jose; Casarejos, Enrique; Cortina Gil, Dolores; Caamaño, Manuel; Farget, Fanny; Fernández Domínguez, Beatriz; Heinz, Andreas; Jurado, Beatriz; Kelić-Heil, Aleksandra; Kurz, Nikolaus; Nociforo, Chiara; Paradela, Carlos; Pietri, Stéphane; Ramos, Diego; Rodríguez-Sànchez, Jose-Luis; Rodríguez-Tajes, Carme; Rossi, Dominic; Schmidt, Karl-Heinz; Simon, Haik; Tassan-Got, Laurent; Vargas, Jossitt; Voss, Bernd; Weick, Helmut

    2015-12-01

    A novel technique for fission studies, based on the inverse kinematics approach, is presented. Following pioneering work in the nineties, the SOFIA Collaboration has designed and built an experimental set-up dedicated to the simultaneous measurement of isotopic yields, total kinetic energies and total prompt neutron multiplicities, by fully identifying both fission fragments in coincidence, for the very first time. This experiment, performed at GSI, permits to study the fission of a wide variety of fissioning systems, ranging from mercury to neptunium, possibly far from the valley of stability. A first experiment, performed in 2012, has provided a large array of unprecedented data regarding the nuclear fission process. An excerpt of the results is presented. With this solid starter, further improvements of the experimental set-up are considered, which are consistent with the expected developments at the GSI facility, in order to measure more fission observables in coincidence. The completeness reached in the SOFIA data, permits to scrutinize the correlations between the interesting features of fission, offering a very detailed insight in this still unraveled mechanism.

  5. A laser flash photolysis-resonance fluorescence kinetics study of the reaction Cl/2P/ + CH4 yields CH3 + HCl

    NASA Technical Reports Server (NTRS)

    Ravishankara, A. R.; Wine, P. H.

    1980-01-01

    The technique of laser flash photolysis-resonance fluorescence is employed to study the kinetics of the reaction Cl(2P) + CH4 yields CH3 + HCl over the temperature range 221-375 K. At temperatures less than or equal to 241 K the apparent bimolecular rate constant is found to be dependent upon the identity of the chemically inert gases in the reaction mixture. For Cl2/CH4/He reaction mixtures (total pressure = 50 torr) different bimolecular rate constants are measured at low and high methane concentrations. For Cl2/CH4/CCl/He and Cl2/CH4/Ar reaction mixtures, the bimolecular rate constant is independent of methane concentration, being approximately equal to the rate constant measured at low methane concentrations for Cl2/CH4/He mixtures. These rate constants are in good agreement with previous results obtained using the discharge flow-resonance fluorescence and competitive chlorination techniques. At 298 K the measured bimolecular rate constant is independent of the identity of the chemically inert gases in the reaction mixture and in good agreement with all previous investigations. The low-temperature results obtained in this investigation and all previous investigations can be rationalized in terms of a model which assumes that the Cl(2P 1/2) state reacts with CH4 much faster than the Cl(2P 3/2) state. Extrapolation of this model to higher temperatures, however, is not straightforward.

  6. Statistical optimization for enhanced yields of probiotic Bacillus coagulans and its phage resistant mutants followed by kinetic modelling of the process.

    PubMed

    Pandey, Kavita R; Joshi, Chetan; Vakil, Babu V

    2016-01-01

    Probiotics are microorganisms which when administered in adequate amounts confer health benefits to the host. A leading pharmaceutical company producing Bacillus coagulans as a probiotic was facing the problem of recurring phage attacks. Two mutants viz. B. co PIII and B. co MIII that were isolated as phage resistant mutants after UV irradiation and MMS treatment of phage sensitive B. coagulans parental culture were characterized at functional and molecular level and were noted to have undergone interesting genetic changes. The non-specific genetic alterations induced by mutagenesis can also lead to alterations in cell performance. Hence, in the current study the parental strain and the two mutants were selected for shake flask optimization. Plackett-Burman design was used to select the significant culture variables affecting biomass production. Evolutionary operation method was applied for further optimization. The study showed wide variations in the nutritional requirements of phage resistant mutants, post exposure to mutagens. An increment of 150, 134 and 152 % was observed in the biomass productions of B. coagulans (parental type) and mutants B.co PIII and B.co MIII respectively, compared to the yield from one-factor-at-a-time technique. Using Logistic and modified Leudeking-Piret equations, biomass accumulation and substrate utilization efficiency of the bioprocess were determined. The experimental data was in agreement with the results predicted by statistical analysis and modelling. The developed model may be useful for controlling the growth and substrate consumption kinetics in large scale fermentation using B. coagulans.

  7. Quantitative Genetics and Functional–Structural Plant Growth Models: Simulation of Quantitative Trait Loci Detection for Model Parameters and Application to Potential Yield Optimization

    PubMed Central

    Letort, Véronique; Mahe, Paul; Cournède, Paul-Henry; de Reffye, Philippe; Courtois, Brigitte

    2008-01-01

    Background and Aims Prediction of phenotypic traits from new genotypes under untested environmental conditions is crucial to build simulations of breeding strategies to improve target traits. Although the plant response to environmental stresses is characterized by both architectural and functional plasticity, recent attempts to integrate biological knowledge into genetics models have mainly concerned specific physiological processes or crop models without architecture, and thus may prove limited when studying genotype × environment interactions. Consequently, this paper presents a simulation study introducing genetics into a functional–structural growth model, which gives access to more fundamental traits for quantitative trait loci (QTL) detection and thus to promising tools for yield optimization. Methods The GREENLAB model was selected as a reasonable choice to link growth model parameters to QTL. Virtual genes and virtual chromosomes were defined to build a simple genetic model that drove the settings of the species-specific parameters of the model. The QTL Cartographer software was used to study QTL detection of simulated plant traits. A genetic algorithm was implemented to define the ideotype for yield maximization based on the model parameters and the associated allelic combination. Key Results and Conclusions By keeping the environmental factors constant and using a virtual population with a large number of individuals generated by a Mendelian genetic model, results for an ideal case could be simulated. Virtual QTL detection was compared in the case of phenotypic traits – such as cob weight – and when traits were model parameters, and was found to be more accurate in the latter case. The practical interest of this approach is illustrated by calculating the parameters (and the corresponding genotype) associated with yield optimization of a GREENLAB maize model. The paper discusses the potentials of GREENLAB to represent environment × genotype

  8. 'Fractional heating' differential scanning calorimetry: a tool to study energetics and kinetics of solid-state reactions in photoactive systems with distributed parameters

    NASA Astrophysics Data System (ADS)

    Sworakowski, Juliusz; Nešpůrek, Stanislav

    1998-11-01

    The technique of differential scanning calorimetry (DSC), used in measurements of thermal effects accompanying solid-state chemical reactions, can be regarded as a thermally stimulated method. Model calculations demonstrate the applicability of the DSC technique in determining parameters controlling the kinetics of solid-state reactions. In particular, it has been shown that the fractional heating technique can be successfully used to analyse DSC curves in case of distributions of kinetic parameters. The method was employed to obtain information about the parameters controlling a thermally driven reaction following UV illumination of photoactive 1-methyl-2,4,4,6-tetraphenyl-1,4-dihydropyridine. Two peaks on DSC curves were distinguished, probably corresponding to different processes associated with reactions responsible for the bleaching of the coloured material. The activation energy and the pre-exponential factor of at least one of them were determined.

  9. 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

    2016-12-02

    The K2 Mg(SO4 )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, K2 Mg(SO4 )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) D0 to (7) Fj (j = 0, 1, 2, 3). The Commission International de I' Eclairage (CIE) chromaticity coordinates were also calculated for the K2 Mg(SO4 )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 K2 Mg (SO4 )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) .

  10. Random regression test day models to estimate genetic parameters for milk yield and milk components in Philippine dairy buffaloes.

    PubMed

    Flores, E B; van der Werf, J

    2015-08-01

    Heritabilities and genetic correlations for milk production traits were estimated from first-parity test day records on 1022 Philippine dairy buffalo cows. Traits analysed included milk (MY), fat (FY) and protein (PY) yields, and fat (Fat%) and protein (Prot%) concentrations. Varying orders of Legendre polynomials (Leg(m)) as well as the Wilmink function (Wil) were used in random regression models. These various models were compared based on log likelihood, Akaike's information criterion, Bayesian information criterion and genetic variance estimates. Six residual variance classes were sufficient for MY, FY, PY and Fat%, while seven residual classes for Prot%. Multivariate analysis gave higher estimates of genetic variance and heritability compared with univariate analysis for all traits. Heritability estimates ranged from 0.25 to 0.44, 0.13 to 0.31 and 0.21 to 0.36 for MY, FY and PY, respectively. Wilmink's function was the better fitting function for additive genetic effects for all traits. It was also the preferred function for permanent environment effects for Fat% and Prot%, but for MY, FY and PY, the Legm was the appropriate function. Genetic correlations of MY with FY and PY were high and they were moderately negative with Fat% and Prot%. To prevent deterioration in Fat% and Prot% and improve milk quality, more weight should be applied to milk component traits.

  11. Novel Structural Parameters of Ig–Ag Complexes Yield a Quantitative Description of Interaction Specificity and Binding Affinity

    PubMed Central

    Marillet, Simon; Lefranc, Marie-Paule; Boudinot, Pierre; Cazals, Frédéric

    2017-01-01

    Antibody–antigen complexes challenge our understanding, as analyses to date failed to unveil the key determinants of binding affinity and interaction specificity. We partially fill this gap based on novel quantitative analyses using two standardized databases, the IMGT/3Dstructure-DB and the structure affinity benchmark. First, we introduce a statistical analysis of interfaces which enables the classification of ligand types (protein, peptide, and chemical; cross-validated classification error of 9.6%) and yield binding affinity predictions of unprecedented accuracy (median absolute error of 0.878 kcal/mol). Second, we exploit the contributions made by CDRs in terms of position at the interface and atomic packing properties to show that in general, VH CDR3 and VL CDR3 make dominant contributions to the binding affinity, a fact also shown to be consistent with the enthalpy–entropy compensation associated with preconfiguration of CDR3. Our work suggests that the affinity prediction problem could be partially solved from databases of high resolution crystal structures of complexes with known affinity. PMID:28232828

  12. Kinetics of excited states of pigment clusters in solubilized light-harvesting complex II: photon density-dependent fluorescence yield and transmittance.

    PubMed Central

    Schödel, R; Hillmann, F; Schrötter, T; Voigt, J; Irrgang, K D; Renger, G

    1996-01-01

    Relative fluorescence yield, phi F, and transmittance, T, were measured in solubilized light-harvesting complex II (LHCII) as a function of photon density, Ip, of monochromatic 645-nm laser pulses (duration: approximately 2.5 ns). Special efforts were made in constructing an optical set-up that allows the accurate determination of the fluorescence from an area of constant Ip, phi F(Ip) starts to decline at approximately 10(14) and drops to values below 0.01% at maximum Ip (approximately 10(19) photons cm-2 pulse-1). T(Ip) decreases only slightly at photon densities of approximately 10(15) but increases steeply at values of > 10(17) photons cm-2 pulse-1. The interpretation of the phi F(Ip) data using the saturation limit of Mauzerall's multiple hit model leads to a unit size of about 10-15 chlorophyll molecules. One interpretation is to attribute this result to a very fast exciton-exciton annihilation of multiple excited states generated within this small domain. Alternatively, based on the assumption that delocalized cluster states within the monomeric/trimeric subunit of LHCII exist, the results can be consistently described by a kinetic model comprising ground, monoexcitonic, and biexcitonic states of clusters and a triplet state that is quenched by carotenoids in LHCII. Within the framework of this model the annihilation of multiple excitations is explained as ultrafast radiationless relaxation of higher excited cluster states. Comparative measurements in diluted acetonic Chl a solution are consistently described by the depletion of the ground state, taking the absorption cross section at the used wavelength. Images FIGURE 1 PMID:8968606

  13. VERY LONG BASELINE NEUTRINO OSCILLATION EXPERIMENTS FOR PRECISE MEASURMENTS OF OSCILLATION PARAMETERS AND SEARCH FOR N MU YIELDS N EPSILON.

    SciTech Connect

    DIWAN,M.; MARCIANO,W.; WENG,W.; BEAVIS,D.; BRENNAN,M.; CHEN,M.C.; FERNOW,R.; ET AL

    2002-10-18

    Brookhaven National Laboratory and collaborators started a neutrino working group to identify new opportunities in the field of neutrino oscillations and explore how our laboratory facilities can be used to explore this field of research. The memo to the working group and the charge are included in Appendix I. This report is the result of the deliberations of the working group. Previously, we wrote a letter of intent to build a new high intensity neutrino beam at BNL. A new intense proton beam will be used to produce a conventional horn focused neutrino beam directed at a detector located in either the Homestake mine in Lead, South Dakota at 2540 km or the Waste Isolation Pilot Plant (WIPP) in Carlsbad, NM at 2880 km. As a continuation of the study that produced the letter of intent, this report examines several items in more detail. We mainly concentrate on the use of water Cherenltov detectors because of their size, resolution, and background rejection capability, and cost. We examine the prospects of building such a detector in the Homestake mine. The accelerator upgrade will be carried out in phases. We expect the first phase to yield a 0.4 MW proton beam and the second phase to result in a 1.0 MW beam. The details of this upgrade will be reported in a companion report. In this report we assume accelerator intensity of 1 MW for calculating event rates and spectra. We also assume a total experimental duration of 5 years with running time of 10{sup 7} seconds per year. We examine the target station and the horn produced neutrino beam with focus on two topics: target and horn design for a 1 MW beam and the broad band spectrum of neutrinos from a 28 GeV proton beam.

  14. Genetic parameters of milk coagulation properties and their relationships with milk yield and quality traits in Italian Holstein cows.

    PubMed

    Cassandro, M; Comin, A; Ojala, M; Dal Zotto, R; De Marchi, M; Gallo, L; Carnier, P; Bittante, G

    2008-01-01

    Milk coagulation properties (MCP) are an important aspect in assessing cheese-making ability. Several studies showed that favorable conditions of milk reactivity with rennet, curd formation rate, and curd strength, as well as curd syneresis, have a positive effect on the entire cheese-making process and subsequently on the ripening of cheese. Moreover, MCP were found to be heritable, but little scientific literature is available about their genetic aspects. The aims of this study were to estimate heritability of MCP and genetic correlations among MCP and milk production and quality traits. A total of 1,071 Italian Holstein cows (progeny of 54 sires) reared in 34 herds in Northern Italy were sampled from January to July 2004. Individual milk samples were collected during the morning milking and analyzed for coagulation time (RCT), curd firmness (a30), pH, titratable acidity, fat, protein, and casein contents, and somatic cell count. About 10% of individual milk samples did not coagulate in 31 min, so they were removed from the analyses. Estimates of heritability for RCT and a30 were 0.25 +/- 0.04 and 0.15 +/- 0.03, respectively. Estimates of genetic correlations between MCP traits and milk production traits were negligible except for a30 with protein and casein contents (0.44 +/- 0.10 and 0.53 +/- 0.09, respectively). Estimates of genetic correlations between MCP traits and somatic cell score were strong and favorable, as well as those between MCP and pH and titratable acidity. Selecting for high casein content, milk acidity, and low somatic cell count might be an indirect way to improve MCP without reducing milk yield and quality traits.

  15. Effect of farming systems on the yield, quality parameters and sensory properties of conventionally and organically grown potato (Solanum tuberosum L.) tubers.

    PubMed

    Brazinskiene, V; Asakaviciute, R; Miezeliene, A; Alencikiene, G; Ivanauskas, L; Jakstas, V; Viskelis, P; Razukas, A

    2014-02-15

    The objectives of this two-year research were to study the impact of two different farming types, conventional and organic, on the yield and sensory properties of five Lithuanian varieties of potato tuber. The parameters and properties examined were: phenolic acids; dry matter and starch content; and the spread and intensity of Phytophthora infestans growth. It was determined that potato yield fluctuates with the variety, but for conventional farming it is significantly (p<0.05) higher than that obtained by organic farming. The farming type has no significant effect (p>0.05) on the content of phenolic acids. No significant effect (p>0.05) of farming type on dry matter and starch content, or sensory properties was found. No significant relation (p>0.05) was found between the content of phenolic acids and P. infestans spread. The spread of P. infestans was faster and infection was heavier in organically grown potatoes.

  16. Effect of the time of application of phosphorus fertilizer on yield and quality parameters of melon crop amended with winery waste compost.

    NASA Astrophysics Data System (ADS)

    Requejo Mariscal, María Isabel; Cartagena, María Carmen; Villena Gordo, Raquel; Arce Martínez, Augusto; Ribas Elcorobarrutia, Francisco; Jesús Cabello Cabello, María; Castellanos Serrano, María Teresa

    2016-04-01

    In Spain, drip irrigation systems are widely used for horticultural crop production. In drip irrigation systems, emitter clogging has been identified as one of the most important concerns. Clogging is closely related to the quality of the irrigation water and the structure of the emitter flow path, and occurs as a result of multiple physical, biological and chemical factors. So, the use of acid fertilizers (e.g. phosphoric acid) in these systems is common to avoid the emitter clogging. Moreover, in this country the use of exhausted grape marc compost as source of nutrients and organic matter has been identified as a good management option of soil fertility, especially in grape-growing areas with a large generation of wastes from the wine and distillery industries. The purpose of this work was to study the effect of the time of application of phosphorus fertilizer with fertirrigation in a melon crop amended with winery waste compost on yield and quality parameters. During two years, the melon crop was grown under field conditions and beside the control treatment, three doses of compost were applied: 6.7, 13.3 and 20.0 t ha-1. All the compost treatments received 120 kg ha-1 of phosphorus fertilizer (phosphoric acid) for the season varying the time of application: The first year phosphorus application started after male and female flowering, and the second year the application started before flowering. Yield and quality parameters were evaluated to assess the suitability of these practices. Acknowledgements: This project has been supported by INIA-RTA2010-00110-C03. Keywords: Phosphorus fertilizer, exhausted grape marc compost, melon crop, yield and quality parameters.

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

    SciTech Connect

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

    2015-07-01

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

  18. A method for the deductive and unique determination of the values of three parameters involved in fractional functions applicable to relaxation kinetics.

    PubMed

    Sakoda, M; Hiromi, K

    1976-12-01

    A novel method is proposed to determine deductively and uniquely the values of three parameters, a, b, and c in a fractional function of the form, y=a+bx/(c+x) where x and y are experimentally obtainable variables. This type of equation is frequently encountered in chemistry and biochemistry involving relaxation kinetics. The method of least squares with the Taylor expansion is employed for direct curve fitting of observed data to the fractional function. Approximate values of the parameters, which are always necessary prior to commending the above procedure, can be obtained by the method of rearrangement after canceling the denominator of fractional functions. This procedure is very simple, but very effective for estimating provisional values of the parameters. Deductive and unique determination of the parameters involved in the fractional function shown above can be accomplished for the first time by the combination of these two procedures. This method is extended to include the analysis of relaxation kinetic data such as those of temperature-jump method where the determination of equilibrium concentrations of reactants in addition to the three parameters is also necessary.

  19. A novel population balance model to investigate the kinetics of in vitro cell proliferation: part II. Numerical solution, parameters' determination, and model outcomes.

    PubMed

    Fadda, Sarah; Cincotti, Alberto; Cao, Giacomo

    2012-03-01

    Based on the general theoretical model developed in Part I of this work, a series of numerical simulations related to the in vitro proliferation kinetics of adherent cells is here presented. First the complex task of assigning a specific value to all the parameters of the proposed population balance (PB) model is addressed, by also highlighting the difficulties arising when performing proper comparisons with experimental data. Then, a parametric sensitivity analysis is performed, thus identifying the more relevant parameters from a kinetics perspective. The proposed PB model can be adapted to describe cell growth under various conditions, by properly changing the value of the adjustable parameters. For this reason, model parameters able to mimic cell culture behavior under microgravity conditions are identified by means of a suitable parametric sensitivity analysis. Specifically, it is found that, as the volume growth parameter is reduced, proliferation slows down while cells arrest in G0/G1 or G2/M depending on the initial distribution of cell population. On the basis of this result, model capabilities have been tested by means of a proper comparison with literature experimental data related to the behavior of synchronized and not-synchronized cells under micro- and standard gravity levels.

  20. Random Regression Models Using Legendre Polynomials to Estimate Genetic Parameters for Test-day Milk Protein Yields in Iranian Holstein Dairy Cattle

    PubMed Central

    Naserkheil, Masoumeh; Miraie-Ashtiani, Seyed Reza; Nejati-Javaremi, Ardeshir; Son, Jihyun; Lee, Deukhwan

    2016-01-01

    The objective of this study was to estimate the genetic parameters of milk protein yields in Iranian Holstein dairy cattle. A total of 1,112,082 test-day milk protein yield records of 167,269 first lactation Holstein cows, calved from 1990 to 2010, were analyzed. Estimates of the variance components, heritability, and genetic correlations for milk protein yields were obtained using a random regression test-day model. Milking times, herd, age of recording, year, and month of recording were included as fixed effects in the model. Additive genetic and permanent environmental random effects for the lactation curve were taken into account by applying orthogonal Legendre polynomials of the fourth order in the model. The lowest and highest additive genetic variances were estimated at the beginning and end of lactation, respectively. Permanent environmental variance was higher at both extremes. Residual variance was lowest at the middle of the lactation and contrarily, heritability increased during this period. Maximum heritability was found during the 12th lactation stage (0.213±0.007). Genetic, permanent, and phenotypic correlations among test-days decreased as the interval between consecutive test-days increased. A relatively large data set was used in this study; therefore, the estimated (co)variance components for random regression coefficients could be used for national genetic evaluation of dairy cattle in Iran. PMID:26954192

  1. Genetic parameters of linear conformation type traits and their relationship with milk yield throughout lactation in mixed-breed dairy goats.

    PubMed

    McLaren, A; Mucha, S; Mrode, R; Coffey, M; Conington, J

    2016-07-01

    Conformation traits are of interest to many dairy goat breeders not only as descriptive traits in their own right, but also because of their influence on production, longevity, and profitability. If these traits are to be considered for inclusion in future dairy goat breeding programs, relationships between them and production traits such as milk yield must be considered. With the increased use of regression models to estimate genetic parameters, an opportunity now exists to investigate correlations between conformation traits and milk yield throughout lactation in more detail. The aims of this study were therefore to (1) estimate genetic parameters for conformation traits in a population of crossbred dairy goats, (2) estimate correlations between all conformation traits, and (3) assess the relationship between conformation traits and milk yield throughout lactation. No information on milk composition was available. Data were collected from goats based on 2 commercial goat farms during August and September in 2013 and 2014. Ten conformation traits, relating to udder, teat, leg, and feet characteristics, were scored on a linear scale (1-9). The overall data set comprised data available for 4,229 goats, all in their first lactation. The population of goats used in the study was created using random crossings between 3 breeds: British Alpine, Saanen, and Toggenburg. In each generation, the best performing animals were selected for breeding, leading to the formation of a synthetic breed. The pedigree file used in the analyses contained sire and dam information for a total of 30,139 individuals. The models fitted relevant fixed and random effects. Heritability estimates for the conformation traits were low to moderate, ranging from 0.02 to 0.38. A range of positive and negative phenotypic and genetic correlations between the traits were observed, with the highest correlations found between udder depth and udder attachment (0.78), teat angle and teat placement (0

  2. Radiographic Trabecular 2D and 3D Parameters of Proximal Femoral Bone Cores Correlate with Each Other and with Yield Stress

    PubMed Central

    Steines, Daniel; Liew, Siau-Way; Arnaud, Claude; Voracek, Rene Vargas; Nazarian, Ara; Müller, Ralph; Snyder, Brian; Hess, Patrick; Lang, Philipp

    2010-01-01

    Introduction We compared morphometric measurements of trabecular patterns in two-dimensional (2D) projection radiographic images of cores from cadaver proximal femoral bones with conceptually equivalent measurements from three-dimensional (3D) μCT images. Methods Seven cadaver proximal femora provided 47 excised cores from seven regions. Digitized radiographs of those cores were processed with software that extracts trabecular patterns. Measurements of their distribution, geometry, and connectivity were compared with 3D parameters of similar definition derived from μCT of those cores. The relationship between 2D and 3D measurements and yield stress was also examined. Results 2D measurements strongly correlated with conceptually equivalent measurements obtained using 3D μCT. In all cases, the correlation coefficients were high, ranging from r=0.84 (p<0.001) to r=0.93 (p<0.001). The correlation coefficients between 2D and 3D measurements and yield stress of the cores were also high (r=0.60 and 0.82, p<0.001 respectively). Conclusions These findings provide correlative and biomechanical evidence supporting the qualitative similarity of 2D microstructural parameters extracted from plain proximal femoral core X-ray images to conceptually equivalent 3D microstuctural measurements of those same cores. PMID:19319618

  3. 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.

  4. A review on zinc and nickel adsorption on natural and modified zeolite, bentonite and vermiculite: examination of process parameters, kinetics and isotherms.

    PubMed

    Malamis, S; Katsou, E

    2013-05-15

    Adsorption and ion exchange can be effectively employed for the treatment of metal-contaminated wastewater streams. The use of low-cost materials as sorbents increases the competitive advantage of the process. Natural and modified minerals have been extensively employed for the removal of nickel and zinc from water and wastewater. This work critically reviews existing knowledge and research on the uptake of nickel and zinc by natural and modified zeolite, bentonite and vermiculite. It focuses on the examination of different parameters affecting the process, system kinetics and equilibrium conditions. The process parameters under investigation are the initial metal concentration, ionic strength, solution pH, adsorbent type, grain size and concentration, temperature, agitation speed, presence of competing ions in the solution and type of adsorbate. The system's performance is evaluated with respect to the overall metal removal and the adsorption capacity. Furthermore, research works comparing the process kinetics with existing reaction kinetic and diffusion models are reviewed as well as works examining the performance of isotherm models against the experimental equilibrium data.

  5. Modeling sugarcane yield with a process-based model from site to continental scale: uncertainties arising from model structure and parameter values

    NASA Astrophysics Data System (ADS)

    Valade, A.; Ciais, P.; Vuichard, N.; Viovy, N.; Caubel, A.; Huth, N.; Marin, F.; Martiné, J.-F.

    2014-06-01

    parameters on a continental scale across the large regions of intensive sugarcane cultivation in Australia and Brazil. The ten parameters driving most of the uncertainty in the ORCHIDEE-STICS modeled biomass at the 7 sites are identified by the screening procedure. We found that the 10 most sensitive parameters control phenology (maximum rate of increase of LAI) and root uptake of water and nitrogen (root profile and root growth rate, nitrogen stress threshold) in STICS, and photosynthesis (optimal temperature of photosynthesis, optimal carboxylation rate), radiation interception (extinction coefficient), and transpiration and respiration (stomatal conductance, growth and maintenance respiration coefficients) in ORCHIDEE. We find that the optimal carboxylation rate and photosynthesis temperature parameters contribute most to the uncertainty in harvested biomass simulations at site scale. The spatial variation of the ranked correlation between input parameters and modeled biomass at harvest is well explained by rain and temperature drivers, suggesting different climate-mediated sensitivities of modeled sugarcane yield to the model parameters, for Australia and Brazil. This study reveals the spatial and temporal patterns of uncertainty variability for a highly parameterized agro-LSM and calls for more systematic uncertainty analyses of such models.

  6. Modeling sugar cane yield with a process-based model from site to continental scale: uncertainties arising from model structure and parameter values

    NASA Astrophysics Data System (ADS)

    Valade, A.; Ciais, P.; Vuichard, N.; Viovy, N.; Huth, N.; Marin, F.; Martiné, J.-F.

    2014-01-01

    parameters on a continental scale across the large regions of intensive sugar cane cultivation in Australia and Brazil. Ten parameters driving most of the uncertainty in the ORCHIDEE-STICS modeled biomass at the 7 sites are identified by the screening procedure. We found that the 10 most sensitive parameters control phenology (maximum rate of increase of LAI) and root uptake of water and nitrogen (root profile and root growth rate, nitrogen stress threshold) in STICS, and photosynthesis (optimal temperature of photosynthesis, optimal carboxylation rate), radiation interception (extinction coefficient), and transpiration and respiration (stomatal conductance, growth and maintenance respiration coefficients) in ORCHIDEE. We find that the optimal carboxylation rate and photosynthesis temperature parameters contribute most to the uncertainty in harvested biomass simulations at site scale. The spatial variation of the ranked correlation between input parameters and modeled biomass at harvest is well explained by rain and temperature drivers, suggesting climate-mediated different sensitivities of modeled sugar cane yield to the model parameters, for Australia and Brazil. This study reveals the spatial and temporal patterns of uncertainty variability for a highly parameterized agro-LSM and calls for more systematic uncertainty analyses of such models.

  7. Genetic parameters of coagulation properties, milk yield, quality, and acidity estimated using coagulating and noncoagulating milk information in Brown Swiss and Holstein-Friesian cows.

    PubMed

    Cecchinato, A; Penasa, M; De Marchi, M; Gallo, L; Bittante, G; Carnier, P

    2011-08-01

    The aim of this study was to estimate heritabilities of rennet coagulation time (RCT) and curd firmness (a(30)) and their genetic correlations with test-day milk yield, composition (fat, protein, and casein content), somatic cell score, and acidity (pH and titratable acidity) using coagulating and noncoagulating (NC) milk information. Data were from 1,025 Holstein-Friesian (HF) and 1,234 Brown Swiss (BS) cows, which were progeny of 54 HF and 58 BS artificial insemination sires, respectively. Milk coagulation properties (MCP) of each cow were measured once using a computerized renneting meter and samples not exhibiting coagulation within 31 min after rennet addition were classified as NC milk. For NC samples, RCT was unobserved. Multivariate analyses, using Bayesian methodology, were performed to estimate the genetic relationships of RCT or a(30) with the other traits and statistical inference was based on the marginal posterior distributions of parameters of concern. For analyses involving RCT, a right-censored Gaussian linear model was used and records of NC milk samples, being censored records, were included as unknown parameters in the model implementing a data augmentation procedure. Rennet coagulation time was more heritable [heritability (h(2))=0.240 and h(2)=0.210 for HF and BS, respectively] than a(30) (h(2)=0.148 and h(2)=0.168 for HF and BS, respectively). Milk coagulation properties were more heritable than a single test-day milk yield (h(2)=0.103 and h(2)=0.097 for HF and BS, respectively) and less heritable than milk composition traits whose heritability ranged from 0.275 to 0.275, with the only exception of fat content of BS milk (h(2)=0.108). A negative genetic correlation, lower than -0.85, was estimated between RCT and a(30) for both breeds. Genetic relationships of MCP with yield and composition were low or moderate and favorable. The genetic correlation of somatic cell score with RCT in BS cows was large and positive and even more positive were

  8. Plasma parameters and active species kinetics in CF4/O2/Ar gas mixture: effects of CF4/O2 and O2/Ar mixing ratios

    NASA Astrophysics Data System (ADS)

    Lee, Junmyung; Kwon, Kwang-Ho; Efremov, A.

    2016-12-01

    The effects of both CF4/O2 and O2/Ar mixing ratios in three-component CF4/O2/Ar mixture on plasma parameters, densities and fluxes of active species determining the dry etching kinetics were analyzed. The investigation combined plasma diagnostics by Langmuir probes and zero-dimensional plasma modeling. It was found that the substitution of CF4 for O2 at constant fraction of Ar in a feed gas produces the non-monotonic change in F atom density, as it was repeatedly reported for the binary CF4/O2 gas mixtures. At the same time, the substitution of Ar for O2 at constant fraction of CF4 results in the monotonic increase in F atom density toward more oxygenated plasmas. The natures of these phenomena as well as theirs possible impacts on the etching/polymerization kinetics were discussed in details.

  9. Detrimental effect of selection for milk yield on genetic tolerance to heat stress in purebred Zebu cattle: Genetic parameters and trends.

    PubMed

    Santana, M L; Pereira, R J; Bignardi, A B; Filho, A E Vercesi; Menéndez-Buxadera, A; El Faro, L

    2015-12-01

    In an attempt to determine the possible detrimental effects of continuous selection for milk yield on the genetic tolerance of Zebu cattle to heat stress, genetic parameters and trends of the response to heat stress for 86,950 test-day (TD) milk yield records from 14,670 first lactations of purebred dairy Gir cows were estimated. A random regression model with regression on days in milk (DIM) and temperature-humidity index (THI) values was applied to the data. The most detrimental effect of THI on milk yield was observed in the stage of lactation with higher milk production, DIM 61 to 120 (-0.099kg/d per THI). Although modest variations were observed for the THI scale, a reduction in additive genetic variance as well as in permanent environmental and residual variance was observed with increasing THI values. The heritability estimates showed a slight increase with increasing THI values for any DIM. The correlations between additive genetic effects across the THI scale showed that, for most of the THI values, genotype by environment interactions due to heat stress were less important for the ranking of bulls. However, for extreme THI values, this type of genotype by environment interaction may lead to an important error in selection. As a result of the selection for milk yield practiced in the dairy Gir population for 3 decades, the genetic trend of cumulative milk yield was significantly positive for production in both high (51.81kg/yr) and low THI values (78.48kg/yr). However, the difference between the breeding values of animals at high and low THI may be considered alarming (355kg in 2011). The genetic trends observed for the regression coefficients related to general production level (intercept of the reaction norm) and specific ability to respond to heat stress (slope of the reaction norm) indicate that the dairy Gir population is heading toward a higher production level at the expense of lower tolerance to heat stress. These trends reflect the genetic

  10. Parameter identifiability and Extended Multiple Studies Analysis of a compartmental model for human vitamin A kinetics: fixing fractional transfer coefficients for the initial steps in the absorptive process.

    PubMed

    Park, Hyunjin; Green, Michael H

    2014-03-28

    In the existing compartmental models of human vitamin A metabolism, parameters related to the absorption of the isotopic oral dose have not been well identified. We hypothesised that fixing some poorly identified parameters related to vitamin A absorption would improve parameter identifiability and add statistical certainty to such models. In the present study, data for serum vitamin A kinetics in nine subjects given [2H8]retinyl acetate orally and a model with absorption fixed at 75 % were used to test this hypothesis. In addition to absorption efficiency, we fixed two other fractional transfer coefficients: one representing the initial processing of the ingested dose and the other representing the direct secretion of retinol bound to retinol-binding protein (RBP) from enterocytes into the plasma. The Windows version of Simulation, Analysis and Modeling software (WinSAAM) was used to fit serum tracer data v. time for each subject. Then, a population model was generated by WinSAAM's Extended Multiple Studies Analysis. All the parameters had fractional standard deviations < 0·5, and none of the pairs of parameters had a correlation coefficient >0·8 (accepted criteria for well-identified parameters). Similar to the values predicted by the original model, total traced mass for retinol was 1160 (sd 468) μmol, and the time for retinol to appear in the plasma bound to RBP was 31·3 (sd 4·4) h. In conclusion, we suggest that this approach holds promise for advancing compartmental modelling of vitamin A kinetics in humans when the dose must be administered orally.

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

    PubMed

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

    2016-06-01

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

  12. An automated image-based method of 3D subject-specific body segment parameter estimation for kinetic analyses of rapid movements.

    PubMed

    Sheets, Alison L; Corazza, Stefano; Andriacchi, Thomas P

    2010-01-01

    Accurate subject-specific body segment parameters (BSPs) are necessary to perform kinetic analyses of human movements with large accelerations, or no external contact forces or moments. A new automated topographical image-based method of estimating segment mass, center of mass (CM) position, and moments of inertia is presented. Body geometry and volume were measured using a laser scanner, then an automated pose and shape registration algorithm segmented the scanned body surface, and identified joint center (JC) positions. Assuming the constant segment densities of Dempster, thigh and shank masses, CM locations, and moments of inertia were estimated for four male subjects with body mass indexes (BMIs) of 19.7-38.2. The subject-specific BSP were compared with those determined using Dempster and Clauser regression equations. The influence of BSP and BMI differences on knee and hip net forces and moments during a running swing phase were quantified for the subjects with the smallest and largest BMIs. Subject-specific BSP for 15 body segments were quickly calculated using the image-based method, and total subject masses were overestimated by 1.7-2.9%.When compared with the Dempster and Clauser methods, image-based and regression estimated thigh BSP varied more than the shank parameters. Thigh masses and hip JC to thigh CM distances were consistently larger, and each transverse moment of inertia was smaller using the image-based method. Because the shank had larger linear and angular accelerations than the thigh during the running swing phase, shank BSP differences had a larger effect on calculated intersegmental forces and moments at the knee joint than thigh BSP differences did at the hip. It was the net knee kinetic differences caused by the shank BSP differences that were the largest contributors to the hip variations. Finally, BSP differences produced larger kinetic differences for the subject with larger segment masses, suggesting that parameter accuracy is more

  13. Sorption of SO(2) and NO from simulated flue gas over rice husk ash (RHA)/CaO/CeO(2) sorbent: evaluation of deactivation kinetic parameters.

    PubMed

    Dahlan, Irvan; Lee, Keat Teong; Kamaruddin, Azlina Harun; Mohamed, Abdul Rahman

    2011-01-30

    In this study, the kinetic parameters of rice husk ash (RHA)/CaO/CeO(2) sorbent for SO(2) and NO sorptions were investigated in a laboratory-scale stainless steel fixed-bed reactor. Data experiments were obtained from our previous results and additional independent experiments were carried out at different conditions. The initial sorption rate constant (k(0)) and deactivation rate constant (k(d)) for SO(2)/NO sorptions were obtained from the nonlinear regression analysis of the experimental breakthrough data using deactivation kinetic model. Both the initial sorption rate constants and deactivation rate constants increased with increasing temperature, except at operating temperature of 170 °C. The activation energy and frequency factor for the SO(2) sorption were found to be 18.0 kJ/mol and 7.37 × 10(5)cm(3)/(g min), respectively. Whereas the activation energy and frequency factor for the NO sorption, were estimated to be 5.64 kJ/mol and 2.19 × 10(4)cm(3)/(g min), respectively. The deactivation kinetic model was found to give a very good agreement with the experimental data of the SO(2)/NO sorptions.

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

    PubMed

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

    2016-10-01

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

  15. Kinetics of lipogenic genes expression in milk purified mammary epithelial cells (MEC) across lactation and their correlation with milk and fat yield in buffalo.

    PubMed

    Yadav, Poonam; Kumar, Parveen; Mukesh, Manishi; Kataria, R S; Yadav, Anita; Mohanty, A K; Mishra, B P

    2015-04-01

    Expression patterns of lipogenic genes (LPL, ABCG2, ACSS2, ACACA, SCD, BDH, LIPIN1, SREBF1, PPARα and PPARγ) were studied in milk purified MEC across different stages of lactation (15, 30, 45, 60, 90, 120 and 240 days relative to parturition) in buffalo. PPARα was the most abundant gene while ABCG2 and ACSS2 had moderate level of expression; whereas expression of SREBF and PPARγ was very low. The expression patterns of some genes (BDH1, ACSS2, and LIPIN1) across lactation were positively correlated with milk yield while negatively correlated with fat yield. SCD also showed weak correlation with milk yield (p, 0.53) and fat yield (p, -0.47). On the other hand, expression pattern of ACACA was negatively correlated with milk yield (p, -0.88) and positively correlated with fat yield (p, 0.62). Strong correlation was observed between genes involved in de novo milk fat synthesis (BDH1, ACSS2, LIPIN2 and SCD) and milk yield.

  16. Kinetics of the reactions of HBr with O3 and HO2: The yield of HBr from HO2 + BrO

    NASA Technical Reports Server (NTRS)

    Mellouki, Abdelwahid; Talukdar, Ranajit K.; Howard, Carleton J.

    1994-01-01

    An upper limit on the yield of HBr from reaction (R1) (HO2 + BrO yields products) has been determined by measuring an upper limit for the rate coefficient of the reverse reaction (R1') (HBr + O3 yields HO2 + BrO). The limits measured at 300 and 441 K were extrapolated to low temperatures to determine that the yield of HBr from reaction (R1) is negligible throughout the stratosphere (less than 0.01% of k(sub 1)). An upper limit for the rate coefficient of the reaction of HO2 with HBr was also determined to be very low less than or equal to 3 x 10(exp -17) cu cm/molecule/sec at 300 K and less than or equal to 3 x 10(exp -16) cu cm/molecule/sec at 400 K. The implications of these results to stratospheric chemistry are discussed.

  17. 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.

  18. 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.

  19. Network topology and parameter estimation: from experimental design methods to gene regulatory network kinetics using a community based approach

    PubMed Central

    2014-01-01

    Background Accurate estimation of parameters of biochemical models is required to characterize the dynamics of molecular processes. This problem is intimately linked to identifying the most informative experiments for accomplishing such tasks. While significant progress has been made, effective experimental strategies for parameter identification and for distinguishing among alternative network topologies remain unclear. We approached these questions in an unbiased manner using a unique community-based approach in the context of the DREAM initiative (Dialogue for Reverse Engineering Assessment of Methods). We created an in silico test framework under which participants could probe a network with hidden parameters by requesting a range of experimental assays; results of these experiments were simulated according to a model of network dynamics only partially revealed to participants. Results We proposed two challenges; in the first, participants were given the topology and underlying biochemical structure of a 9-gene regulatory network and were asked to determine its parameter values. In the second challenge, participants were given an incomplete topology with 11 genes and asked to find three missing links in the model. In both challenges, a budget was provided to buy experimental data generated in silico with the model and mimicking the features of different common experimental techniques, such as microarrays and fluorescence microscopy. Data could be bought at any stage, allowing participants to implement an iterative loop of experiments and computation. Conclusions A total of 19 teams participated in this competition. The results suggest that the combination of state-of-the-art parameter estimation and a varied set of experimental methods using a few datasets, mostly fluorescence imaging data, can accurately determine parameters of biochemical models of gene regulation. However, the task is considerably more difficult if the gene network topology is not completely

  20. The effect of marine algae in the ration of high-yielding dairy cows during transition on metabolic parameters in serum and follicular fluid around parturition.

    PubMed

    Hostens, M; Fievez, V; Vlaeminck, B; Buyse, J; Leroy, J; Piepers, S; De Vliegher, S; Opsomer, G

    2011-09-01

    Sixteen Holstein cows were assigned to 2 groups to evaluate the caloric and metabolic effect of feeding marine algae (ALG) from 3 wk prepartum until 12 wk postpartum. Milk production characteristics and the profiles of hormones and metabolites in the serum were monitored from -7 to 46 d in milk (DIM) and in follicular fluid (FF) from 14 to 46 DIM. All cows received a corn- and grass silage-based partially mixed ration supplemented with concentrate and protein supplement. In the diet of the ALG group, 2 kg of the concentrate was replaced by a concentrate containing ALG (44 g/d of docosahexaenoic acid). Diets were isocaloric (net energy basis) and equal in intestinal digestible protein. The ALG diet increased milk yield (41.2 vs. 38.2 kg/d) and decreased milk fat yield (1.181 vs. 1.493 kg/d) and milk fat content (31.6 vs. 40.7 g/kg). Protein yield (1.336 vs. 1.301 kg/d) was not affected but a tendency toward decreased milk protein content (32.8 vs. 34.7 g/kg) was observed. Marine algae supplementation increased the β-hydroxybutyric acid (BHBA) concentration in FF of the ALG cows compared with that in the controls (0.992 vs. 0.718 mmol/L). The total protein concentration in FF was decreased in ALG (62.9 vs. 67.6 g/L). Plasma and serum metabolites did not significantly differ between treatments except for a tendency toward a lower concentration of urea in the serum of the control compared with ALG (4.69 vs. 5.13 mmol/L). Based on metabolizable energy calculations, a daily energy-sparing effect of 3.48 Mcal was obtained due to milk fat depression (MFD). The concomitant increase in milk yield suggests that at least part of this spared energy is used to stimulate milk production. Theoretically, 3.48 Mcal of ME could lead to an increase in milk yield of 7.43 kg/d, which is higher than the observed 3 kg/d. However, when evaluating nutrient requirements during MFD in early lactation, we calculated that increased milk production is caused by a propionate-saving effect of 2

  1. Crystal Growth Simulations To Establish Physically Relevant Kinetic Parameters from the Empirical Kolmogorov-Johnson-Mehl-Avrami Model

    SciTech Connect

    Dill, Eric D.; Folmer, Jacob C.W.; Martin, James D.

    2013-12-05

    A series of simulations was performed to enable interpretation of the material and physical significance of the parameters defined in the Kolmogorov, Johnson and Mehl, and Avrami (KJMA) rate expression commonly used to describe phase boundary controlled reactions of condensed matter. The parameters k, n, and t0 are shown to be highly correlated, which if unaccounted for seriously challenge mechanistic interpretation. It is demonstrated that rate measurements exhibit an intrinsic uncertainty without precise knowledge of the location and orientation of nucleation with respect to the free volume into which it grows. More significantly, it is demonstrated that the KJMA rate constant k is highly dependent on sample size. However, under the simulated conditions of slow nucleation relative to crystal growth, sample volume and sample anisotropy correction affords a means to eliminate the experimental condition dependence of the KJMA rate constant, k, producing the material-specific parameter, the velocity of the phase boundary, vpb.

  2. Kinetic approach to the formation of 3D electromagnetic structures in flows of expanding plasma coronas. II. flow anisotropy parameters

    NASA Astrophysics Data System (ADS)

    Gubchenko, V. M.

    2015-12-01

    The formation of magnetic structures in moving hot solar coronal plasma and hot collisionless laser-produced plasma, as determined by nonlinear criteria for weak and strong magnetization on the basis of the friction parameter Γ B and Alfven number M A, is considered within the Vlasov and Maxwell equations in the second part of the work. The flow velocities are lower then the thermal electron velocity. The energy and pulse anisotropy parameters of a flow, which determine its electromagnetic properties in the Cherenkov resonance line, are calculated by shape of particle distribution function (PDF). The ratio of these parameters is the Q-factor G V ; it characterizes the electromagnetic properties of a plasma flow and is expressed via the ratio of diamagnetic and resistive current densities or via the ratio of irregular and diamagnetic plasma scales. A particle flow is similar to a conductive medium at G V ≪ 1 and a diamagnetic medium at G V ≫ 1. The following cases are considered. (1) A plasma flow is specified by an isotropic PDF and interacts with distributed magnetization. Expressions for anisotropy parameters are derived, 3D field structures in the tail wake are found, and a possibility of topological reconstruction into a compact state under variation in the parameter G V is shown. (2) A plasma flow is specified by an isotropic PDF; a steady-state diamagnetic current layer, characterized by an anisotropic PDF, is immersed inside it. The system is in the diamagnetic state G ≫ 1. The generalized anisotropy parameter is calculated and a possibility of the excitation of three types of diamagnetic structures with low resistive currents is shown. (3) The nonlinear dynamics of anisotropic quasi-current-free plasma ( G =-1), in which the diamagnetic and resistive current densities locally compensate each other in the phase space of particle velocities, is studied. This dynamics is implemented in the long wavelength limit in plasma with an anisotropic PDF.

  3. 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 (BFA), portal blood flow, blood volume, mean transit time, permeability-surface area product, fractional interstitial volume (vI), extraction fraction, mean intracellular water molecule lifetime (τC), and fractional intracellular volume (vC) 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 vI (P = 0.010), and WX-ETK-model-derived τC (P = 0.023) and vC (P = 0.042) were statistically significant prognostic biomarkers for 1YS. Increase in the WX-DP-model-derived BFA (P = 0.025) and decrease in the WX-TK, WX-ETK, WX-AATH, and WX-DP-model-derived vC (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 vC was an effective prognostic biomarker for advanced HCC treated with sunitinib. PMID:26366997

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

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

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

  5. Kinetic Parameters of Secondary Carbide Precipitation in High-Cr White Iron Alloyed by Mn-Ni-Mo-V Complex

    NASA Astrophysics Data System (ADS)

    Efremenko, V. G.; Chabak, Yu. G.; Brykov, M. N.

    2013-05-01

    This study presents kinetics of precipitation of secondary carbides in 14.55%Cr-Mn-Ni-Mo-V white cast iron during the destabilization heat treatment. The as-cast iron was heat treated at temperatures in the range of 800-1100 °C with soaking up to 6 h. Investigation was carried out by optical and electron microscopy, dilatometric analysis, Ms temperature measurement, and bulk hardness evaluation. TTT-curve of precipitation process of secondary carbides (M7C3, M23C6, M3C2) has been constructed in this study. It was determined that the precipitation occurs at the maximum rate at 950 °C where the process is started after 10 s and completed within 160 min further. The precipitation leads to significant increase of Ms temperature and bulk hardness; large soaking times at destabilization temperatures cause coarsening of secondary carbides and decrease in particles number, followed by decrease in hardness. The results obtained are discussed in terms of solubility of carbon in the austenite and diffusion activation of Cr atoms. The precipitation was found to consist of two stages with activation energies of 196.5 kJ/g-mole at the first stage and 47.1 kJ/g-mole at the second stage.

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

  7. Steady-State Kinetics of Br(2P 1/2) yields CO2(101) Electronic-to-Vibrational Energy Transfer Laser System.

    DTIC Science & Technology

    2011-07-21

    an ongoing project at AFIT to develop and characterize the technology of photolytically-pumped molecular lasers. In the process of conducting this work...results were obtained in both cases, indicating more detailed modeling of kinetic processes is called for. Additionally, an unexplained long-term decay in... process is monitored via the 2.71 ptm Br(2 P,/2) and 4.3 gm C0 2(101) side-fluorescence emissions, under steady-state conditions, to gain information

  8. Kinetics of the reactions of HBr with O{sub 3} and HO{sub 2}: The yield of HBr from HO{sub 2} + BrO

    SciTech Connect

    Mellouki, A.; Talukdar, R.K.; Howard, C.J.

    1994-11-20

    An upper limit on the yield of HBr from reaction (R1) (HO{sub 2} + BrO {yields} products) has been determined by measuring an upper limit for the rate coefficient of the reverse reaction (R1{prime}) (HBr + O{sub 3} {yields} HO{sub 2} + BrO). The limits measured at 300 and 441 K were extrapolated to low temperatures to determine that the yield of HBr from reaction (R1) is negligible throughout the stratosphere (<0.01% of k{sub 1}). An upper limit for the rate coefficient of the reaction of HO{sub 2} with HBr was also determined to be very low {le} 3 x 10{sup {minus}17}cm{sup 3}molecule{sup {minus}1}s{sup {minus}1} at 300 K and {le} 3 x 10{sup {minus}16}cm{sup 3}molecule{sup {minus}1}s{sup {minus}1} at 400 K. The implications of these results to stratospheric chemistry are discussed. 18 refs., 1 fig., 6 tabs.

  9. Calibration-free estimates of batch process yields and detection of process upsets using in situ spectroscopic measurements and nonisothermal kinetic models: 4-(dimethylamino)pyridine- catalyzed esterification of butanol.

    PubMed

    Gemperline, Paul; Puxty, Graeme; Maeder, Marcel; Walker, Dwight; Tarczynski, Frank; Bosserman, Mary

    2004-05-01

    In this paper, we report the use of an NIR fiber-optic spectrometer with a high-speed diode array for calibration-free monitoring and modeling of the reaction of acetic anhydride with butanol using the catalyst 4-(dimethylamino)pyridine in a microscale batch reactor. Acquisition of spectra at 5 ms/scan gave information relevant for modeling these fast batch processes with a single multibatch kinetic model. Nonlinear fitting of a first-principles model directly to the reaction spectra gave calibration-free estimates of time-dependent concentration profiles and pure component spectra. The amount of catalyst was varied between different batches to permit accurate estimation of its effect in the multiway model. A wide range of different models with increasing complexity could be fit to each batch individually with low residuals and apparent low lack of fit. However, only one model properly estimated the concentration profiles when all five batches were fitted simultaneously in a multiway kinetic model. Inclusion of on-line temperature measurements and use of an Arrhenius model for the estimated rate constant gave significantly improved model fits compared to an isothermal kinetic model. Augmentation of prerun batches with data from an additional batch permitted model-based forecasts of reaction trajectories, reaction yield, reaction end points, and process upsets. One batch with added water to simulate a process upset was easily detected by the calibration free process model.

  10. Simple tumor profile chart based on cell kinetic parameters and histologic grade is useful for estimating the natural growth rate of hepatocellular carcinoma.

    PubMed

    Nakajima, Tomoki; Moriguchi, Michihisa; Mitsumoto, Yasuhide; Katagishi, Tatsuo; Kimura, Hiroyuki; Shintani, Hiroyuki; Deguchi, Takeshi; Okanoue, Takeshi; Kagawa, Keizo; Ashihara, Tsukasa

    2002-01-01

    Thirty-four untreated hepatocellular carcinomas (HCCs) with known growth rates were classified into 5 groups on a tumor profile chart based on their doubling time (DT), Ki-67-positive index (Ki-67-PI), apoptotic index (Apo-I), and histologic grade. The slow-growing HCCs (DT > 100 days) consisted of well-differentiated tumors with slight cell kinetic imbalance and were divided into groups A and B. Group A had Apo-I values <3%, and most tumors had Ki-67-PI values <10%, whereas group B had Apo-I values of 3 per thousand to 10 per thousand and Ki-67-PI values of 10% to 20%. The HCCs with intermediate growth rates, which had Ki-67-PI values similar to those of the tumors in group B, were divided into groups C and D based on differences in cell kinetics: group C consisted of well-differentiated tumors, most of which had Apo-I values <3 per thousand, and group D consisted of moderately or poorly differentiated tumors with Apo-I values between 10 per thousand and 20 per thousand. The rapidly growing tumors (DT < 50 days, group E) had higher Ki-67-PI values than other groups and a wide range of Apo-I values. Rapidly growing tumors were mostly moderately or poorly differentiated, with a large cell kinetic imbalance in favor of cell production. This grouping system is useful for approximating the growth rate of HCCs in a clinical setting, even when only histologic parameters are available.

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

    SciTech Connect

    Zizin, M. N.; Zizina, S. N.; Kryakvin, L. V.; Pitilimov, V. A.; Tereshonok, V. A.

    2011-12-15

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

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

    PubMed

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

    2009-02-01

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

  13. Determination of the kinetic parameters for phospholipase C (Bacillus cereus) on different phospholipid substrates using a chromogenic assay based on the quantitation of inorganic phosphate.

    PubMed

    Hergenrother, P J; Martin, S F

    1997-08-15

    The kinetic parameters of the phosphatidylcholine-preferring phospholipase C from Bacillus cereus (PLCBc) have been evaluated for phosphatidylcholine, phosphatidylethanolamine, and phosphatidylserine substrates with a new assay based on the quantitation of inorganic phosphate (Pi). Treatment of the phosphomonoester product of the PLCBc-catalyzed hydrolysis of these phospholipids with alkaline phosphatase releases Pi. This Pi forms a complex with ammonium molybdate that is then reduced by ascorbic acid to provide a blue molybdenum chromogen with an absorbance maximum at 700 nm. This highly sensitive assay may be used to determine accurately less than 5 nmol of Pi in solution. Performing the assay in 96-well plates provides a rapid and convenient method to evaluate a variety of phospholipids as substrates for PLCBc. The assay has been utilized to ascertain the kinetic constants for the PLCBc-catalyzed hydrolysis of 1,2-dihexanoyl-sn-glycero-3-phosphocholine, 1,2-dihexanoyl-sn-glycero-3-phosphoethanolamine, and 1,2-dihexanoyl-sn-glycero-3-phospho-L-serine. It is found that these compounds are substrates for the enzyme with their VmaxS being in the order of phosphatidylcholine > phosphatidylethanolamine > phosphatidylserine.

  14. Structural characterization, thermoluminescence studies and kinetic parameters of SrSO4:Eu nanophosphors under X-ray and gamma excitations

    NASA Astrophysics Data System (ADS)

    Jayasudha, S.; Madhukumar, K.; Nair, C. M. K.; Nair, Resmi G.; Anandakumar, V. M.; Elias, Thayal Singh

    2016-02-01

    Nanostructured SrSO4:Eu phosphors with high thermoluminescence (TL) emission temperatures have been synthesized through a controlled chemical precipitation method. Structural analysis and TL studies under both γ-ray and X-ray excitations were done. The phosphors were characterized using Powder X-ray diffraction, X-ray photoelectron spectroscopy, SEM, TEM, thermogravimetry, UV-VIS and photoluminescence studies. The average crystallite size estimated using PXRD data is found to be around 40 nm. XPS and PL studies reveal that Eu2 + ions are the luminescence emission centres in the phosphor. The phosphor is found to be highly TL sensitive to both γ-rays and X-rays with very high emission temperature which is not reported so far. The emission behaviour is suitable for environmental radiation dosimetry applications. The TL glow curve shows well-defined isolated high temperature emission peak at 312 °C under 2 Gy γ-excitation and 284 °C for low energy diagnostic X-ray irradiation and 271 °C for high energy therapeutic X-rays. Chen's peak shape method is applied to obtain the kinetic parameters behind the TL emission. The TL mechanism is found to follow second order kinetics, suggesting the probability of re-trapping of charge carriers.

  15. Structural characterization, thermoluminescence studies and kinetic parameters of SrSO4:Eu nanophosphors under X-ray and gamma excitations.

    PubMed

    Jayasudha, S; Madhukumar, K; Nair, C M K; Nair, Resmi G; Anandakumar, V M; Elias, Thayal Singh

    2016-02-15

    Nanostructured SrSO4:Eu phosphors with high thermoluminescence (TL) emission temperatures have been synthesized through a controlled chemical precipitation method. Structural analysis and TL studies under both γ-ray and X-ray excitations were done. The phosphors were characterized using Powder X-ray diffraction, X-ray photoelectron spectroscopy, SEM, TEM, thermogravimetry, UV-VIS and photoluminescence studies. The average crystallite size estimated using PXRD data is found to be around 40nm. XPS and PL studies reveal that Eu(2+) ions are the luminescence emission centres in the phosphor. The phosphor is found to be highly TL sensitive to both γ-rays and X-rays with very high emission temperature which is not reported so far. The emission behaviour is suitable for environmental radiation dosimetry applications. The TL glow curve shows well-defined isolated high temperature emission peak at 312°C under 2Gy γ-excitation and 284°C for low energy diagnostic X-ray irradiation and 271°C for high energy therapeutic X-rays. Chen's peak shape method is applied to obtain the kinetic parameters behind the TL emission. The TL mechanism is found to follow second order kinetics, suggesting the probability of re-trapping of charge carriers.

  16. 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

  17. Organic nitrate and secondary organic aerosol yield from NO3 oxidation of β-pinene evaluated using a gas-phase kinetics/aerosol partitioning model

    NASA Astrophysics Data System (ADS)

    Fry, J. L.; Kiendler-Scharr, A.; Rollins, A. W.; Wooldridge, P. J.; Brown, S. S.; Fuchs, H.; Dubé, W.; Mensah, A.; Dal Maso, M.; Tillmann, R.; Dorn, H.-P.; Brauers, T.; Cohen, R. C.

    2009-02-01

    The yields of organic nitrates and of secondary organic aerosol (SOA) particle formation were measured for the reaction NO3+β-pinene under dry and humid conditions in the atmosphere simulation chamber SAPHIR at Research Center Jülich. These experiments were conducted at low concentrations of NO3 (NO3+N2O5<10 ppb) and β-pinene (peak~15 ppb), with no seed aerosol. SOA formation was observed to be prompt and substantial (~50% mass yield under both dry conditions and at 60% RH), and highly correlated with organic nitrate formation. The observed gas/aerosol partitioning of organic nitrates can be simulated using an absorptive partitioning model to derive an estimated vapor pressure of the condensing nitrate species of pvap~5×10-6 Torr (6.67×10-4 Pa), which constrains speculation about the oxidation mechanism and chemical identity of the organic nitrate. Once formed the SOA in this system continues to evolve, resulting in measurable aerosol volume decrease with time. The observations of high aerosol yield from NOx-dependent oxidation of monoterpenes provide an example of a significant anthropogenic source of SOA from biogenic hydrocarbon precursors. Estimates of the NO3+β-pinene SOA source strength for California and the globe indicate that NO3 reactions with monoterpenes are likely an important source (0.5-8% of the global total) of organic aerosol on regional and global scales.

  18. Organic nitrate and secondary organic aerosol yield from NO3 oxidation of β-pinene evaluated using a gas-phase kinetics/aerosol partitioning model

    NASA Astrophysics Data System (ADS)

    Fry, J. L.; Kiendler-Scharr, A.; Rollins, A. W.; Wooldridge, P. J.; Brown, S. S.; Fuchs, H.; Dube, W.; Mensah, A.; Dal Maso, M.; Tillmann, R.; Dorn, H.-P.; Brauers, T.; Cohen, R. C.

    2008-10-01

    The yields of organic nitrates and of secondary organic aerosol (SOA) particle formation were measured for the reaction NO3+β-pinene under dry and humid conditions in the atmosphere simulation chamber SAPHIR at Research Center Jülich. These experiments were conducted at low concentrations of NO3 (NO3+N2O5<10 ppb) and β-pinene (peak~15 ppb), with no seed aerosol. SOA formation was observed to be prompt and substantial (~50% mass yield under both dry conditions and at 60% RH), and highly correlated with organic nitrate formation. The observed gas/aerosol partitioning of organic nitrates can be simulated using an absorptive partitioning model to derive an estimated vapor pressure of the condensing nitrate species of pvap~5×10-6 Torr (6.67×10-4 Pa), which constrains speculation about the oxidation mechanism and chemical identity of the organic nitrate. Once formed the SOA in this system continues to evolve, resulting in measurable aerosol volume decrease with time. The observations of high aerosol yield from NOx-dependent oxidation of monoterpenes provide an example of a significant anthropogenic source of SOA from biogenic hydrocarbon precursors. Estimates of the NO3+β-pinene SOA source strength for California and the globe indicate that NO3 reactions with monoterpenes are likely an important source (0.5 8% of the global total) of organic aerosol on regional and global scales.

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

    PubMed

    Cai, Junmeng; Li, Tao; Liu, Ronghou

    2011-02-01

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

  20. Limitations in the clinical usefulness of single-dose pharmacokinetic studies of drugs and a bayesian approach for the estimation of kinetic parameters.

    PubMed

    Prandota, Joseph

    2004-01-01

    This review presents several clinical examples indicating that physiological changes in the body dependent and/or independent of developmental age, genetic polymorphisms, different disease states, acute and/or chronic inflammations, and physicochemical properties of drugs as well as some environmental factors, such as viral infections, may exert a significant effect on the first-time assessment of kinetic parameters of drug absorption, disposition, metabolism, and excretion after a single-dose administration in children and adults. The available pharmacokinetic data in the literature suggest that one must be cautious in interpretation and practical use of pharmacokinetic variables derived from either single-dose studies or bayesian methods, especially in a pediatric population.

  1. Effect of next-nearest neighbor interactions on the dynamic order parameter of the Kinetic Ising model in an oscillating field

    NASA Astrophysics Data System (ADS)

    Baez, William D.; Datta, Trinanjan

    We study the effects of next-nearest neighbor (NNN) interactions in the two-dimensional ferromagnetic kinetic Ising model exposed to an oscillating field. By tuning the interaction ratio (p =JNNN /JNN) of the NNN (JNNN) to the nearest-neighbor (NN) interaction (JNN) we find that the model undergoes a transition from a regime in which the dynamic order parameter Q is equal to zero to a phase in which Q is not equal to zero. From our studies we conclude that the model can exhibit an interaction induced transition from a deterministic to a stochastic state. Furthermore, we demonstrate that the systemsˆˆe2ˆˆ80ˆˆ99 metastable lifetime is sensitive not only to the lattice size, external field amplitude, and temperature (as found in earlier studies) but also to additional interactions present in the system.

  2. Kinetic and Energetic Parameters of Carob Wastes Fermentation by Saccharomyces cerevisiae: Crabtree Effect, Ethanol Toxicity, and Invertase Repression.

    PubMed

    Rodrigues, B; Peinado, J M; Raposo, S; Constantino, A; Quintas, C; Lima-Costa, M E

    2015-06-01

    Carob waste is a useful raw material for the second-generation ethanol because 50% of its dry weight is sucrose, glucose, and fructose. To optimize the process, we have studied the influence of the initial concentration of sugars on the fermentation performance of Saccharomyces cerevisiae. With initial sugar concentrations (S0) of 20 g/l, the yeasts were derepressed and the ethanol produced during the exponential phase was consumed in a diauxic phase. The rate of ethanol consumption decreased with increasing S0 and disappeared at 250 g/l when the Crabtree effect was complete and almost all the sugar consumed was transformed into ethanol with a yield factor of 0.42 g/g. Sucrose hydrolysis was delayed at high S0 because of glucose repression of invertase synthesis, which was triggered at concentrations above 40 g/l. At S0 higher than 250 g/l, even when glucose had been exhausted, sucrose was hydrolyzed very slowly, probably due to an inhibition at this low water activity. Although with lower metabolic rates and longer times of fermentation, 250 g/l is considered the optimal initial concentration because it avoids the diauxic consumption of ethanol and maintains enough invertase activity to consume all the sucrose, and also avoids the inhibitions due to lower water activities at higher S0.

  3. Sonochemical degradation of ethyl paraben in environmental samples: Statistically important parameters determining kinetics, by-products and pathways.

    PubMed

    Papadopoulos, Costas; Frontistis, Zacharias; Antonopoulou, Maria; Venieri, Danae; Konstantinou, Ioannis; Mantzavinos, Dionissios

    2016-07-01

    The sonochemical degradation of ethyl paraben (EP), a representative of the parabens family, was investigated. Experiments were conducted at constant ultrasound frequency of 20 kHz and liquid bulk temperature of 30 °C in the following range of experimental conditions: EP concentration 250-1250 μg/L, ultrasound (US) density 20-60 W/L, reaction time up to 120 min, initial pH 3-8 and sodium persulfate 0-100mg/L, either in ultrapure water or secondary treated wastewater. A factorial design methodology was adopted to elucidate the statistically important effects and their interactions and a full empirical model comprising seventeen terms was originally developed. Omitting several terms of lower significance, a reduced model that can reliably simulate the process was finally proposed; this includes EP concentration, reaction time, power density and initial pH, as well as the interactions (EP concentration)×(US density), (EP concentration)×(pHo) and (EP concentration)×(time). Experiments at an increased EP concentration of 3.5mg/L were also performed to identify degradation by-products. LC-TOF-MS analysis revealed that EP sonochemical degradation occurs through dealkylation of the ethyl chain to form methyl paraben, while successive hydroxylation of the aromatic ring yields 4-hydroxybenzoic, 2,4-dihydroxybenzoic and 3,4-dihydroxybenzoic acids. By-products are less toxic to bacterium V. fischeri than the parent compound.

  4. Steam explosion pretreatment of wheat straw to improve methane yields: investigation of the degradation kinetics of structural compounds during anaerobic digestion.

    PubMed

    Theuretzbacher, Franz; Lizasoain, Javier; Lefever, Christopher; Saylor, Molly K; Enguidanos, Ramon; Weran, Nikolaus; Gronauer, Andreas; Bauer, Alexander

    2015-03-01

    Wheat straw can serve as a low-cost substrate for energy production without competing with food or feed production. This study investigated the effect of steam explosion pretreatment on the biological methane potential and the degradation kinetics of wheat straw during anaerobic digestion. It was observed that the biological methane potential of the non steam exploded, ground wheat straw (276 l(N) kg VS(-1)) did not significantly differ from the best steam explosion treated sample (286 l(N) kg VS(-1)) which was achieved at a pretreatment temperature of 140°C and a retention time of 60 min. Nevertheless degradation speed was improved by the pretreatment. Furthermore it was observed that compounds resulting from chemical reactions during the pretreatment and classified as pseudo-lignin were also degraded during the anaerobic batch experiments. Based on the rumen simulation technique, a model was developed to characterise the degradation process.

  5. Heterogeneity of the coumarin anticoagulant targeted vitamin K epoxide reduction system. Study of kinetic parameters in susceptible and resistant mice (Mus musculus domesticus).

    PubMed

    Lasseur, Romain; Grandemange, Agnès; Longin-Sauvageon, Christiane; Berny, Philippe; Benoit, Etienne

    2006-01-01

    Vitamin K epoxide reductase (VKOR) activity in liver microsomes from a susceptible and a genetically warfarin-resistant strain of mice (Mus Musculus domesticus) was analyzed to determine the mechanism of resistance to this 4-hydroxycoumarin derivative. Kinetic parameters for VKOR were calculated for each strain by incubating liver microsomes with vitamin K epoxide +/- warfarin. In susceptible mice, an Eadie-Hofstee plot of the data was not linear and suggested the involvement of at least two different components. Apparent kinetic parameters were obtained by nonlinear regression using a Michaelis--Menten model, which takes into account two enzymatic components. Component A presents a high Km and a high Vm, and as a consequence only an enzymatic efficiency Vm/Km was obtained (0.0024 mL/min/mg). Estimated warfarin Ki was 0.17 microM. Component B presented an apparent Km of 12.73 microM, an apparent Vm of 0.32 nmol/min/mg, and an apparent Ki for warfarin of 6.0 microM. In resistant mice, the enzymatic efficiency corresponding to component A was highly decreased (0.0003-0.00066 mL/min/mg) while the Ki for warfarin was not modified. The apparent Vm of component B was poorly modified between susceptible and resistant mice. The apparent Km of component B observed in resistant mice was similar to the Km observed in susceptible mice. These modifications of the catalytic properties are associated with a single nucleotide polymorphism (T175G) in the VKOR-C1 gene, which corresponds to a Trp59Gly mutation in the protein.

  6. Inhibition and activation of enzymes. The effect of a modifier on the reaction rate and on kinetic parameters.

    PubMed

    Fontes, R; Ribeiro, J M; Sillero, A

    2000-01-01

    A combined analysis of enzyme inhibition and activation is presented, based on a rapid equilibrium model assumption in which one molecule of enzyme binds one molecule of substrate (S) and/or one molecule of a modifier X. The modifier acts as activator (essential or non-essential), as inhibitor (total or partial), or has no effect on the reaction rate (v), depending on the values of the equilibrium constants, the rate constants of the limiting velocity steps, and the concentration of substrate ([S]). Different possibilities have been analyzed from an equation written to emphasize that v = f([X]) is, in general and at a fixed [S], a hyperbolic function. Formulas for Su (the value of [S], different from zero, at which v is unaffected by the modifier) and v(su) (v at that particular [S]) were deduced. In Lineweaver-Burk plots, the straight lines related to different [X] generally cross in a point (P) with coordinates (Su, v(su)). In certain cases, point P is located in the first quadrant which implies that X acts as activator, as inhibitor, or has no effect, depending on [S]. Furthermore, we discuss: (1) the apparent Vmax and Km displayed by the enzyme in different situations; (2) the degree of effect (inhibition or activation) observed at different concentrations of substrate and modifier; (3) the concept of Ke, a parameter that depends on the concentration of substrate and helps to evaluate the effect of the modifier: it equals the value of [X] at which the increase or decrease in the reaction rate is half of that achieved at saturating [X]. Equations were deduced for the general case and for particular situations, and used to obtain computer-drawn graphs that are presented and discussed. Formulas for apparent Vmax, Km and Ke have been written in a way making it evident that these parameters can be expressed as pondered means.

  7. Estimation of Genetic Parameters for First Lactation Monthly Test-day Milk Yields using Random Regression Test Day Model in Karan Fries Cattle.

    PubMed

    Singh, Ajay; Singh, Avtar; Singh, Manvendra; Prakash, Ved; Ambhore, G S; Sahoo, S K; Dash, Soumya

    2016-06-01

    A single trait linear mixed random regression test-day model was applied for the first time for analyzing the first lactation monthly test-day milk yield records in Karan Fries cattle. The test-day milk yield data was modeled using a random regression model (RRM) considering different order of Legendre polynomial for the additive genetic effect (4th order) and the permanent environmental effect (5th order). Data pertaining to 1,583 lactation records spread over a period of 30 years were recorded and analyzed in the study. The variance component, heritability and genetic correlations among test-day milk yields were estimated using RRM. RRM heritability estimates of test-day milk yield varied from 0.11 to 0.22 in different test-day records. The estimates of genetic correlations between different test-day milk yields ranged 0.01 (test-day 1 [TD-1] and TD-11) to 0.99 (TD-4 and TD-5). The magnitudes of genetic correlations between test-day milk yields decreased as the interval between test-days increased and adjacent test-day had higher correlations. Additive genetic and permanent environment variances were higher for test-day milk yields at both ends of lactation. The residual variance was observed to be lower than the permanent environment variance for all the test-day milk yields.

  8. Inverse method to estimate kinetic degradation parameters of grape anthocyanins in wheat flour under simultaneously changing temperature and moisture.

    PubMed

    Lai, K P K; Dolan, K D; Ng, P K W

    2009-06-01

    Thermal and moisture effects on grape anthocyanin degradation were investigated using solid media to simulate processing at temperatures above 100 degrees C. Grape pomace (anthocyanin source) mixed with wheat pastry flour (1: 3, w/w dry basis) was used in both isothermal and nonisothermal experiments by heating the same mixture at 43% (db) initial moisture in steel cells in an oil bath at 80, 105, and 145 degrees C. To determine the effect of moisture on anthocyanin degradation, the grape pomace-wheat flour mixture was heated isothermally at 80 degrees C at constant moisture contents of 10%, 20%, and 43% (db). Anthocyanin degradation followed a pseudo first-order reaction with moisture. Anthocyanins degraded more rapidly with increasing temperature and moisture. The effects of temperature and moisture on the rate constant were modeled according to the Arrhenius and an exponential relationship, respectively. The nonisothermal reaction rate constant and activation energy (mean +/- standard error) were k(80 degrees C, 43% (db) moisture) = 2.81 x 10(-4)+/- 1.1 x 10(-6) s(-1) and DeltaE = 75273 +/- 197 J/g mol, respectively. The moisture parameter for the exponential model was 4.28 (dry basis moisture content)(-1). One possible application of this study is as a tool to predict the loss of anthocyanins in nutraceutical products containing grape pomace. For example, if the process temperature history and moisture history in an extruded snack fortified with grape pomace is known, the percentage anthocyanin loss can be predicted.

  9. In vitro release of metoclopramide from hydrophobic matrix tablets. influence of hydrodynamic conditions on kinetic release parameters.

    PubMed

    Frutos, P; Pabón, C; Lastres, J L; Frutos, G

    2001-10-01

    There has been growing interest in the subject of drug delivery and the design and evaluation of controlled-release systems. The simplest way to control the release of an active agent is to disperse it in an inert polymeric matrix. Controlled-release systems are of interest because they are technologically simple, relatively cheap, and practically unaffected by physiological changes. In this study, a new matrix system was formed by an active principle, metoclopramide hydrochloride, scattered into a biocompatible hydrophobic polymerical mesh, polyamide 12, to achieve sustained and controlled delivery of metoclopramide hydrochloride. This research was conducted to investigate the in vitro drug release behavior from these new inert polymeric matrix tablets. The drug release process was investigated both experimentally and by means of mathematical models. Different models were applied for the evaluation of drug release data. On the basis of our results, a biexponential equation was proposed, Q=Qfast(1)(1 - e(-Kfast t)) + Qslow(2)(1 - e(-Kslow t)), in an attempt to explain the mechanism responsible for the release process. Additionally, the influence of the experimental conditions of the dissolution devices, such as rate of flow and pH of dissolution medium, on the parameters that characterize the release mechanism was studied, and it was found that the main factor was the hydrodynamic condition of rate of flow.

  10. Spin Saturation Transfer Difference NMR (SSTD NMR): A New Tool to Obtain Kinetic Parameters of Chemical Exchange Processes

    PubMed Central

    Quirós, María Teresa; Macdonald, Colin; Angulo, Jesús; Muñoz, María Paz

    2016-01-01

    This detailed protocol describes the new Spin Saturation Transfer Difference Nuclear Magnetic Resonance protocol (SSTD NMR), recently developed in our group to study processes of mutual-site chemical exchange that are difficult to analyze by traditional methods. As the name suggests, this method combines the Spin Saturation Transfer method used for small molecules, with the Saturation Transfer Difference (STD) NMR method employed for the study of protein-ligand interactions, by measuring transient spin saturation transfer along increasing saturation times (build-up curves) in small organic and organometallic molecules undergoing chemical exchange. Advantages of this method over existing ones are: there is no need to reach coalescence of the exchanging signals; the method can be applied as long as one signal of the exchanging sites is isolated; there is no need to measure T1 or reach steady state saturation; rate constant values are measured directly, and T1 values are obtained in the same experiment, using only one set of experiments. To test the method, we have studied the dynamics of the hindered rotation of N,N-dimethylamides, for which much data is available for comparison. The thermodynamic parameters obtained using SSTD are very similar to the reported ones (spin-saturation transfer techniques and line-shape analysis). The method can be applied to more challenging substrates that cannot be studied by previous methods. We envisage that the simple experimental set up and the wide applicability of the method to a great variety of substrates will make this a common technique amongst organic and organometallic chemists without extensive expertise in NMR. PMID:27911361

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

    PubMed

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

    2013-03-01

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

  12. Evolution of a mini-scale biphasic dissolution model: Impact of model parameters on partitioning of dissolved API and modelling of in vivo-relevant kinetics.

    PubMed

    Locher, Kathrin; Borghardt, Jens M; Frank, Kerstin J; Kloft, Charlotte; Wagner, Karl G

    2016-08-01

    Biphasic dissolution models are proposed to have good predictive power for the in vivo absorption. The aim of this study was to improve our previously introduced mini-scale dissolution model to mimic in vivo situations more realistically and to increase the robustness of the experimental model. Six dissolved APIs (BCS II) were tested applying the improved mini-scale biphasic dissolution model (miBIdi-pH-II). The influence of experimental model parameters including various excipients, API concentrations, dual paddle and its rotation speed was investigated. The kinetics in the biphasic model was described applying a one- and four-compartment pharmacokinetic (PK) model. The improved biphasic dissolution model was robust related to differing APIs and excipient concentrations. The dual paddle guaranteed homogenous mixing in both phases; the optimal rotation speed was 25 and 75rpm for the aqueous and the octanol phase, respectively. A one-compartment PK model adequately characterised the data of fully dissolved APIs. A four-compartment PK model best quantified dissolution, precipitation, and partitioning also of undissolved amounts due to realistic pH profiles. The improved dissolution model is a powerful tool for investigating the interplay between dissolution, precipitation and partitioning of various poorly soluble APIs (BCS II). In vivo-relevant PK parameters could be estimated applying respective PK models.

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

    PubMed

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

    2014-04-21

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

  14. High-pressure anaerobic digestion up to 100 bar: influence of initial pressure on production kinetics and specific methane yields.

    PubMed

    Merkle, Wolfgang; Baer, Katharina; Haag, Nicola Leonard; Zielonka, Simon; Ortloff, Felix; Graf, Frank; Lemmer, Andreas

    2017-02-01

    To ensure an efficient use of biogas produced by anaerobic digestion, in some cases it would be advisable to upgrade the biogenic gases and inject them into the transnational gas grids. To investigate biogas production under high-pressure conditions up to 100 bar, new pressure batch methane reactors were developed for preliminary lab-scale experiments with a mixture of grass and maize silage hydrolysate. During this investigation, the effects of different initial pressures (1, 50 and 100 bar) on pressure increase, gas production and the specific methane yield using nitrogen as inert gas were determined. Based on the experimental findings increasing initial pressures alter neither significantly, further pressure increases nor pressure increase rates. All supplied organic acids were degraded and no measurable inhibition of the microorganisms was observed. The results show that methane reactors can be operated at operating pressures up to 100 bar without any negative effects on methane production.

  15. Pressure and temperature dependence kinetics study of the NO + BrO yielding NO2 + Br reaction - Implications for stratospheric bromine photochemistry

    NASA Technical Reports Server (NTRS)

    Watson, R. T.; Sander, S. P.; Yung, Y. L.

    1979-01-01

    The reactivity of NO with BrO radicals over a wide range of pressure (100-700 torr) and temperature (224-398 K) is investigated using the flash photolysis-ultraviolet absorption technique. The flash photolysis system consists of a high-pressure xenon arc light source, a reaction cell/gas filter/flash lamp combination, and a 216.5 half-meter monochromator/polychromator/spectrography for wavelength selectivity. The details of the reaction and its corresponding Arrhenius expression are identified. The results are compared with previous measurements, and atmospheric implications of the reaction are discussed. The NO + BrO yielding NO2 + Br reaction is shown to be important in controlling the concentration ratios of BrO/Br and BrO/HBr in the stratosphere, but this reaction does not affect the catalytic efficiency of BrOx in ozone destruction.

  16. Kinetics of O(1D) + H2O and O(1D) + H2: absolute rate coefficients and O(3P) yields between 227 and 453 K.

    PubMed

    Vranckx, Stijn; Peeters, Jozef; Carl, Shaun

    2010-08-28

    The rate coefficients for the crucial atmospheric reactions of O((1)D) with H(2)O and H(2), k(1) and k(2), were measured over a wide temperature range using O((1)D) detection based on the chemiluminescence reaction of O((1)D) with C(2)H. Analyzing the decays of the chemiluminescence intensities yielded a value for k(1)(T) of (1.70 x 10(-10)exp[36 K/T]) cm(3) s(-1). Multiplying or dividing k(1)(T) by a factor f(T) = 1.04 exp(5.59(|1 K/T- 1/287|)), gives the 95% confidence limits; our new determination, in good agreement with previous studies, further reduces the uncertainty in k(1). An extended study of k(2) yielded a temperature independent rate constant of (1.35 +/- 0.05) x 10(-10) cm(3) s(-1). This precise value, based on an extended set of determinations with very low scatter, is significantly larger than the current recommendations, as were two other recent k(2) determinations. Secondly, the fractions of O((1)D) quenched to O((3)P) by H(2)O and H(2), k(1b)/k(1) and k(2b)/k(2), were precisely determined from fits to chemiluminescence decays. A temperature-independent value for k(1b)/k(1) of 0.010 +/- 0.003 was found. For the quenching fraction k(2b)/k(2) a value of 0.007 +/- 0.007 was obtained at room temperature. Both determinations are significantly smaller than values and upper limits from previous studies.

  17. Toward full-chip prediction of yield-limiting contact patterning failure: correlation of simulated image parameters to advanced contact metrology metrics

    NASA Astrophysics Data System (ADS)

    Sturtevant, John L.; Chou, Dyiann

    2006-03-01

    Electrical failure due to incomplete contacts or vias has arisen as one of the primary modes of yield loss for 130 nm and below designs in manufacturing. Such failures are generally understood to arise from both random and systematic sources. The addition of redundant vias, where possible, has long been an accepted DFM practice for mitigating the impact of random defects. Incomplete vias are often characterized by having a diameter near the target dimension but a depth of less than 100% of target. As such, it is a difficult problem to diagnose and debug in-line, since bright and dark field optical inspection systems cannot typically distinguish between a closed, partially open and fully open contact. Advanced metrology systems have emerged in recent years to meet this challenge, but no perfect manufacturing solution has yet been identified for full field verification of all contacts. Voltage Contrast (VC) SEM metrology biases the wafer to directly measure electrical conductivity after fill / polish, and can therefore easily discern a lack of electrical connection to the underlying conductor caused by incomplete photo, etch, or fill processing. While an entire wafer can in principal be VC scanned, throughput limitations dictate very sparse sampling in manufacturing. SEM profile grading (PG) leverages the rich content of the secondary electron waveform to decipher information about the bottom of the contact. Several authors have demonstrated an excellent response of the Profile Grade to intentional defocus vectors. However, the SEM can only target discreet or single digit groupings of contacts, and therefore requires intelligent guidance to identify those contacts which are most prone to failure, enabling protection of the fab WIP. An a-priori knowledge of which specific contacts in a layout are most likely to fail would prove very useful for proactive inspection in manufacturing. Model based pre-manufacturing verification allows for such knowledge to be communicated

  18. Characterisation of endometrial gene expression and metabolic parameters in beef heifers yielding viable or non-viable embryos on Day 7 after insemination.

    PubMed

    Beltman, M E; Forde, N; Furney, P; Carter, F; Roche, J F; Lonergan, P; Crowe, M A

    2010-01-01

    The aim of the present study was to compare the hormonal and metabolic characteristics and endometrial gene expression profiles in beef heifers yielding either a viable or degenerate embryo on Day 7 after insemination as a means to explain differences in embryo survival. Oestrus was synchronised in cross-bred beef heifers (n = 145) using a controlled internal drug release (CIDR)-prostaglandin protocol. Heifers (n = 102) detected in standing oestrus (within 24-48 h after CIDR removal) were inseminated 12-18 h after detection of oestrus (Day 0) with frozen-thawed semen from a single ejaculate of a bull with proven fertility. Blood samples were collected from Day 4 to Day 7 after oestrus to measure progesterone (on Days 4, 5 and 7), insulin and insulin-like growth factor (IGF)-I (on Days 4 and 6) and urea (on Day 7) concentrations. All animals were killed on Day 7. Uterine pH was determined at the time of death. Animals from which an embryo was recovered were classified as either having a viable embryo (morula/blastocyst stage; n = 32) or a retarded embryo (arrested at the two- to 16-cell stage; n = 19). In addition, 14 single-celled unfertilised oocytes were recovered, giving an overall recovery rate of 64%. There was no significant difference in the blood parameters determined or uterine pH at the time of death between heifers with either a viable or retarded embryo. The relative abundance of nine transcripts (i.e. MOGAT1, PFKB2, LYZ2, SVS8, UHRF1, PTGES, AGPAT4, DGKA and HGPD) of 53 tested in the endometrial tissue differed between heifers with a viable or retarded embryo. Both LYZ2 and UHRF1 are associated with regulation of the immune system; PFKFB2 is a mediator in glycolysis; MOGAT, AGPAT4 and DGKA belong to the triglyceride synthesis pathway; and PTGES and HGPD belong to the prostaglandin pathway. Both these metabolic pathways are important for early embryonic development. In conclusion, retarded embryo development in the present study was not related to serum

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

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

    PubMed

    Ratelle, Mylène; Coté, Jonathan; Bouchard, Michèle

    2015-12-01

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

  1. Prospective evaluation of cell kinetics, yields and donor experiences during a single large-volume apheresis versus two smaller volume consecutive day collections of allogeneic peripheral blood stem cells.

    PubMed

    Bolan, Charles D; Carter, Charles S; Wesley, Robert A; Yau, Yu Ying; Barrett, A John; Childs, Richard W; Read, Elizabeth J; Leitman, Susan F

    2003-03-01

    We report cell kinetics, yields and donation experiences of 20 demographically matched allogeneic peripheral blood stem cell (PBSC) donors who were prospectively assigned to undergo either a single 25 l or two consecutive daily 15 l (15 l x 2) apheresis procedures. Procedures were performed using prophylactic intravenous calcium administration after standard granulocyte colony-stimulating factor (GCSF) mobilization (10 microg/kg/d). Central line placements (two each), initial CD34 cell counts (0.077 vs 0.078 x 10(9)/l) and yields (7.9 vs 8.1 x 10(8) CD34 cells) were similar in the two groups; however, 25 l donors spent significantly less time both in the clinic (7.5 vs 10.8 h) and with central venous catheters in place (8.5 vs 29.5 h) than 15 l x 2 donors. End-procedure platelet counts were below 100 x 10(9)/l in one out of 10 25 l donors versus five out of 10 in 15 l x 2 donors (41%vs 53% mean decrease in platelet counts, P = 0.02). PBSC collection efficiency increased by 37% after 15 l of the 25-l volume had been processed, compared with no significant change during 15 l x 2 procedures. Results similar to these prospective findings were also observed in CD34 yields, symptoms and platelet counts in additional 25 l and 15 l procedures performed during the same period and evaluated retrospectively. This study indicates that a single 25-l apheresis procedure results in similar yields and symptoms, but less donor thrombocytopenia and inconvenience than two consecutive daily 15-l procedures.

  2. Temperature dependent kinetics (195-798 K) and H atom yields (298-498 K) from reactions of (1)CH(2) with acetylene, ethene, and propene.

    PubMed

    Gannon, K L; Blitz, M A; Liang, C H; Pilling, M J; Seakins, P W; Glowacki, D R

    2010-09-09

    The rate coefficients for the removal of the excited state of methylene, (1)CH(2) (a(1)A(1)), by acetylene, ethene, and propene have been studied over the temperature range 195-798 K by laser flash photolysis, with (1)CH(2) being monitored by laser-induced fluorescence. The rate coefficients of all three reactions exhibit a negative temperature dependence that can be parametrized as k((1)CH(2)+C(2)H(2)) = (3.06 +/- 0.11) x 10(-10) T ((-0.39+/-0.07)) cm(3) molecule(-1) s(-1), k((1)CH(2)+C(2)H(4)) = (2.10 +/- 0.18) x 10(-10) T ((-0.84+/-0.18)) cm(3) molecule(-1) s(-1), k((1)CH(2)+C(3)H(6)) = (3.21 +/- 0.02) x 10(-10) T ((-0.13+/-0.01)) cm(3) molecule(-1) s(-1), where the errors are statistical at the 2sigma level. Removal of (1)CH(2) occurs by chemical reaction and electronic relaxation to ground state triplet methylene. The H atom yields from the reactions of (1)CH(2) with acetylene, ethene, and propene have been determined by laser-induced fluorescence over the temperature range 298-498 K. For the reaction with propene, H atom yields are close to the detection limit, but for acetylene and ethene, the fraction of H atom production is approximately 0.88 and 0.71, respectively, at 298 K, rising to unity by 398 K, with the balance of the reaction with acetylene presumed to be electronic relaxation. Experimental constraints limit studies to a maximum of 1 Torr of bath gas; master equation calculations using an approach that allows treatment of intermediates with deep energy wells have been carried out to explore the role of collisional stabilization for the reaction of (1)CH(2) with acetylene. Stabilization is calculated to be insignificant under the experimental conditions, but does become significant at higher pressures. Between pressures of 100 and 1000 Torr, propyne and allene are formed in similar amounts with a slight preference for propyne. At higher pressures propyne formation becomes about a factor two greater than that of allene, and above 10(5) Torr (300 < T

  3. Kinetics of microbial growth on pentachlorophenol.

    PubMed Central

    Klecka, G M; Maier, W J

    1985-01-01

    Batch and fed-batch experiments were conducted to examine the kinetics of pentachlorophenol utilization by an enrichment culture of pentachlorophenol-degrading bacteria. The Haldane modification of the Monod equation was found to describe the relationship between the specific growth rate and substrate concentration. Analysis of the kinetic parameters indicated that the maximum specific growth rate and yield coefficients are low, with values of 0.074 h-1 and 0.136 g/g, respectively. The Monod constant (Ks) was estimated to be 60 micrograms/liter, indicating a high affinity of the microorganisms for the substrate. However, high concentrations (KI = 1,375 micrograms/liter) were shown to be inhibitory for metabolism and growth. These kinetic parameters can be used to define the optimal conditions for the removal of pentachlorophenol in biological treatment systems. PMID:3977315

  4. Assessment of total- and partial-body irradiation in a baboon model: preliminary results of a kinetic study including clinical, physical, and biological parameters.

    PubMed

    Hérodin, Francis; Richard, Sandrine; Grenier, Nancy; Arvers, Philippe; Gérome, Patrick; Baugé, Stéphane; Denis, Josiane; Chaussard, Hervé; Gouard, Stéphane; Mayol, Jean-François; Agay, Diane; Drouet, Michel

    2012-08-01

    This biodosimetry study used irradiated baboons to investigate the efficacy of a kinetic multiparameter (clinical, physical, and biological) approach for discriminating partial-body irradiation (PBI) and total-body irradiation (TBI). Animals were unilaterally (front) exposed to 60Co gamma rays (8 to 32 cGy min) using either TBI or vertical left hemi-body irradiation (HBI), as follows: 2.5 Gy TBI (n = 2), 5 Gy TBI (n = 2), 5 Gy HBI (n = 2), and 10 Gy HBI (n = 2). Midline tissue doses were measured at the anterior iliac crest level with an ionization chamber, and body dosimetry was performed using thermoluminescent dosimeters. Blood samples were collected before exposure and from 1 h until 200 d after irradiation. Clinical status, complete blood cell count, biochemical parameters, and cytogenetic analysis were evaluated. The partial least square discriminant analysis chosen for statistical analysis showed that the four groups of irradiated baboons were clearly separated. However, the dicentric chromosome assay may not distinguish HBI from TBI in confounding situations where equivalent whole-body doses are similar and the time of exposure is sufficient for peripheral blood lymphocyte homogenization. Interestingly, as bone marrow shielding in HBI animals prevented aplasia from happening, hematologic parameters such as the platelet count and Flt-3 ligand level helped to distinguish HBI and TBI. Moreover, the ratio of neutrophil to lymphocyte counts, creatine kinase, and citrulline levels may be discriminating biomarkers of dose or injury. Both early and delayed clinical signs and bioindicators appear to be useful for assessment of heterogeneous irradiation.

  5. 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.

  6. Dependence of the kinetic and thermodynamic parameters on hydrophilic-lipophilic character of alprazolam, clonazepam, diazepam, doxepin and haloperidol in alkaline environment.

    PubMed

    Maślanka, Anna; Krzek, Jan; Szlósarczyk, Marek; Żmudzki, Paweł; Wach, Katarzyna

    2013-10-15

    Examination of the stability of clonazepam, diazepam, alprazolam, haloperidol, and doxepin in basic solutions was performed, together with an assessment of the kinetic (k, t0.1i t0.5) and thermodynamic (Ea, ΔH(++)i ΔS(++)) stability-indicating parameters, which were compared with the lipophilicity (logP) of the studied drugs. It was observed that the calculated values of Ea, ΔH(++) and ΔS(++) for the studied drugs increased from 41.04 kJ/mol to 125.50 kJ/mol, from 37.82 kJ/mol to 122.24 kJ/mol and from -167.09 J/Kmol to 53.02 J/Kmol, respectively, along with an increase of lipophilicity (logP) from 2.12 to 4.30 for the most hydrophilic alprazolam to the most lipophilic haloperidol. The degradation products were identified using UPLC/MS/MS method.

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

    SciTech Connect

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

    1999-12-05

    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 naphthalene 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.

  8. Subcritical hydrothermal liquefaction of cattle manure to bio-oil: Effects of conversion parameters on bio-oil yield and characterization of bio-oil.

    PubMed

    Yin, Sudong; Dolan, Ryan; Harris, Matt; Tan, Zhongchao

    2010-05-01

    In this study, cattle manure was converted to bio-oil by subcritical hydrothermal liquefaction in the presence of NaOH. The effects of conversion temperature, process gas, initial conversion pressure, residence time and mass ratio of cattle manure to water on the bio-oil yield were studied. The bio-oil was characterized in terms of elemental composition, higher heating value, ultraviolet-visible (UV/Vis) spectroscopy, Fourier transform infrared spectroscopy (FTIR), gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Results showed that the bio-oil yield depended on the conversion temperature and the process gas. Higher initial conversion pressure, longer residence time and larger mass ratio of cattle manure to water, however, had negative impacts on the bio-oil yield. The higher heating value of bio-oil was 35.53MJ/kg on average. The major non-polar components of bio-oil were toluene, ethyl benzene and xylene, which are components of crude oil, gasoline and diesel.

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

    SciTech Connect

    Geslot, Benoit; Pepino, Alexandra; Blaise, Patrick; Mellier, Frederic; Kochetkov, Anatoly; Vittiglio, Guido; Billebaud, Annick

    2015-07-01

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

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

    SciTech Connect

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

    2013-03-01

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

  11. Biohydrogen production based on the evaluation of kinetic parameters of a mixed microbial culture using glucose and fruit-vegetable waste as feedstocks.

    PubMed

    Garcia-Peña, E I; Canul-Chan, M; Chairez, I; Salgado-Manjarez, E; Aranda-Barradas, J

    2013-09-01

    Hydrogen (H2) production from the organic fraction of solid waste such as fruit and vegetable waste (FVW) is a novel and feasible energy technology. Continuous application of this process would allow for the simultaneous treatment of organic residues and energy production. In this study, batch experiments were conducted using glucose as substrate, and data of H2 production obtained were successfully adjusted by a logistic model. The kinetic parameters (μ max = 0.101 h(-1), K s = 2.56 g/L) of an H2-producing microbial culture determined by the Monod and Haldane-Andrews growth models were used to establish the continuous culture conditions. This strategy led to a productive steady state in continuous culture. Once the steady state was reached in the continuous reactor, a maximum H2 production of 700 mL was attained. The feasibility of producing H2 from the FVW obtained from a local market in Mexico City was also evaluated using batch conditions. The effect of the initial FVW concentration on the H2 production and waste organic material degradation was determined. The highest H2 production rate (1.7 mmol/day), the highest cumulative H2 volume (310 mL), and 25 % chemical oxygen demand (COD) removal were obtained with an initial substrate (FVW) concentration of 37 g COD/L. The lowest H2 production rates were obtained with relatively low initial substrate concentrations of 5 and 11 g COD/L. The H2 production rates with FVW were also characterized by the logistic model. Similar cumulative H2 production was obtained when glucose and FVW were used as substrates.

  12. Biosorption of Cr(VI) by Ceratocystis paradoxa MSR2 Using Isotherm Modelling, Kinetic Study and Optimization of Batch Parameters Using Response Surface Methodology

    PubMed Central

    Ramalingam, Chidambaram

    2015-01-01

    This study is focused on the possible use of Ceratocystis paradoxa MSR2 native biomass for Cr(VI) biosorption. The influence of experimental parameters such as initial pH, temperature, biomass dosage, initial Cr(VI) concentration and contact time were optimized using batch systems as well as response surface methodology (RSM). Maximum Cr(VI) removal of 68.72% was achieved, at an optimal condition of biomass dosage 2g L−1, initial Cr(VI) concentration of 62.5 mg L−1 and contact time of 60 min. The closeness of the experimental and the predicted values exhibit the success of RSM. The biosorption mechanism of MSR2 biosorbent was well described by Langmuir isotherm and a pseudo second order kinetic model, with a high regression coefficient. The thermodynamic study also revealed the spontaneity and exothermic nature of the process. The surface characterization using FT-IR analysis revealed the involvement of amine, carbonyl and carboxyl groups in the biosorption process. Additionally, desorption efficiency of 92% was found with 0.1 M HNO3. The Cr(VI) removal efficiency, increased with increase in metal ion concentration, biomass concentration, temperature but with a decrease in pH. The size of the MSR2 biosorbent material was found to be 80 μm using particle size analyzer. Atomic force microscopy (AFM) visualizes the distribution of Cr(VI) on the biosorbent binding sites with alterations in the MSR2 surface structure. The SEM-EDAX analysis was also used to evaluate the binding characteristics of MSR2 strain with Cr(VI) metals. The mechanism of Cr(VI) removal of MSR2 biomass has also been proposed. PMID:25822726

  13. Interference effect in the dipole and nondipole anisotropy parameters of the Kr 4p photoelectrons in the vicinity of the Kr (3d){sup -1{yields}}np resonant excitations

    SciTech Connect

    Ricz, S.; Ricsoka, T.; Holste, K.; Borovik, A. Jr.; Bernhardt, D.; Schippers, S.; Mueller, A.; Koever, A.; Varga, D.

    2010-04-15

    The angular distribution of the Kr 4p photoelectrons was investigated in the photon energy range of the (3d){sup -1{yields}}np resonant excitations. The experimental dipole ({beta}) and nondipole ({gamma} and {delta}) anisotropy parameters were determined for the spin-orbit components of the Kr 4p shell. A simple theoretical model was developed for the description of the photoionization and excitation processes. An interference effect was observed between the direct photoionization and the resonant excitation participator Auger decay processes in the photon energy dependence of the experimental anisotropy parameters.

  14. Sediment Loads and Yield, and Selected Water-Quality Parameters in Clear Creek, Carson City and Douglas County, Nevada, Water Years 2004-07

    USGS Publications Warehouse

    Seiler, Ralph L.; Wood, James L.

    2009-01-01

    Some reaches of Clear Creek above U.S. Highway 395 have experienced severe erosion as a result of fires, extreme precipitation events, and past and current human activities in the basin. Previous evaluations of erosion in the basin have concluded that most of the sediment produced and transported in the basin was associated with U.S. Highway 50, a four-lane highway that roughly parallels Clear Creek through much of the basin. During this study (water years 2004-07), construction of roads and a large residential area and golf course in the area began and are likely to affect water quality and sediment transport in the basin. Sediment data were collected between October 2003 and September 2007 (water years 2004-07) from three sites along Clear Creek. Annual suspended-sediment load was estimated to range from 1,456 tons in water year 2006 to only 100 tons in water year 2004, which corresponds to suspended-sediment yields of 93.9 tons per square mile per year in 2006 to 6.4 tons per square mile per year in 2004. In water year 2006, the suspended-sediment load on December 31, 2005, alone exceeded the combined annual load for water years 2004, 2005, and 2007. Bedload sediment was estimated to comprise 73 percent of total sediment load in the creek. Mean annual suspended-sediment yield in Clear Creek basin was much greater than yields in the Logan House, Edgewood, and Glenbrook Creek basins in the adjacent Lake Tahoe basin. Comparison of data collected during this study with data collected by university researchers in the 1970s is inconclusive as to whether fundamental changes in basin sediment characteristics have occurred during the 30-year period because different methods and sampling locations were used in the earlier studies.

  15. Use of Nonspecific, Glutamic Acid-Free, Media and High Glycerol or High Amylase as Inducing Parameters for Screening Bacillus Isolates Having High Yield of Polyglutamic Acid.

    PubMed

    Baxi, Nandita N

    2014-01-01

    Out of fifty-five Bacillus isolates obtained from ten different regional locations and sources, seven showed the ability to consistently produce specific extracellular polymeric substance (EPS) on rich as well as synthetic but nonspecific media which did not contain glutamic acid. The isolates were identified as either Bacillus licheniformis or Bacillus subtilis. The EPS from all isolates was resistant to alpha protease, proteinase K, and was thus of high molecular weight. Further it was detected after SDS-PAGE by methylene blue but not by coomassie blue R staining as in case of proteins with high proportion of acidic amino acids. Cell-free EPS, after acid hydrolysis, showed absence of carbohydrates and presence of only glutamic acid. Thus the native the EPS from all seven isolates was confirmed to be gamma polyglutamic acid (PGA) and not exopolysaccharide. The Bacillus isolate T which produced maximum polymer on all media tested had higher amylase: protease activity as compared to other strains. If inoculum was developed in rich medium as compared to synthetic medium, the PGA produced increased by twofold in the subsequent synthetic production medium. Similarly, use of inoculum consisting of young and vegetative cells also increased the PGA production by twofold though amount of inoculum did not affect yield of PGA. Though PGA was produced in even in the absence of glutamic acid supplementation in the production medium by all isolates, the yield of PGA increased by fourfold in the presence glutamic acid and the maximum yield was 30 g/l for isolate K. The supplementation of glutamine instead of glutamic acid into the medium caused an increase in the viscosity of the non-Newtonian solution of PGA.

  16. Kinetic investigation of wood pyrolysis

    SciTech Connect

    Thurner, F.; Mann, U.; Beck, S. R.

    1980-06-01

    The objective of this investigation was to determine the kinetics of the primary reactions of wood pyrolysis. A new experimental method was developed which enabled us to measure the rate of gas, tar, and char production while taking into account the temperature variations during the wood heating up. The experimental method developed did not require any sophisticated instruments. It facilitated the collection of gas, tar and residue (unreacted wood and char) as well as accurate measurement of the temperature inside the wood sample. Expressions relating the kinetic parameters to the measured variables were derived. The pyrolysis kinetics was investigated in the range of 300 to 400/sup 0/C at atmospheric pressure and under nitrogen atmosphere. Reaction temperature and mass fractions of gas, tar, and residue were measured as a function of time. Assuming first-order reactions, the kinetic parameters were determined using differential method. The measured activation energies of wood pyrolysis to gas, tar, and char were 88.6, 112.7, and 106.5 kJ/mole, respectively. These kinetic data were then used to predict the yield of the various pyrolysis products. It was found that the best prediction was obtained when an integral-mean temperature obtained from the temperature-time curve was used as reaction temperature. The pyrolysis products were analyzed to investigate the influence of the pyrolysis conditions on the composition. The gas consisted mainly of carbon dioxide, carbon monoxide, oxygen, and C/sub 3//sup +/-compounds. The gas composition depended on reaction time as well as reactor temperature. The tar analysis indicated that the tar consisted of about seven compounds. Its major compound was believed to be levoglucosan. Elemental analysis for the char showed that the carbon content increased with increasing temperature.

  17. Bayesian inference of genetic parameters for test-day milk yield, milk quality traits, and somatic cell score in Burlina cows.

    PubMed

    Penasa, M; Cecchinato, A; Battagin, M; De Marchi, M; Pretto, D; Cassandro, M

    2010-01-01

    The aim of the study was to infer (co)variance components for daily milk yield, fat and protein contents, and somatic cell score (SCS) in Burlina cattle (a local breed in northeast Italy). Data consisted of 13,576 monthly test-day records of 666 cows (parities 1 to 8) collected in 10 herds between 1999 and 2009. Repeatability animal models were implemented using Bayesian methods. Flat priors were assumed for systematic effects of herd test date, days in milk, and parity, as well as for permanent environmental, genetic, and residual effects. On average, Burlina cows produced 17.0 kg of milk per day, with 3.66 and 3.33 percent of fat and protein, respectively, and 358,000 cells per mL of milk. Marginal posterior medians (highest posterior density of 95%) of heritability were 0.18 (0.09-0.28), 0.28 (0.21-0.36), 0.35 (0.25-0.49), and 0.05 (0.01-0.11) for milk yield, fat content, protein content, and SCS, respectively. Marginal posterior medians of genetic correlations between the traits were low and a 95 percent Bayesian confidence region included zero, with the exception of the genetic correlation between fat and protein contents. Despite the low number of animals in the population, results suggest that genetic variance for production and quality traits exists in Burlina cattle.

  18. A study of the spray injection Reynolds number effects on gasoline yields of an FCC riser reactor

    SciTech Connect

    Bowman, B. J.; Zhou, C. Q.; Chang, S. L.; Lottes, S. A.

    2000-04-03

    A computational analysis of the combined effects of feed oil injection parameters in a commercial-scale fluidized catalytic cracking riser reactor was performed using a three-phase, multiple species kinetic cracking computer code. The analysis showed that the injection operating parameters (droplet diameter and injection velocity) had strong impacts on the gasoline yields of the FCC unit. A spray injection Reynolds number combining the two parameters was defined. A correlation between the spray injection Reynolds number and the gasoline product yields for various feed injection conditions was developed. A range of spray injection Reynolds number for the maximum gasoline yield was identified.

  19. New kinetic parameters for rat liver arginase measured at near-physiological steady-state concentrations of arginine and Mn2+.

    PubMed Central

    Maggini, S; Stoecklin-Tschan, F B; Mörikofer-Zwez, S; Walter, P

    1992-01-01

    A cytosolic cell-free system from rat liver containing the last three enzymes of the urea cycle, a number of cofactors and the substrates aspartate and citrulline was shown to synthesize urea at near-physiological rates ranging between 0.40 and 1.25 mumol/min per g of liver. This system was used to determine the kinetic parameters for arginase. With saturating amounts of Mn2+ (30 microM), arginine remained at a steady-state concentration of 5-35 microM depending on the aspartate and citrulline supply. Vmax. at micromolar arginine concentrations was between 1.10 and 1.25 mumol/min per g of liver, the K0.5 (arginine) between 6.0 and 6.5 microM and positive co-operativity was observed (Hill coefficient 2). Omission of Mn2+ caused a significant accumulation of arginine during the incubation, suggesting a regulatory effect of arginase. Under these conditions, Vmax. was 1.10-1.65 mumol/min per g of liver and the Km (arginine) increased up to 14.4-21.1 microM. The apparent Ka for Mn2+ in the presence of physiological concentrations of ATP, Mg2+ and arginine was calculated to be maximally 8 microM. Initial-velocity experiments with millimolar arginine concentrations as the direct substrate gave the following results, which are in good agreement with literature data. In the absence of Mn2+, Vmax. was 71.3 mumol/min per g of liver and the Km (arginine) 1.58 mM. With 30 microM-Mn2+, Vmax. was 69.4 mumol/min per g of liver and the Km (arginine) decreased to 0.94 mM. On the basis of our results, we propose the presence of high-affinity and low-affinity sites for arginine on rat liver arginase and postulate that alterations in arginase activity arising from changes in the concentration of arginine and of the cofactor Mn2+ may contribute to the regulation of ureagenesis in vivo. PMID:1590754

  20. Sensitivity of kinetic macro parameters to changes in dopamine synthesis, storage, and metabolism: a simulation study for [¹⁸F]FDOPA PET by a model with detailed dopamine pathway.

    PubMed

    Matsubara, Keisuke; Watabe, Hiroshi; Kumakura, Yoshitaka; Hayashi, Takuya; Endres, Christopher J; Minato, Kotaro; Iida, Hidehiro

    2011-08-01

    Quantitative interpretation of brain [¹⁸F]FDOPA PET data has been made possible by several kinetic modeling approaches, which are based on different assumptions about complex [¹⁸F]FDOPA metabolic pathways in brain tissue. Simple kinetic macro parameters are often utilized to quantitatively evaluate metabolic and physiological processes of interest, which may include DDC activity, vesicular storage, and catabolism from (18) F-labeled dopamine to DOPAC and HVA. A macro parameter most sensitive to the changes of these processes would be potentially beneficial to identify impaired processes in a neurodegenerative disorder such as Parkinson's disease. The purpose of this study is a systematic comparison of several [¹⁸F]FDOPA macro parameters in terms of sensitivities to process-specific changes in simulated time-activity curve (TAC) data of [¹⁸F]FDOPA PET. We introduced a multiple-compartment kinetic model to simulate PET TACs with physiological changes in the dopamine pathway. TACs in the alteration of dopamine synthesis, storage, and metabolism were simulated with a plasma input function obtained by a non-human primate [¹⁸F]FDOPA PET study. Kinetic macro parameters were calculated using three conventional linear approaches (Gjedde-Patlak, Logan, and Kumakura methods). For simulated changes in dopamine storage and metabolism, the slow clearance rate (k(loss) ) as calculated by the Kumakura method showed the highest sensitivity to these changes. Although k(loss) performed well at typical ROI noise levels, there was large bias at high noise level. In contrast, for simulated changes in DDC activity it was found that K(i) and V(T), estimated by Gjedde-Patlak and Logan method respectively, have better performance than k(loss).

  1. Kinetics of ethanol production from sugarcane bagasse enzymatic hydrolysate concentrated with molasses under cell recycle.

    PubMed

    de Andrade, Rafael Ramos; Maugeri Filho, Francisco; Maciel Filho, Rubens; da Costa, Aline Carvalho

    2013-02-01

    In this work, a kinetic model for ethanol fermentation from sugarcane bagasse enzymatic hydrolysate concentrated with molasses was developed. A model previously developed for fermentation of pure molasses was modified by the inclusion of a new term for acetic acid inhibition on microorganism growth rate and the kinetic parameters were estimated as functions of temperature. The influence of the hydrolysate on the kinetic parameters is analyzed by comparing with the parameters from fermentation of pure molasses. The impact of cells recycling in the kinetic parameters is also evaluated, as well as on the ethanol yield and productivity. The model developed described accurately most of the fermentations performed in several successive batches for temperatures from 30 to 38°C.

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

    NASA Astrophysics Data System (ADS)

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

    1990-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  4. HCl yield and chemical kinetics study of the reaction of Cl atoms with CH3I at the 298K temperature using the infra-red tunable diode laser absorption spectroscopy.

    PubMed

    Sharma, R C; Blitz, M; Wada, R; Seakins, P W

    2014-07-15

    Pulsed ArF excimer laser (193 nm)-CW infrared (IR) tunable diode laser Herriott type absorption spectroscopic technique has been made for the detection of product hydrochloric acid HCl. Absorption spectroscopic technique is used in the reaction chlorine atoms with methyl iodide (Cl+CH3I) to the study of kinetics on reaction Cl+CH3I and the yield of (HCl). The reaction of Cl+CH3I has been studied with the support of the reaction Cl+C4H10 (100% HCl) at temperature 298 K. In the reaction Cl+CH3I, the total pressure of He between 20 and 125 Torr at the constant concentration of [CH3I] 7.0×10(14) molecule cm(-3). In the present work, we estimated adduct formation is very important in the reaction Cl+CH3I and reversible processes as well and CH3I molecule photo-dissociated in the methyl [CH3] radical. The secondary chemistry has been studied as CH3+CH3ICl = product, and CH3I+CH3ICl = product2. The system has been modeled theoretically for secondary chemistry in the present work. The calculated and experimentally HCl yield nearly 65% at the concentration 1.00×10(14) molecule cm(-3) of [CH3I] and 24% at the concentration 4.0×10(15) molecule cm(-3) of [CH3I], at constant concentration 4.85×10(12) molecule cm(-3) of [CH3], and at 7.3×10(12) molecule cm(-3) of [Cl]. The pressure dependent also studied product of HCl at the constant [CH3], [Cl] and [CH3I]. The experimental results are also very good matching with the modelling work at the reaction CH3+CH3ICl = product (k = (2.75±0.35)×10(-10) s(-1)) and CH3I+CH3ICl = product2 (k = 1.90±0.15)×10(-12) s(-1). The rate coefficients of the reaction CH3+CH3ICl and CH3I+CH3ICl has been made in the present work. The experimental results has been studied by two method (1) phase locked and (2) burst mode.

  5. DIRECT COMPARISON OF KINETIC AND LOCAL EQUILIBRIUM FORMULATIONS FOR SOLUTE TRANSPORT AFFECTED BY SURFACE REACTIONS.

    USGS Publications Warehouse

    Bahr, Jean M.; Rubin, Jacob

    1987-01-01

    Modeling transport of reacting solutes in porous media often requires a choice between models based on the local equilibrium assumption (LEA) and models involving reaction kinetics. Direct comparison of the mathematical formulations for these two types of transport models can aid in this choice. For cases of transport affected by surface reaction, such a comparison is made possible by a new derivation procedure. This procedure yields a kinetics-based formulation that is the sum of the LEA formulation and one or more kinetically influenced terms. The dimensionless form of the new kinetics-based formulation facilitates identification of critical parameter groupings which control the approach to transport behavior consistent with LEA model predictions. Results of numerical experiments demonstrate that criteria for LEA applicability can be expressed conveniently in terms of these parameter groupings. The derivation procedure is demonstrated for examples of surface reactions including first-order reversible sorption, Langmuir-type kinetics and binary, homovalent ion exchange.

  6. Kinetic analysis of HO{sub 2} addition to ethylene, propene, and isobutene, and thermochemical parameters of alkyl hydroperoxides and hydroperoxide alkyl radicals

    SciTech Connect

    Chen, C.J.; Bozzelli, J.W.

    2000-06-01

    Thermochemical kinetic analysis for the reactions of HO{sub 2} radical addition to the primary, secondary, and tertiary carbon-carbon double bonds of ethylene, propene, and isobutene are studied using canonical transition state theory (TST). Thermochemical properties of reactants, alkyl hydroperoxides (ROOH), hydroperoxy alkyl radicals (R-OOH), and transition states (TSs) are determined by ab initio and density functional calculations. Enthalpies of formation ({Delta}H{sub f 298}{degree}) of product radicals (R-OOH) are determined using isodesmic reactions with group balance at MP4(full)6-31G(d,p)/MP2(full)/6-31G(d), MP2(full)/6-31G(d), complete basis set model chemistry (CBS-q with MP2(full)/6-31g(d) and B3LYP/6-31g(d) optimized geometries), and density functional (B3LYP/6-31g(d) and B3LYP/6-311+g(3df,2p)//B3LYP/6-31g(d)) calculations. {Delta}H{sub f 298}{degree} of TSs are obtained from the {Delta}H{sub f 298}{degree} of reactants plus energy differences between reactants and TSs. Entropies (S{sub 298}{degree}) and heat capacities (Cp(T) 300 {le} T/K {le} 1,500) contributions from vibrational, translational, and external rotational are calculated using the rigid-rotor-harmonic-oscillator approximation based on geometric parameters and vibrational frequencies obtained at MP2(full)/6-31G(d) and B3LYP/6-31G(d) levels of theory. Selected potential barriers of internal rotations for hydroperoxy alkyl radicals and TSs are calculated at MP2(full)/6-31G(d) and CBS-Q//MP2(full)/6-31G(d) levels. Contributions from hindered rotors of S{sub 298}{degree} and Cp(T) are calculated by the method of Pitzer and Gwinn and by summation over the energy levels obtained by direct diagonalization of the Hamiltonian matrix of hindered internal rotations when the potential barriers of internal rotations are available. calculated rate constants obtained at CBS-q/MP2(full)/6-31G(d) and CBS-q//B3LYP/6-31G(d) levels of theory show similar trends with experimental data: HO{sub 2} radical

  7. Site-specific experiments on folding/unfolding of Jun coiled coils: thermodynamic and kinetic parameters from spin inversion transfer nuclear magnetic resonance at leucine-18.

    PubMed

    d'Avignon, D André; Bretthorst, G Larry; Holtzer, Marilyn Emerson; Schwarz, Kathleen A; Angeletti, Ruth Hogue; Mints, Lisa; Holtzer, Alfred

    2006-10-15

    The 32-residue leucine zipper subsequence, called here Jun-lz, associates in benign media to form a parallel two-stranded coiled coil. Studies are reported of its thermal unfolding/folding transition by circular dichroism (CD) on samples of natural isotopic abundance and by both equilibrium and spin inversion transfer (SIT) nuclear magnetic resonance (NMR) on samples labeled at the leucine-18 alpha-carbon with 99% 13C. The data cover a wide range of temperature and concentration, and show that Jun-lz unfolds below room temperature, being far less stable than some other leucine zippers such as GCN4. 13C-NMR shows two well-separated resonances. We ascribe the upfield one to 13C spins on unfolded single chains and the downfield one to 13C spins on coiled-coil dimers. Their relative intensities provide a measure of the unfolding equilibrium constant. In SIT NMR, the recovery of the equilibrium magnetization after one resonance is inverted is modulated in part by the unfolding and folding rate constants, which are accessible from the data. Global Bayesian analysis of the equilibrium and SIT NMR data provide values for the standard enthalpy, entropy, and heat capacity of unfolding, and show the latter to be unusually large. The CD results are compatible with the NMR findings. Global Bayesian analysis of the SIT NMR data yields the corresponding activation parameters for unfolding and folding. The results show that both reaction directions are activated processes. Activation for unfolding is entropy driven, enthalpy opposed. Activation for folding is strongly enthalpy opposed and somewhat entropy opposed, falsifying the idea that the barrier for folding is solely due to a purely entropic search for properly registered partners. The activation heat capacity is much larger for folding, so almost the entire overall change is due to the folding direction. This latter finding, if it applies to GCN4 leucine zippers, clears up an extant apparent disagreement between folding rate

  8. Comparative studies of glow peaks and kinetic trapping parameters of LiF(Mg,Cu), LiF(Mg,Cu,P), LiF(Mg,Cu,Si) and LiF(Mg,Cu,Na,Si) single crystals

    NASA Astrophysics Data System (ADS)

    Laopaiboon, R.; Bootjomchai, C.; Pencharee, S.; Laopaiboon, J.

    2014-02-01

    Glow curve structure and kinetic trapping parameter of the thermoluminescent (TL) phosphors based on LiF(Mg,Cu) LiF(Mg,Cu,P) LiF(Mg,Cu,Si) and LiF(Mg,Cu,Na,Si) single crystals were investigated (denoted as SMC, SMCP, SMCS and SMCNS, respectively). Wet mixing and drying before TL phosphors production in single-crystal form were achieved by the Bridgeman method. The transparent solid single crystals were cut to the size of 5.0×5.0×0.6 mm3 for use as thermoluminescence dosimeters (TLD). Four different types of TLD were irradiated with X-ray photon energy 128 keV in the dose of 3 mGy after dual step pre-irradiation annealing. From the glow curve structure, the geometrical factors (μ) were calculated. The graph created by Chen confirms the first-order kinetics. Moreover, the glow curve shape results in more fading of the TLD 100 sample than the SMCS and SMCNS samples. It is evident that the kinetic trapping parameters depend on the type of dopant. The frequency factors of all TLD single crystals are higher than TLD100 (poly-crystal). These results are useful to provide the TL trapping and recombination centers for these materials.

  9. Erbium hydride thermal desorption : controlling kinetics.

    SciTech Connect

    Ferrizz, Robert Matthew

    2007-08-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report show that hydride film processing parameters directly impact thermal stability. Issues to be addressed include desorption kinetics for dihydrides and trihydrides, and the effect of film growth parameters, loading parameters, and substrate selection on desorption kinetics.

  10. Pyromat II micropyrolysis of source rocks and oil shales: Effects of native content and sample size on T sub max values and kinetic parameters

    SciTech Connect

    Reynolds, J.G.; Murray, A.

    1991-01-01

    The Pyromat 2 micropyrolyzer can routinely measure kinetics on standard shales and source rocks. However, when examining samples which have high native bitumen contents, samples with high TOC and native bitumen contents, asphaltenes, tar sands, and other non-kerogen type materials, the pyrolysis profiles sometimes deviate from normal expected behavior. Some of the deviant features are: (1) evolution before the maximum assigned to kerogen breakdown, (2) broadening of the maximum assigned to kerogen breakdown and shifting in T{sub max} with increasing sample size, and (3) artifacts in activation energy distributions derived in kinetic analyses. This report examines these features in more detail and offers potential experimental solutions to circumvent problems created by these features. 9 refs., 9 figs., 5 tabs.

  11. Temperature-Dependent Kinetics Studies of the Reactions Br((sup 2)P3/2) + H2S yields SH + HBr and Br((sup 2)P3/2) + CH3SH yields CH3S + HBr. Heats of Formation of SH and CH3S Radicals

    NASA Technical Reports Server (NTRS)

    Nicovich, J. M.; Kreutter, K. D.; vanDijk, C. A.; Wine, P. H.

    1997-01-01

    Time resolved resonance fluorescence detection of Br(sup 2)P3/2) atom disappearance or appearance following 266-nm laser flash photolysis of CF2Br2/H2S/H2/N2, CF2Br2/CH3SH/H2/N2, Cl2CO/H2S/HBr/N2, and CH3SSCH3/HBr/H2/N2 mixtures has been employed to study the kinetics of the reactions Br((sup 2)P3/2) + H2S = SH + HBr (1,-1) and Br((sup2)P3/2) + CH3SH = CH3S + HBr (2, -2) as a function of temperature over the range 273-431K. Arrhenius expressions in units of 10(exp -12) cu cm/molecule/s which describe the results are k1 = (14.2 +/- 3.4) exp[(-2752 +/- 90)/T],(k-1) = (4.40 +/- 0.92) exp[(-971 +/- 73)/T],k(2) = (9.24 +/- 1.15) exp[(-386 +/- 41)/T], and k(-2) = (1.46 +/-0.21) exp[(-399 +/-41)/T; errors are 2 sigma and represent precision only. By examining Br((sup 2)P3/2) equilibrium kinetics following 355nm laser flash photolysis of Br2/CH3SH/H2/N2 mixtures, a 298 K rate coefficient of (1.7 +/- 0.5) x 10(exp -10) cu cm/molecule/s has been obtained for the reaction CH3S + Br2 yields CH3SBr + Br. To our knowledge, these are the first kinetic data reported for each of the reactions studied. Measured rate coefficients, along with known rate coefficients for similar radical + H2S, CH3SH, HBr,Br2 reactions are considered in terms of possible correlations of reactivity with reaction thermochemistry and with IP - EA, the difference between the ionization potential of the electron donor and the electron affinity of the electron acceptor. Both thermochemical and charge-transfer effects appear to be important in controlling observed reactivities. Second and third law analyses of the equilibrium data for reactions 1 and 2 have been employed to obtain the following enthalpies of reaction in units of kcal/mol: for reaction 1, Delta-H(298) = 3.64 +/- 0.43 and Delta-H(0) = 3.26 +/-0.45; for reaction 2, Delta-H(298) = -0.14 +/- 0.28 and Delta-H(0) = -0.65 +/- 0.36. Combining the above enthalpies of reaction with the well-known heats of formation of Br, HBr, H2S, and CH3SH gives the

  12. Determination on Monod kinetic coefficients for volatile hydrophobic organic compounds

    SciTech Connect

    Guha, S.; Jaffe, P.R.

    1996-06-20

    A new procedure is presented to determine Monod kinetic coefficients and the microbial yield coefficient for volatile hydrophobic compounds such as phenanthrene. Batch experiments were conducted with a mixed culture capable of degrading phenanthrene. The phenanthrene disappearance and carbon dioxide production were monitored with time. A maximum likelihood estimator was formulated to fit the set of equations that describe the system to the measured data. The model takes into account a number of processes such as partition onto the apparatus, volatilization, and partition onto the biomass. The parameters required to describe these processes were obtained by independent experiments. The yield coefficient could be determined within a small range. However, the specific growth rate and the half-saturation constant were found to vary widely, with pairs of them describing the system adequately. It was shown that partition and volatilization processes can significantly affect the determination of the yield and Monod kinetic coefficients and need to be taken into account.

  13. Genetic parameters of cheese yield and curd nutrient recovery or whey loss traits predicted using Fourier-transform infrared spectroscopy of samples collected during milk recording on Holstein, Brown Swiss, and Simmental dairy cows.

    PubMed

    Cecchinato, A; Albera, A; Cipolat-Gotet, C; Ferragina, A; Bittante, G

    2015-07-01

    Cheese yield is the most important technological parameter in the dairy industry in many countries. The aim of this study was to infer (co)variance components for cheese yields (CY) and nutrient recoveries in curd (REC) predicted using Fourier-transform infrared (FTIR) spectroscopy of samples collected during milk recording on Holstein, Brown Swiss, and Simmental dairy cows. A total of 311,354 FTIR spectra representing the test-day records of 29,208 dairy cows (Holstein, Brown Swiss, and Simmental) from 654 herds, collected over a 3-yr period, were available for the study. The traits of interest for each cow consisted of 3 cheese yield traits (%CY: fresh curd, curd total solids, and curd water as a percent of the weight of the processed milk), 4 curd nutrient recovery traits (REC: fat, protein, total solids, and the energy of the curd as a percent of the same nutrient in the processed milk), and 3 daily cheese production traits (daily fresh curd, total solids, and the water of the curd per cow). Calibration equations (freely available upon request to the corresponding author) were used to predict individual test-day observations for these traits. The (co)variance components were estimated for the CY, REC, milk production, and milk composition traits via a set of 4-trait analyses within each breed. All analyses were performed using REML and linear animal models. The heritabilities of the %CY were always higher for Holstein and Brown Swiss cows (0.22 to 0.33) compared with Simmental cows (0.14 to 0.18). In general, the fresh cheese yield (%CYCURD) showed genetic variation and heritability estimates that were slightly higher than those of its components, %CYSOLIDS and %CYWATER. The parameter RECPROTEIN was the most heritable trait in all the 3 breeds, with values ranging from 0.32 to 0.41. Our estimation of the genetic relationships of the CY and REC with milk production and composition revealed that the current selection strategies used in dairy cattle are expected

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

    PubMed

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

    2016-02-01

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

  15. Influence of synthesis parameters on the growth of CdS nanoparticles in colloidal solution and determination of growth kinetics using Karhunen Loeve decomposition

    NASA Astrophysics Data System (ADS)

    Barglik-Chory, Ch.; Münster, A. F.; Strohm, H.; Remenyi, Ch.; Müller, G.

    2003-06-01

    The growth of CdS nanoparticles during aging at ambient temperature is investigated with respect to the type of stabilizer, the concentration of the colloidal solution, and the molar ratio of sulfide to cadmium. The UV/Vis absorption spectra recorded within a period of seven days are analyzed by Karhunen-Loeve decomposition. It revealed a single process with first-order decomposition kinetics for each of the measured time series, and the respective rate constants are calculated. An explanation describing possible mechanisms for the observed ripening of the colloids is given.

  16. An analytical model of nonproportional scintillator light yield in terms of recombination rates

    SciTech Connect

    Bizarri, G.; Moses, W. W.; Singh, J.; Vasil'ev, A. N.; Williams, R. T.

    2009-02-15

    Analytical expressions for the local light yield as a function of the local deposited energy (-dE/dx) and total scintillation yield integrated over the track of an electron of initial energy E are derived from radiative and/or nonradiative rates of first through third order in density of electronic excitations. The model is formulated in terms of rate constants, some of which can be determined independently from time-resolved spectroscopy and others estimated from measured light yield efficiency as a constraint assumed to apply in each kinetic order. The rates and parameters are used in the theory to calculate scintillation yield versus primary electron energy for comparison to published experimental results on four scintillators. Influence of the track radius on the yield is also discussed. Results are found to be qualitatively consistent with the observed scintillation light yield. The theory can be applied to any scintillator if the rates of the radiative and nonradiative processes are known.

  17. Kinetics of the biodegradation of green table olive wastewaters by aerobic and anaerobic treatments.

    PubMed

    Beltran, J; Gonzalez, T; Garcia, J

    2008-06-15

    The biodegradation of the organic pollutant matter present in green table olive wastewater (GTOW) is studied in batch reactors by an aerobic biodegradation and by an anaerobic digestion. In the aerobic biodegradation, the evolution of the substrate (in terms of chemical and biochemical oxygen demand), biomass, and total polyphenolic compounds present in the wastewater are followed during the process, and a kinetic study is performed using Contois' model, which when applied to the experimental results provides the kinetic parameter of this model, resulting in a modified Contois' equation (q=3.3S/(0.31S(0)X+X), gCOD/gVSS d(-1)). Other kinetic parameters were determined: the cellular yield coefficient (YX/S=5.7x10(-2) gVSS/gCOD) and the kinetic constant of cellular death phase (kd=0.16 d(-1)). Similarly, in the anaerobic digestion, the evolution of the substrate digested and the methane produced are followed, and the kinetic study is conducted using a modified Monod model combined with the Levenspiel model, due to the presence of inhibition effects. This model leads to the determination of the kinetic parameters: kinetic constant when no inhibitory substance is present (kM0=8.4x10(-2) h(-1)), critical substrate concentration of inhibition (TP*=0.34 g/L) and inhibitory parameter (n=2.25).

  18. Comparison between genetic parameters of cheese yield and nutrient recovery or whey loss traits measured from individual model cheese-making methods or predicted from unprocessed bovine milk samples using Fourier-transform infrared spectroscopy.

    PubMed

    Bittante, G; Ferragina, A; Cipolat-Gotet, C; Cecchinato, A

    2014-10-01

    Cheese yield is an important technological trait in the dairy industry. The aim of this study was to infer the genetic parameters of some cheese yield-related traits predicted using Fourier-transform infrared (FTIR) spectral analysis and compare the results with those obtained using an individual model cheese-producing procedure. A total of 1,264 model cheeses were produced using 1,500-mL milk samples collected from individual Brown Swiss cows, and individual measurements were taken for 10 traits: 3 cheese yield traits (fresh curd, curd total solids, and curd water as a percent of the weight of the processed milk), 4 milk nutrient recovery traits (fat, protein, total solids, and energy of the curd as a percent of the same nutrient in the processed milk), and 3 daily cheese production traits per cow (fresh curd, total solids, and water weight of the curd). Each unprocessed milk sample was analyzed using a MilkoScan FT6000 (Foss, Hillerød, Denmark) over the spectral range, from 5,000 to 900 wavenumber × cm(-1). The FTIR spectrum-based prediction models for the previously mentioned traits were developed using modified partial least-square regression. Cross-validation of the whole data set yielded coefficients of determination between the predicted and measured values in cross-validation of 0.65 to 0.95 for all traits, except for the recovery of fat (0.41). A 3-fold external validation was also used, in which the available data were partitioned into 2 subsets: a training set (one-third of the herds) and a testing set (two-thirds). The training set was used to develop calibration equations, whereas the testing subsets were used for external validation of the calibration equations and to estimate the heritabilities and genetic correlations of the measured and FTIR-predicted phenotypes. The coefficients of determination between the predicted and measured values in cross-validation results obtained from the training sets were very similar to those obtained from the whole

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

    PubMed Central

    Hafke, Jens B.; Höll, Sabina-Roxana; Kühn, Christina; van Bel, Aart J. E.

    2013-01-01

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

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

    PubMed

    Hafke, Jens B; Höll, Sabina-Roxana; Kühn, Christina; van Bel, Aart J E

    2013-01-01

    Apart from cut aphid stylets in combination with electrophysiology, no attempts have been made thus far to measure in vivo sucrose-uptake properties of sieve elements. We investigated the kinetics of sucrose uptake by single sieve elements and phloem parenchyma cells in Vicia faba plants. To this end, microelectrodes were inserted into free-lying phloem cells in the main vein of the youngest fully-expanded leaf, half-way along the stem, in the transition zone between the autotrophic and heterotrophic part of the stem, and in the root axis. A top-to-bottom membrane potential gradient of sieve elements was observed along the stem (-130 mV to -110 mV), while the membrane potential of the phloem parenchyma cells was stable (approx. -100 mV). In roots, the membrane potential of sieve elements dropped abruptly to -55 mV. Bathing solutions having various sucrose concentrations were administered and sucrose/H(+)-induced depolarizations were recorded. Data analysis by non-linear least-square data fittings as well as by linear Eadie-Hofstee (EH) -transformations pointed at biphasic Michaelis-Menten kinetics (2 MM, EH: K m1 1.2-1.8 mM, K m2 6.6-9.0 mM) of sucrose uptake by sieve elements. However, Akaike's Information Criterion (AIC) favored single MM kinetics. Using single MM as the best-fitting model, K m values for sucrose uptake by sieve elements decreased along the plant axis from 1 to 7 mM. For phloem parenchyma cells, higher K m values (EH: K m1 10 mM, K m2 70 mM) as compared to sieve elements were found. In preliminary patch-clamp experiments with sieve-element protoplasts, small sucrose-coupled proton currents (-0.1 to -0.3 pA/pF) were detected in the whole-cell mode. In conclusion (a) K m values for sucrose uptake measured by electrophysiology are similar to those obtained with heterologous systems, (b) electrophysiology provides a useful tool for in situ determination of K m values, (c) As yet, it remains unclear if one or two uptake systems are involved in sucrose

  1. Kinetic Atom.

    ERIC Educational Resources Information Center

    Wilson, David B.

    1981-01-01

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

  2. Enzyme Kinetics.

    ERIC Educational Resources Information Center

    Moe, Owen; Cornelius, Richard

    1988-01-01

    Conveys an appreciation of enzyme kinetic analysis by using a practical and intuitive approach. Discusses enzyme assays, kinetic models and rate laws, the kinetic constants (V, velocity, and Km, Michaels constant), evaluation of V and Km from experimental data, and enzyme inhibition. (CW)

  3. Non-Michaelis-Menten kinetics in cytochrome P450-catalyzed reactions.

    PubMed

    Atkins, William M

    2005-01-01

    The cytochrome P450 monooxygenases (CYPs) are the dominant enzyme system responsible for xenobiotic detoxification and drug metabolism. Several CYP isoforms exhibit non-Michaelis-Menten, or "atypical," steady state kinetic patterns. The allosteric kinetics confound prediction of drug metabolism and drug-drug interactions, and they challenge the theoretical paradigms of allosterism. Both homotropic and heterotropic ligand effects are now widely documented. It is becoming apparent that multiple ligands can simultaneously bind within the active sites of individual CYPs, and the kinetic parameters change with ligand occupancy. In fact, the functional effect of any specific ligand as an activator or inhibitor can be substrate dependent. Divergent approaches, including kinetic modeling and X-ray crystallography, are providing new information about how multiple ligand binding yields complex CYP kinetics.

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

    PubMed

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

    2007-04-26

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

  5. Dynamic crystallization kinetics and nucleation parameters of a new generation of nanocomposites based on isotactic polypropylene and MoS2 inorganic nanotubes.

    PubMed

    Naffakh, Mohammed; Remskar, Maja; Marco, Carlos; Gómez-Fatou, Marián A

    2011-03-31

    Differential scanning calorimetry (DSC) and time-resolved synchrotron X-ray diffraction have been used to investigate the dynamic crystallization behavior and crystalline structure of novel nanocomposites based on isotactic polypropylene (iPP) and molybdenum disulfide inorganic nanotubes (INT-MoS(2)). The influence of the INT-MoS(2) content and different cooling rates on the crystallization behavior has been studied. The crystallization exothermic peak shifted to higher temperature, and the overall crystallization time was reduced by increasing the INT-MoS(2). The dynamic crystallization kinetics was analyzed using the Ozawa-Avrami method, which was successful in describing the dynamic crystallization behavior of these new nanocomposites. On the other hand, study of the nucleation activity using the Dobreva method revealed that the INT-MoS(2) had an efficient nucleation effect on the monoclinic crystal form of iPP. Moreover, this effect was corroborated by the results of the crystallization activation energy, calculated using Kissinger and Takhor methods, which also confirmed the fact that the addition of INT-MoS(2) made the molecular chains easier to crystallize and increased the crystallization rate of iPP.

  6. Evaluation of kinetics parameters in the X-irradiated TSL studies of RE3+-doped (RE=Eu, Tb) ZnO nanorods for dosimetric applications

    NASA Astrophysics Data System (ADS)

    Pal, Partha P.; Manam, J.

    2013-07-01

    This paper reports the detail description of the structural and thermoluminescence of the RE3+-doped (RE=Eu, Tb) ZnO nanorods prepared by adopting co-precipitation method. Formation of as synthesized ZnO nanorods were confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD pattern showed monophasic nature of the as prepared ZnO doped with Eu3+ and Tb3+ ions. The SEM image elaborates the nanorod morphology of RE3+ doped ZnO with diameter ranging between 60-90 nm and length between 600-900 nm. The thermoluminescence spectra of the X-ray irradiated ZnO:Eu3+ and ZnO:Tb3+ show the prominent peak for the broad glow curve peaked at 365 °C and 350 °C, respectively, which have been generated via the recombination of the released electrons from the traps upon thermal stimulation. The peaks are found to obey first order kinetics and the activation energy for the ZnO:Eu3+ and ZnO:Tb3+ samples, estimated via isothermal luminescence glow peak decay method, are found to be 0.8 eV and 0.9 eV respectively. Furthermore, the TL dose response and reproducibility were also studied in details, which could be very useful to establish the potentiality of the present phosphors in the field of radiation dosimetry.

  7. A theoretical discussion of the use of the Lineweaver-Burk plot to estimate kinetic parameters of intestinal transport in the presence of unstirred water layers.

    PubMed

    Thomson, A B

    1981-09-01

    Transport of a solute molecule from the bulk phase in the intestinal lumen into the mucosal cells is determined by the rate of movement of the solute molecule across two barriers, the unstirred water layers (UWL) and the microvillus membrane. Failure to account for the effect of the resistance offered by the UWL introduces significant errors into the estimate of kinetic constants of carrier-mediated transport, and these errors may be further magnified by the use of the Lineweaver-Burk plot. This study was under taken to determine use of this plot under conditions that depict the effect of varying the effective resistance of the UWL, the distribution of transport sites along the villus (fn), the passive permeability coefficient (P), the maximal transport rate (Jdm), and the Michaelis constant (Km). Theoretical curves derived from a new equation demonstrate that (1) the Lineweaver-Burk plot is linear under only a limited number of conditions, and even then may lead to serous over- or under-estimation of Jdm and Km; (2) failure to correct for passive permeation may give rise to additional quantitative discrepancies between the true and apparent values of Jdm and Km; and (3) the qualitative characteristics of a carrier-mediated intestinal transport system may be ascertained only after correction for the contribution of passive permeation, and after correction for the effective resistance of the UWL.

  8. Effects of particle size and coating on toxicologic parameters, fecal elimination kinetics and tissue distribution of acutely ingested silver nanoparticles in a mouse model.

    PubMed

    Bergin, Ingrid L; Wilding, Laura A; Morishita, Masako; Walacavage, Kim; Ault, Andrew P; Axson, Jessica L; Stark, Diana I; Hashway, Sara A; Capracotta, Sonja S; Leroueil, Pascale R; Maynard, Andrew D; Philbert, Martin A

    2016-01-01

    Consumer exposure to silver nanoparticles (AgNP) via ingestion can occur due to incorporation of AgNP into products such as food containers and dietary supplements. AgNP variations in size and coating may affect toxicity, elimination kinetics or tissue distribution. Here, we directly compared acute administration of AgNP of two differing coatings and sizes to mice, using doses of 0.1, 1 and 10 mg/kg body weight/day administered by oral gavage for 3 days. The maximal dose is equivalent to 2000× the EPA oral reference dose. Silver acetate at the same doses was used as ionic silver control. We found no toxicity and no significant tissue accumulation. Additionally, no toxicity was seen when AgNP were dosed concurrently with a broad-spectrum antibiotic. Between 70.5% and 98.6% of the administered silver dose was recovered in feces and particle size and coating differences did not significantly influence fecal silver. Peak fecal silver was detected between 6- and 9-h post-administration and <0.5% of the administered dose was cumulatively detected in liver, spleen, intestines or urine at 48 h. Although particle size and coating did not affect tissue accumulation, silver was detected in liver, spleen and kidney of mice administered ionic silver at marginally higher levels than those administered AgNP, suggesting that silver ion may be more bioavailable. Our results suggest that, irrespective of particle size and coating, acute oral exposure to AgNP at doses relevant to potential human exposure is associated with predominantly fecal elimination and is not associated with accumulation in tissue or toxicity.

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

    PubMed

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

    2016-12-01

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

  10. Nonphotochemical hole burning and dispersive kinetics in amorphous solids

    SciTech Connect

    Kenney, M.J.

    1990-09-21

    Results covering burn intensities in the nW to {mu}W/cm{sup 2} range, of dispersive hole growth kinetics are reported for Oxazine 720 in glycerol glasses and polyvinyl alcohol polymer films and their deuterated analogues. A theoretical model which employs a distribution function for the hole burning rate constant based upon a Gaussian distribution for the tunnel parameter is shown to accurately describe the kinetic data. This model incorporates the linear electron-phonon coupling. A method for calculating the nonphotochemical quantum yield is presented which utilizes the Gaussian distribution of tunnel parameters. The quantum yield calculation can be extended to determine a quantum yield as a function of hole depth. The effect of spontaneous hole filling is shown to be insignificant over the burn intensity range studied. Average relaxation rates for hole burning are {approximately}8 orders of magnitude greater than for hole filling. The dispersive kinetics of hole burning are observed to be independent over the temperature range of these experiments, 1.6 to 7.0 K. 6 refs., 20 figs., 1 tab.

  11. An application of population kinetics analysis to estimate pharmacokinetic parameters of sodium tungstate after multiple-dose during preclinical studies in rats.

    PubMed

    Le Lamer, Sophie; Cros, Gérard; Piñol, Carmen; Fernández-Alvarez, Josepha; Bressolle, Françoise

    2002-02-01

    The purpose of this study was to use a population approach in the preclinical development program of sodium tungstate in the rat in order i) to compute individual pharmacokinetic parameters of this compound after repeated oral administrations, until the 4-week toxicology study, using an empirical Bayes methodology; and ii) to study the influence of the administered dose, of the gender and of the duration of treatment on the pharmacokinetic parameters. Four studies were used representing a mixture of single intravenous administration and multiple oral administrations. The treatment duration ranged from 7 to 28 days. Intravenous dose was 9 mg/kg; three different oral doses were tested, 50, 100 and 200 mg/kg/day. Plasma concentration profiles versus time were compatible with a two-compartment model. A significant gender effect was found on bioavailability. The duration of treatment and the administered dose did not significantly explain part of the interindividual variability of pharmacokinetic parameters. The absorption of tungsten was rapid (1-3 hr). Total plasma clearance and elimination half-life averaged 2.8 ml/min/kg and 3.04 hr in males, and 3 ml/min/kg and 2.74 hr in females. The bioavailability was on an average 70%; being significantly higher in females than in males (0.78 versus 0.61). This compartmental approach should be considered as complementary to the usual non-compartmental approach used for analysis of preclinical data and should be a valuable tool to characterise the pharacokinetic/pharmacodynamic behaviour of a drug.

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

    PubMed

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

    2016-07-01

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

  13. Effect of Mn and Cr additions on kinetics of recrystallization and parameters of grain-boundary relaxation of Al-4.9Mg alloy

    NASA Astrophysics Data System (ADS)

    Mikhailovskaya, A. V.; Golovin, I. S.; Zaitseva, A. A.; Portnoi, V. K.; Dröttboom, P.; Cifre, J.

    2013-03-01

    Methods of microstructural analysis, measurements of hardness, and temperature and time dependences of internal friction (TDIF and TDIF(iso), respectively) have been used to study recrystallization in cold-rolled alloys and grain-boundary relaxation in annealed alloys. A complex analysis of the effect of additions of transition metals (Mn, Cr) on the magnitude of the activation energy of the background of the internal friction in deformed and annealed states and on the activation parameters of grain-boundary relaxation has been performed. Methods of amplitude dependences of internal friction (ADIF) have been used to determine the critical amplitude that corresponds to the beginning of microplastic deformation in the alloys at different temperatures.

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

    NASA Astrophysics Data System (ADS)

    Parimaladevi, P.; Srinivasan, K.

    2014-09-01

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

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

    PubMed

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

    2014-02-01

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

  16. Stochastic Kinetics of Nascent RNA

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  17. Mesophilic digestion kinetics of manure slurry.

    PubMed

    Karim, Khursheed; Klasson, K Thomas; Drescher, Sadie R; Ridenour, Whitney; Borole, Abhijeet P; Al-Dahhan, Muthanna H

    2007-09-01

    Anaerobic digestion kinetics study of cow manure was performed at 35 degrees C in bench-scale gas-lift digesters (3.78 l working volume) at eight different volatile solids (VS) loading rates in the range of 1.11-5.87 g l-1 day-1. The digesters produced methane at the rates of 0.44-1.18 l l-1 day-1, and the methane content of the biogas was found to increase with longer hydraulic retention time (HRT). Based on the experimental observations, the ultimate methane yield and the specific methane productivity were estimated to be 0.42 l CH4 (g VS loaded)-1 and 0.45 l CH4 (g VS consumed)-1, respectively. Total and dissolved chemical oxygen demand (COD) consumptions were calculated to be 59-17% and 78-43% at 24.4-4.6 days HRTs, respectively. Maximum concentration of volatile fatty acids in the effluent was observed as 0.7 g l-1 at 4.6 days HRT, while it was below detection limit at HRTs longer than 11 days. The observed methane production rate did not compare well with the predictions of Chen and Hashimoto's [1] and Hill's [2] models using their recommended kinetic parameters. However, under the studied experimental conditions, the predictions of Chen and Hashimoto's [1] model compared better to the observed data than that of Hill's [2] model. The nonlinear regression analysis of the experimental data was performed using a derived methane production rate model, for a completely mixed anaerobic digester, involving Contois kinetics [3] with endogenous decay. The best fit values for the maximum specific growth rate (micro m) and dimensionless kinetic parameter (K) were estimated as 0.43 day-1 and 0.89, respectively. The experimental data were found to be within 95% confidence interval of the prediction of the derived methane production rate model with the sum of residual squared error as 0.02.

  18. Effect of driver impedance on dense plasma focus Z-pinch neutron yield

    SciTech Connect

    Sears, Jason E-mail: schmidt36@llnl.gov; Link, Anthony E-mail: schmidt36@llnl.gov; Schmidt, Andrea E-mail: schmidt36@llnl.gov; Welch, Dale

    2014-12-15

    The Z-pinch phase of a dense plasma focus (DPF) heats the plasma by rapid compression and accelerates ions across its intense electric fields, producing neutrons through both thermonuclear and beam-target fusion. Driver characteristics have empirically been shown to affect performance, as measured by neutron yield per unit of stored energy. We are exploring the effect of driver characteristics on DPF performance using particle-in-cell (PIC) simulations of a kJ scale DPF. In this work, our PIC simulations are fluid for the run-down phase and transition to fully kinetic for the pinch phase, capturing kinetic instabilities, anomalous resistivity, and beam formation during the pinch. The anode-cathode boundary is driven by a circuit model of the capacitive driver, including system inductance, the load of the railgap switches, the guard resistors, and the coaxial transmission line parameters. It is known that the driver impedance plays an important role in the neutron yield: first, it sets the peak current achieved at pinch time; and second, it affects how much current continues to flow through the pinch when the pinch inductance and resistance suddenly increase. Here we show from fully kinetic simulations how total neutron yield depends on the impedance of the driver and the distributed parameters of the transmission circuit. Direct comparisons between the experiment and simulations enhance our understanding of these plasmas and provide predictive design capability for neutron source applications.

  19. 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

  20. Kinetic analysis for macrocyclizations involving anionic template at the transition state.

    PubMed

    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 S(N)2 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.

  1. Study on kinetic model of microwave thermocatalytic treatment of biomass tar model compound.

    PubMed

    Anis, Samsudin; Zainal, Z A

    2014-01-01

    Kinetic model parameters for toluene conversion under microwave thermocatalytic treatment were evaluated. The kinetic rate constants were determined using integral method based on experimental data and coupled with Arrhenius equation for obtaining the activation energies and pre-exponential factors. The model provides a good agreement with the experimental data. The kinetic model was also validated with standard error of 3% on average. The extrapolation of the model showed a reasonable trend to predict toluene conversion and product yield both in thermal and catalytic treatments. Under microwave irradiation, activation energy of toluene conversion was lower in the range of 3-27 kJ mol(-1) compared to those of conventional heating reported in the literatures. The overall reaction rate was six times higher compared to conventional heating. As a whole, the kinetic model works better for tar model removal in the absence of gas reforming within a level of reliability demonstrated in this study.

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

    PubMed

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

    2009-01-30

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

  3. Assessment of bioethanol yield by S. cerevisiae grown on oil palm residues: Monte Carlo simulation and sensitivity analysis.

    PubMed

    Samsudin, Mohd Dinie Muhaimin; Mat Don, Mashitah

    2015-01-01

    Oil palm trunk (OPT) sap was utilized for growth and bioethanol production by Saccharomycescerevisiae with addition of palm oil mill effluent (POME) as nutrients supplier. Maximum yield (YP/S) was attained at 0.464g bioethanol/g glucose presence in the OPT sap-POME-based media. However, OPT sap and POME are heterogeneous in properties and fermentation performance might change if it is repeated. Contribution of parametric uncertainty analysis on bioethanol fermentation performance was then assessed using Monte Carlo simulation (stochastic variable) to determine probability distributions due to fluctuation and variation of kinetic model parameters. Results showed that based on 100,000 samples tested, the yield (YP/S) ranged 0.423-0.501g/g. Sensitivity analysis was also done to evaluate the impact of each kinetic parameter on the fermentation performance. It is found that bioethanol fermentation highly depend on growth of the tested yeast.

  4. Determination of kinetic and equilibrium parameters of the batch adsorption of Mn(II), Co(II), Ni(II) and Cu(II) from aqueous solution by black carrot (Daucus carota L.) residues.

    PubMed

    Güzel, Fuat; Yakut, Hakan; Topal, Giray

    2008-05-30

    In this study, the effect of temperature on the adsorption of Mn(II), Ni(II), Co(II) and Cu(II) from aqueous solution by modified carrot residues (MCR) was investigated. The equilibrium contact times of adsorption process for each heavy metals-MCR systems were determined. Kinetic data obtained for each heavy metal by MCR at different temperatures were applied to the Lagergren equation, and adsorption rate constants (kads) at these temperatures were determined. These rate constants related to the adsorption of heavy metal by MCR were applied to the Arrhenius equation, and activation energies (Ea) were determined. In addition, the isotherms for adsorption of each heavy metal by MCR at different temperatures were also determined. These isothermal data were applied to linear forms of isotherm equations that they fit the Langmuir adsorption isotherm, and the Langmuir constants (qm and b) were calculated. b constants determined at different temperatures were applied to thermodynamic equations, and thermodynamic parameters such as enthalpy (Delta H), free energy (Delta G), and entropy (Delta S) were calculated and these values show that adsorption of heavy metal on MCR was an endothermic process and process of adsorption was favoured at high temperatures.

  5. Testing the nonlocal kinetic energy functional of an inhomogeneous, two-dimensional degenerate Fermi gas within the average density approximation

    NASA Astrophysics Data System (ADS)

    Towers, J.; van Zyl, B. P.; Kirkby, W.

    2015-08-01

    In a recent paper [B. P. van Zyl et al., Phys. Rev. A 89, 022503 (2014), 10.1103/PhysRevA.89.022503], the average density approximation (ADA) was implemented to develop a parameter-free, nonlocal kinetic energy functional to be used in the orbital-free density functional theory of an inhomogeneous, two-dimensional (2D) Fermi gas. In this work, we provide a detailed comparison of self-consistent calculations within the ADA with the exact results of the Kohn-Sham density functional theory and the elementary Thomas-Fermi (TF) approximation. We demonstrate that the ADA for the 2D kinetic energy functional works very well under a wide variety of confinement potentials, even for relatively small particle numbers. Remarkably, the TF approximation for the kinetic energy functional, without any gradient corrections, also yields good agreement with the exact kinetic energy for all confining potentials considered, although at the expense of the spatial and kinetic energy densities exhibiting poor pointwise agreement, particularly near the TF radius. Our findings illustrate that the ADA kinetic energy functional yields accurate results for both the local and global equilibrium properties of an inhomogeneous 2D Fermi gas, without the need for any fitting parameters.

  6. Comparison of egg and high yielding MDCK cell-derived live attenuated influenza virus for commercial production of trivalent influenza vaccine: in vitro cell susceptibility and influenza virus replication kinetics in permissive and semi-permissive cells.

    PubMed

    Hussain, Althaf I; Cordeiro, Melissa; Sevilla, Elizabeth; Liu, Jonathan

    2010-05-14

    Currently MedImmune manufactures cold-adapted (ca) live, attenuated influenza vaccine (LAIV) from specific-pathogen free (SPF) chicken eggs. Difficulties in production scale-up and potential exposure of chicken flocks to avian influenza viruses especially in the event of a pandemic influenza outbreak have prompted evaluation and development of alternative non-egg based influenza vaccine manufacturing technologies. As part of MedImmune's effort to develop the live attenuated influenza vaccine (LAIV) using cell culture production technologies we have investigated the use of high yielding, cloned MDCK cells as a substrate for vaccine production by assessing host range and virus replication of influenza virus produced from both SPF egg and MDCK cell production technologies. In addition to cloned MDCK cells the indicator cell lines used to evaluate the impact of producing LAIV in cells on host range and replication included two human cell lines: human lung carcinoma (A549) cells and human muco-epidermoid bronchiolar carcinoma (NCI H292) cells. The influenza viruses used to infect the indicators cell lines represented both the egg and cell culture manufacturing processes and included virus strains that composed the 2006-2007 influenza seasonal trivalent vaccine (A/New Caledonia/20/99 (H1N1), A/Wisconsin/67/05 (H3N2) and B/Malaysia/2506/04). Results from this study demonstrate remarkable similarity between influenza viruses representing the current commercial egg produced and developmental MDCK cell produced vaccine production platforms. MedImmune's high yielding cloned MDCK cells used for the cell culture based vaccine production were highly permissive to both egg and cell produced ca attenuated influenza viruses. Both the A549 and NCI H292 cells regardless of production system were less permissive to influenza A and B viruses than the MDCK cells. Irrespective of the indicator cell line used the replication properties were similar between egg and the cell produced

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

    PubMed

    Kuby, S A; Roy, R N

    1976-05-04

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

  8. Parallel versus Off-Pathway Michaelis-Menten Mechanism for Single-Enzyme Kinetics of a Fluctuating Enzyme.

    PubMed

    Kumar, Ashutosh; Maity, Hiranmay; Dua, Arti

    2015-07-09

    Recent fluorescence spectroscopy measurements of the turnover time distribution of single-enzyme turnover kinetics of β-galactosidase provide evidence of Michaelis-Menten kinetics at low substrate concentration. However, at high substrate concentrations, the dimensionless variance of the turnover time distribution shows systematic deviations from the Michaelis-Menten prediction. This difference is attributed to conformational fluctuations in both the enzyme and the enzyme-substrate complex and to the possibility of both parallel- and off-pathway kinetics. Here, we use the chemical master equation to model the kinetics of a single fluctuating enzyme that can yield a product through either parallel- or off-pathway mechanisms. An exact expression is obtained for the turnover time distribution from which the mean turnover time and randomness parameters are calculated. The parallel- and off-pathway mechanisms yield strikingly different dependences of the mean turnover time and the randomness parameter on the substrate concentration. In the parallel mechanism, the distinct contributions of enzyme and enzyme-substrate fluctuations are clearly discerned from the variation of the randomness parameter with substrate concentration. From these general results, we conclude that an off-pathway mechanism, with substantial enzyme-substrate fluctuations, is needed to rationalize the experimental findings of single-enzyme turnover kinetics of β-galactosidase.

  9. Nonparametric analysis of nonexponential and multidimensional kinetics. I. Quantifying rate dispersion, rate heterogeneity, and exchange dynamics.

    PubMed

    Berg, Mark A; Kaur, Harveen

    2017-02-07

    The quantification of nonexponential (dispersed) kinetics has relied on empirical functions, which yield parameters that are neither unique nor easily related to the underlying mechanism. Multidimensional kinetics provide more information on dispersed processes, but a good approach to their analysis is even less clear than for standard, one-dimensional kinetics. This paper is the first in a series that analyzes kinetic data in one or many dimensions with a scheme that is nonparametric: it quantifies nonexponential decays without relying on a specific functional form. The quantities obtained are directly related to properties of the mechanism causing the rate dispersion. Log-moments of decays, which parallel the standard moments of distributions (mean, standard deviation, etc.), are introduced for both one- and multi-dimensional decays. Kinetic spectra are defined to visualize the data. The utility of this approach is demonstrated on a simple, but general, model of dispersed kinetics-a nonexponential homogeneous decay combined with slowly exchanging rate heterogeneity. The first log-moments give a geometric-mean relaxation time. Second log-moments quantify the magnitude of rate dispersion, the fraction of the dispersion due to heterogeneity, and the dynamics of exchange between different rate subensembles. A suitable combination of these moments isolates exchange dynamics from three-dimensional kinetics without contamination by the rate-filtering effects that were identified in a recent paper [M. A. Berg and J. R. Darvin, J. Chem. Phys. 145, 054119 (2016)].

  10. Mutations that decrease DNA binding of the processivity factor of the herpes simplex virus DNA polymerase reduce viral yield, alter the kinetics of viral DNA replication, and decrease the fidelity of DNA replication.

    PubMed

    Jiang, Changying; Hwang, Ying T; Randell, John C W; Coen, Donald M; Hwang, Charles B C

    2007-04-01

    The processivity subunit of the herpes simplex virus DNA polymerase, UL42, is essential for viral replication and possesses both Pol- and DNA-binding activities. Previous studies demonstrated that the substitution of alanine for each of four arginine residues, which reside on the positively charged surface of UL42, resulted in decreased DNA binding affinity and a decreased ability to synthesize long-chain DNA by the polymerase. In this study, the effects of each substitution on the production of viral progeny, viral DNA replication, and DNA replication fidelity were examined. Each substitution mutant was able to complement the replication of a UL42 null mutant in transient complementation assays and to support the replication of plasmid DNA containing herpes simplex virus type 1 (HSV-1) origin sequences in transient DNA replication assays. Mutant viruses containing each substitution and a lacZ insertion in a nonessential region of the genome were constructed and characterized. In single-cycle growth assays, the mutants produced significantly less progeny virus than the control virus containing wild-type UL42. Real-time PCR assays revealed that these UL42 mutants synthesized less viral DNA during the early phase of infection. Interestingly, during the late phase of infection, the mutant viruses synthesized larger amounts of viral DNA than the control virus. The frequencies of mutations of the virus-borne lacZ gene increased significantly in the substitution mutants compared to those observed for the control virus. These results demonstrate that the reduced DNA binding of UL42 is associated with significant effects on virus yields, viral DNA replication, and replication fidelity. Thus, a processivity factor can influence replication fidelity in mammalian cells.

  11. Taylor-Couette instability in thixotropic yield stress fluids

    NASA Astrophysics Data System (ADS)

    Jenny, Mathieu; Kiesgen de Richter, Sébastien; Louvet, Nicolas; Skali-Lami, Salahedine; Dossmann, Yvan

    2017-02-01

    We consider the flow of thixotropic yield stress fluids between two concentric cylinders. To account for the fluid thixotropy, we use Hou\\vska's model [Hou\\vska, Ph.D. thesis, Czech Technical University, Prague, 1981] with a single structural parameter driven by a kinetic equation. Because of the yield stress and the geometric inhomogeneity of the stress, only a part of the material in the gap may flow. Depending on the breakdown rate of the structural parameter, the constitutive relation can lead to a nonmonotonic flow curve. This nonmonotonic behavior is known to induce a discontinuity in the slope of the velocity profile within the flowing material, called shear banding. Thus, for fragile structures, a shear-banded flow characterized by a very sharp transition between the flowing and the static regions may be observed. For stronger structures, the discontinuity disappears and a smooth transition between the flowing and the static regions is observed. The consequences of the thixotropy on the linear stability of the azimuthal flow are studied in a large range of parameters. Although the thixotropy allows shear banding in the base flow, it does not modify fundamentally the linear stability of the Couette flow compared to a simple yield stress fluid. The apparent shear-thinning behavior depends on the thixotropic parameters of the fluid and the results about the onset of the Taylor vortices in shear-thinning fluids are retrieved. Nevertheless, the shear banding modifies the stratification of the viscosity in the flowing zone such that the critical conditions are mainly driven by the width of the flowing region.

  12. 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.

  13. 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.

  14. Simple model relating recombination rates and non-proportional light yield in scintillators

    SciTech Connect

    Moses, William W.; Bizarri, Gregory; Singh, Jai; Vasil'ev, Andrey N.; Williams, Richard T.

    2008-09-24

    We present a phenomenological approach to derive an approximate expression for the local light yield along a track as a function of the rate constants of different kinetic orders of radiative and quenching processes for excitons and electron-hole pairs excited by an incident {gamma}-ray in a scintillating crystal. For excitons, the radiative and quenching processes considered are linear and binary, and for electron-hole pairs a ternary (Auger type) quenching process is also taken into account. The local light yield (Y{sub L}) in photons per MeV is plotted as a function of the deposited energy, -dE/dx (keV/cm) at any point x along the track length. This model formulation achieves a certain simplicity by using two coupled rate equations. We discuss the approximations that are involved. There are a sufficient number of parameters in this model to fit local light yield profiles needed for qualitative comparison with experiment.

  15. Yield Advances in Peanut

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Average yields of peanut in the U.S. set an all time record of 4,695 kg ha-1 in 2012. This far exceeded the previous record yield of 3,837 kg ha-1 in 2008. Favorable weather conditions undoubtedly contributed to the record yields in 2012; however, these record yields would not have been achievable...

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

    PubMed

    Noé, Frank; Clementi, Cecilia

    2015-10-13

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

  17. Kinetic roughening: how directionality changes the game

    NASA Astrophysics Data System (ADS)

    Araujo, Nuno

    The nonequilibrium evolution of growing interfaces has attracted many experimental and theoretical studies over decades. One of the most popular theoretical approaches considers kinetic discrete models to describe particle aggregation on substrates. Albeit simple, these models are expected to contain the relevant physics. Inspired by recent advances in the production of functionalized colloidal particles, with attractive patches on their surface, we have proposed a stochastic model to study the effect of directionality and selective pairwise interactions on the kinetics of aggregation. We find a nontrivial dependence of the bulk and surface properties on the strength and flexibility of the patch-patch interactions, and on the spatial-patch distribution. For three-patch particles, sustained growth is only observed for a finite-range of the distance between patches, yielding two absorbing phase transitions and a tricritical flexibility. For four-patch particles with two distinct patches, i.e. strong and weak bonds, and sufficiently different bonding probabilities, the scaling properties of the interface crossover from the universality class of Kardar-Parisi-Zhang to the critical class of Kardar-Parisi-Zhang with quenched disorder. The latter is observed for an extended range of the parameters revealing the presence of a self-organized critical mechanism. Implications of our findings beyond functionalized particles are also discussed.

  18. Magnetic field and temperature dependencies shed light on the recombination kinetics of a transition metal donor/acceptor system.

    PubMed

    von Feilitzsch, T; Härter, P; Schiemann, O; Michel-Beyerle, M E; Steiner, U E; Gilch, P

    2005-11-02

    The radical pair recombination of an intramolecular electron-transfer system containing a transition metal moiety has been addressed by femtosecond spectroscopy. The radical pair is formed by ultrafast electron transfer (90 fs) from a ferrocene residue to a photoexcited Nile blue moiety. Its recombination proceeds on the picosecond time scale in a multiexponential fashion. The kinetic pattern is a manifestation of spin processes competing with electron transfer. Magnetic field effects on these kinetics allow one to disentangle the two contributions. Their temperature dependencies yield the activation parameters of the two processes. The discussion focuses on the mechanism of electron spin relaxation. Strong evidence for the Orbach/Kivelson mechanism will be given.

  19. Compartmental analysis of (11C)flumazenil kinetics for the estimation of ligand transport rate and receptor distribution using positron emission tomography

    SciTech Connect

    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.

  20. Tolrestat kinetics

    SciTech Connect

    Hicks, D.R.; Kraml, M.; Cayen, M.N.; Dubuc, J.; Ryder, S.; Dvornik, D.

    1984-10-01

    The kinetics of tolrestat, a potent inhibitor of aldose reductase, were examined. Serum concentrations of tolrestat and of total /sup 14/C were measured after dosing normal subjects and subjects with diabetes with /sup 14/C-labeled tolrestat. In normal subjects, tolrestat was rapidly absorbed and disappearance from serum was biphasic. Distribution and elimination t 1/2s were approximately 2 and 10 to 12 hr, respectively, after single and multiple doses. Unchanged tolrestat accounted for the major portion of /sup 14/C in serum. Radioactivity was rapidly and completely excreted in urine and feces in an approximate ratio of 2:1. Findings were much the same in subjects with diabetes. In normal subjects, the kinetics of oral tolrestat were independent of dose in the 10 to 800 mg range. Repetitive dosing did not result in unexpected cumulation. Tolrestat was more than 99% bound to serum protein; it did not compete with warfarin for binding sites but was displaced to some extent by high concentrations of tolbutamide or salicylate.

  1. Nonparametric analysis of nonexponential and multidimensional kinetics. I. Quantifying rate dispersion, rate heterogeneity, and exchange dynamics

    NASA Astrophysics Data System (ADS)

    Berg, Mark A.; Kaur, Harveen

    2017-02-01

    The quantification of nonexponential (dispersed) kinetics has relied on empirical functions, which yield parameters that are neither unique nor easily related to the underlying mechanism. Multidimensional kinetics provide more information on dispersed processes, but a good approach to their analysis is even less clear than for standard, one-dimensional kinetics. This paper is the first in a series that analyzes kinetic data in one or many dimensions with a scheme that is nonparametric: it quantifies nonexponential decays without relying on a specific functional form. The quantities obtained are directly related to properties of the mechanism causing the rate dispersion. Log-moments of decays, which parallel the standard moments of distributions (mean, standard deviation, etc.), are introduced for both one- and multi-dimensional decays. Kinetic spectra are defined to visualize the data. The utility of this approach is demonstrated on a simple, but general, model of dispersed kinetics—a nonexponential homogeneous decay combined with slowly exchanging rate heterogeneity. The first log-moments give a geometric-mean relaxation time. Second log-moments quantify the magnitude of rate dispersion, the fraction of the dispersion due to heterogeneity, and the dynamics of exchange between different rate subensembles. A suitable combination of these moments isolates exchange dynamics from three-dimensional kinetics without contamination by the rate-filtering effects that were identified in a recent paper [M. A. Berg and J. R. Darvin, J. Chem. Phys. 145, 054119 (2016)].

  2. Chemical kinetics modeling

    SciTech Connect

    Westbrook, C.K.; Pitz, W.J.

    1993-12-01

    This project emphasizes numerical modeling of chemical kinetics of combustion, including applications in both practical combustion systems and in controlled laboratory experiments. Elementary reaction rate parameters are combined into mechanisms which then describe the overall reaction of the fuels being studied. Detailed sensitivity analyses are used to identify those reaction rates and product species distributions to which the results are most sensitive and therefore warrant the greatest attention from other experimental and theoretical research programs. Experimental data from a variety of environments are combined together to validate the reaction mechanisms, including results from laminar flames, shock tubes, flow systems, detonations, and even internal combustion engines.

  3. Kinetic study on biomass gasification

    SciTech Connect

    Bingyan, X.; Chuangzhi, W.; Zhengfen, L.; Guang, Z.X. )

    1992-09-01

    An experimental apparatus, with the features of fast heating rate and continuous record of reaction parameters, was developed to study kinetics of fast pyrolysis. The temperature effects, at a range of 400 C to 900 C, on pyrolysis rate, products profile, gas quality and quantity, and so on, were studied and the results are listed and analyzed. The effect of secondary reaction of gas phase at 700 C was tested and the regression result is expressed in an experimental formula. Based on the experimental results, the three-stage-reaction mechanism module is suggested. The kinetic expression to calculate gas formation rate is concluded as: d{alpha}/dt = A exp({minus}E/RT)(1 {minus} {alpha}){sup n}. The kinetic parameters of A, E, and n at different temperatures are given in the paper.

  4. Cationic polyvinylamine binding to anionic microgels yields kinetically controlled structures.

    PubMed

    Wen, Quan; Vincelli, Andrew M; Pelton, Robert

    2012-03-01

    Polyvinylamine (PVAm) binding (absorption and adsorption) to carboxylated microgels gave colloidally stable, cationic microgels that can be centrifuged, washed, freeze dried, and redispersed in water with no loss in colloidal stability. Because both PVAm and the carboxylated microgels are pH sensitive, changes in microgel swelling and electrophoretic mobility in response to pH change can be positive or negative depending upon pH and the PVAm content of the microgels. For a given PVAm molecular weight, the steady-state saturated mass fraction of bound PVAm in the microgels varied by a factor of four in our experiments. We proposed that the PVAm content at saturation was controlled by the relative rates of the initial attachment of PVAm chains versus the rate of attached chain spreading on and into the microgel structure. This explanation was further supported by a series of quartz crystal microbalance measurements. Finally, PVAm binding to two types of PNIPAM microgels shows general features recently reported for other polyelectrolyte types. Specifically: (1) for surface localized anionic charges on the microgels, the mass fraction of bound PVAm increased with PVAm molecular weight and vice versa; (2) in virtually all conditions, the quantity of adsorbed cationic ammonium groups was much greater than the carboxylate content of the microgel; and (3) sodium chloride additions lowered the mass fraction of bound PVAm.

  5. Kinetics and model development for enzymatic synthesis of fructo-oligosaccharides using fructosyltransferase.

    PubMed

    Kashyap, Rahul; Palai, Tapas; Bhattacharya, Prashant K

    2015-12-01

    Experimental investigations were made to synthesize fructo-oligosaccharides (FOS) from sucrose using fructosyltransferase. The influence of various parameters such as temperature (45-55 °C), pH (4-5), initial sucrose concentration (ISC: 300-500 g/L) and enzyme concentration (4-32 U/mL) were varied. A maximum FOS yield of 60% was observed at ISC 500 g/L, pH 4.5 with enzyme activity 32 U/mL and at 55 °C. It was confirmed that 1-kestose (tri-) was the major product of FOS as compared to nystose (tetra-) and fructosylnystose (penta-saccharides). Further, the reaction rate increases with increase in temperature. From separate sets of experiments, it was observed that FOS formation was affected by glucose inhibition. Apart from the increase in the rate of FOS formation with increasing enzyme activity, the final values of FOS yield increase though till 16 U/mL and thereafter attain plateau. A kinetic model was also developed, based on Michaelis-Menten kinetics, and a five-step ten-parameter model, including glucose inhibition, was obtained. Model was solved using COPASI(®) (version 4.8) solver for kinetic parameter estimations followed by time course simulations.

  6. 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…

  7. Kinetic buffers.

    PubMed

    Alibrandi, Giuseppe; Fabbrizzi, Luigi; Licchelli, Maurizio; Puglisi, Antonio

    2015-01-12

    This paper proposes a new type of molecular device that is able to act as an inverse proton sponge to slowly decrease the pH inside a reaction vessel. This makes the automatic monitoring of the concentration of pH-sensitive systems possible. The device is a composite formed of an alkyl chloride, which kinetically produces acidity, and a buffer that thermodynamically modulates the variation in pH value. Profiles of pH versus time (pH-t plots) have been generated under various experimental conditions by computer simulation, and the device has been tested by carrying out automatic spectrophotometric titrations, without using an autoburette. To underline the wide variety of possible applications, this new system has been used to realize and monitor HCl uptake by a di-copper(II) bistren complex in a single run, in a completely automatic experiment.

  8. Reinvestigation of the elementary chemical kinetics of the reaction C2H5(•) + HBr (HI) → C2H6 + Br(•) (I(•)) in the range 293-623 K and its implication on the thermochemical parameters of C2H5(•) free radical.

    PubMed

    Leplat, N; Wokaun, A; Rossi, M J

    2013-11-14

    A reinvestigation of the absolute rate constants of the metathesis reactions C2H5• + HBr → C2H6 + Br• (R1) and C2H5• + HI → C2H6 + I• (R2) has been performed and led to the following Arrhenius expressions: k1 = 3.69(±0.95) × 10–11 exp(−10.62(±0.66)/RT), k2 = 1.20(±0.38) × 10–11 exp(−7.12(±1.059)/RT) in the temperature range 293–623 K (A/cm3 molecule–1 s–1, Ea/kJ mol–1). The study has been performed using a Knudsen reactor coupled to single-photon (VUV) photoionization mass spectrometer (SPIMS). Hydrocarbon free radicals have been generated externally before admission into the Knudsen reactor according to two different chemical schemes, enabling the generation of thermalized C2H5• free radicals. A minor correction to k1 and k2 for the wall loss of C2H5• (kw) has been applied throughout the temperature range. The obtained results are consistent regarding both the disappearance of C2H5• and the formation of closed shell products (n-C4H10, C2H4, C2H6), indicating that the chemical mechanism is largely understood and complete. Thermochemical parameters for C2H5• free radical resulting from the present kinetic measurements are discussed and point toward a slightly lower value for the standard heat of formation ΔfH298°(C2H5•) compared to some presently recommended values. On the basis of the present results and suitable data on the reverse reaction taken from the literature, we recommend ΔfH298°(C2H5•) = 117.3 ± 3.1 kJ/mol resulting from an average of “third law” evaluations using S298°(C2H5•) = 242.9 ± 4.6 J/K mol. The present work yields a standard heat of formation in satisfactory agreement with the results obtained by W. Tsang (ΔfH298°(C2H5•) = 119 ± 2 kJ/mol) despite using two very different experimental techniques.

  9. Kinetic studies of ICF implosions

    DOE PAGES

    Kagan, Grigory; Herrmann, H. W.; Kim, Y. -H.; ...

    2016-05-26

    Here, kinetic effects on inertial confinement fusion have been investigated. In particular, inter-ion-species diffusion and suprathermal ion distribution have been analyzed. The former drives separation of the fuel constituents in the hot reacting core and governs mix at the shell/fuel interface. The latter underlie measurements obtained with nuclear diagnostics, including the fusion yield and inferred ion burn temperatures. Basic mechanisms behind and practical consequences from these effects are discussed.

  10. Large-scale reactive molecular dynamics simulation and kinetic modeling of high-temperature pyrolysis of the Gloeocapsomorphaprisca microfossils.

    PubMed

    Zou, Chenyu; Raman, Sumathy; van Duin, Adri C T

    2014-06-12

    The ability to predict accurately the thermal conversion of complex carbonaceous materials is of value in both petroleum exploration and refining operations. Modeling the thermal cracking of kerogen under basinal heating conditions improves the predrill prediction of oil and gas yields and quality, thereby ultimately lowering the exploration risk. Modeling the chemical structure and reactivity of asphaltene from petroleum vacuum residues enables prediction of coke formation and properties in refinery processes, thereby lowering operating cost. The chemical structure-chemical yield modeling (CS-CYM) developed by Freund et al. is more rigorous, time-consuming, and requires a great deal of chemical insight into reaction network and reaction kinetics. The present work explores the applicability of a more fundamental atomistic simulation using the quantum mechanically based reactive force field to predict the product yield and overall kinetics of decomposition of two biopolymers, namely, the Kukersite and Gutternberg. Reactive molecular dynamics (RMD) simulations were performed on systems consisting of 10(4) to 10(5) atoms at different densities and temperatures to derive the overall kinetic parameters and a lumped kinetic model for pyrolysis. The kinetic parameters derived from the simulated pyrolysis of an individual component and the mixture of all four components in Guttenberg reveal the role of cross-talk between the fragments and enhanced reactivity of component A by radicals from other components. The Arrhenius extrapolation of the model yields reasonable prediction for the overall barrier for cracking. Because simulations were run at very high temperature (T > 1500 K) to study cracking within the simulation time of up to 1 ns, it, however, led to the entropically favored ethylene formation as a dominant decomposition route. Future work will focus on evaluating the applicability of accelerated reactive MD approaches to study cracking.

  11. Probabilistic multicompartmental model for interpreting DGT kinetics in sediments.

    PubMed

    Ciffroy, P; Nia, Y; Garnier, J M

    2011-11-15

    Extensive research has been performed on the use of the DIFS (DGT-Induced Fluxes in Soils and Sediments) model to interpret diffusive gradients in thin-film, or DGT, measurements in soils and sediments. The current report identifies some areas where the DIFS model has been shown to yield poor results and proposes a model to address weaknesses. In particular, two major flaws in the current approaches are considered: (i) many studies of accumulation kinetics in DGT exhibit multiple kinetic stages and (ii) several combinations of the two fitted DIFS parameters can yield identical results, leaving the question of how to select the 'best' combination. Previously, problem (i) has been addressed by separating the experimental data sets into distinct time segments. To overcome these problems, a model considering two types of particulate binding sites is proposed, instead of the DIFS model which assumed one single particulate pool. A probabilistic approach is proposed to fit experimental data and to determine the range of possible physical parameters using Probability Distribution Functions (PDFs), as opposed to single values without any indication of their uncertainty. The new probabilistic model, called DGT-PROFS, was tested on three different formulated sediments which mainly differ in the presence or absence of iron oxides. It was shown that a good fit can be obtained for the complete set of data (instead of DIFS-2D) and that a range of uncertainty values for each modeling parameter can be obtained. The interpretation of parameter PDFs allows one to distinguish between a variety of geochemical behaviors, providing useful information on metal dynamics in sediments.

  12. Yield Improvement in Steel Casting (Yield II)

    SciTech Connect

    Richard A. Hardin; Christoph Beckermann; Tim Hays

    2002-02-18

    This report presents work conducted on the following main projects tasks undertaken in the Yield Improvement in Steel Casting research program: Improvement of Conventional Feeding and Risering Methods, Use of Unconventional Yield Improvement Techniques, and Case Studies in Yield Improvement. Casting trials were conducted and then simulated using the precise casting conditions as recorded by the participating SFSA foundries. These results present a statistically meaningful set of experimental data on soundness versus feeding length. Comparisons between these casting trials and casting trials performed more than forty years ago by Pellini and the SFSA are quite good and appear reasonable. Comparisons between the current SFSA feeding rules and feeding rules based on the minimum Niyama criterion reveal that the Niyama-based rules are generally less conservative. The niyama-based rules also agree better with both the trials presented here, and the casting trails performed by Pellini an d the SFSA years ago. Furthermore, the use of the Niyama criterion to predict centerline shrinkage for horizontally fed plate sections has a theoretical basis according to the casting literature reviewed here. These results strongly support the use of improved feeding rules for horizontal plate sections based on the Niyama criterion, which can be tailored to the casting conditions for a given alloy and to a desired level of soundness. The reliability and repeatability of ASTM shrinkage x-ray ratings was investigated in a statistical study performed on 128 x-rays, each of which were rated seven different times. A manual ''Feeding and Risering Guidelines for Steel Castings' is given in this final report. Results of casting trials performed to test unconventional techniques for improving casting yield are presented. These use a stacked arrangement of castings and riser pressurization to increase the casting yield. Riser pressurization was demonstrated to feed a casting up to four time s the

  13. Atmospheric Nitrogen Fluorescence Yield

    NASA Technical Reports Server (NTRS)

    Adams, J. H., Jr.; Christl, M. J.; Fountain, W. F.; Gregory, J. C.; Martens, K. U.; Sokolsky, Pierre; Whitaker, Ann F. (Technical Monitor)

    2001-01-01

    Several existing and planned experiments estimate the energies of ultra-high energy cosmic rays from air showers using the atmospheric nitrogen fluorescence. The nitrogen fluorescence yield from air shower electrons depends on the atmospheric composition. We will discuss the uncertainties in the fluorescence yield form electrons in the real atmosphere and describe a concept for a small balloon payload to measure the atmospheric fluorescence yield as a function of attitude.

  14. Phenanthrene biodegradation kinetics in unsaturated soils

    SciTech Connect

    Johnson, C.R.; Scow, K.M.

    1995-12-31

    Organic compounds when sorbed to soil solids are thought to be unavailable to soil microorganisms. The biodegradation kinetics of sorbed chemicals should thus be influenced by sorption/desorption processes as well as by the metabolic capacities of soil microbes. In the research, phenanthrene, a hydrophobic polyaromatic hydrocarbon, was used as a model compound to investigate the biodegradation kinetics of strongly sorbing organic compounds in soil. Biodegradation kinetics for phenanthrene in seven soils with moisture contents near field capacity were measured during a six and one half month experiment. Phenanthrene biodegradation rates initially increased in all soils and then declined. The declining portion of the biodegradation rate versus time plots exhibited either first order or biphasic kinetics. Both first order and biphasic kinetics are consistent with models which link microbial degradation to substrate sorption/desorption from equilibrium and kinetically controlled sorption sites. No single rate constant or analytical expression adequately captured the complexity of the observed biodegradation rates. This result is again consonant with a process derived from coupled biological and physical systems. Biodegradation kinetics were quantified using a combination of fitted and descriptive parameters. Significant correlations exist between several of the descriptive parameters. The correlations observed between descriptive biodegradation parameters mirror correlations expected from the hypothesized underlying biological process and help evince the influence this underlying process exerts on observed biodegradation kinetics.

  15. Kinetic and stoichiometric characterization for efficient enhanced biological phosphorus removal (EBPR) process at high temperatures.

    PubMed

    Liau, Kee Fui; Shoji, Tadashi; Ong, Ying Hui; Chua, Adeline Seak May; Yeoh, Hak Koon; Ho, Pei Yee

    2015-04-01

    A recently reported stable and efficient EBPR system at high temperatures around 30 °C has led to characterization of kinetic and stoichiometric parameters of the Activated Sludge Model no. 2d (ASM2d). Firstly, suitable model parameters were selected by identifiability analysis. Next, the model was calibrated and validated. ASM2d was found to represent the processes well at 28 and 32 °C except in polyhyroxyalkanoate (PHA) accumulation of the latter. The values of the kinetic parameters for PHA storage (q PHA), polyphosphate storage (q PP) and growth (μ PAO) of polyphosphate-accumulating organisms (PAOs) at 28 and 32 °C were found to be much higher than those reported by previous studies. Besides, the value of the stoichiometric parameter for the requirement of polyphosphate for PHA storage (Y PO4) was found to decrease as temperature rose from 28 to 32 °C. Values of two other stoichiometric parameters, i.e. the growth yield of heterotrophic organisms (Y H) and PAOs (Y PAO), were high at both temperatures. These calibrated parameters imply that the extremely active PAOs of the study were able to store PHA, store polyphosphate and even utilize PHA for cell growth. Besides, the parameters do not follow the Arrhenius correlation due to the previously reported unique microbial clade at 28 and 32 °C, which actively performs EBPR at high temperatures.

  16. Predictions of biochar yield and elemental composition during torrefaction of forest residues.

    PubMed

    Bach, Quang-Vu; Chen, Wei-Hsin; Chu, Yen-Shih; Skreiberg, Øyvind

    2016-09-01

    In this work, a direct prediction method coupled with a consecutive reaction model is developed to estimate the biochar yield and elemental composition in a biomass torrefaction process. Norway forest residues were chosen as feedstock and torrefied at different temperatures under nitrogen atmosphere in a thermogravimetric analyzer. Obtained data were modeled to predict the mass loss during torrefaction. Distributions of initial, intermediate and final solid products as well as torrefaction kinetic parameters are reported. Thereafter, a direct method to predict the elemental composition of biochar is introduced. The results show that the decomposition of initial biomass to form an intermediate solid has higher conversion rate than the degradation of the intermediate. Moreover, the predictions reproduce well the experimental thermogravimetric curves and show composition trends similar to the literature data. This method is useful for the design and optimization of industrial torrefaction processes with predictable biochar yield and elemental composition.

  17. Production of high hydroxytyrosol yields via tyrosol conversion by Pseudomonas aeruginosa immobilized resting cells.

    PubMed

    Bouallagui, Zouhaier; Sayadi, Sami

    2006-12-27

    An immobilized whole cell system was successfully performed to produce the most powerful antioxidant, hydroxytyrosol. Bioconversion of tyrosol into hydroxytyrosol was achieved via the immobilization of Pseudomonas aeruginosa resting cells in calcium alginate beads. Immobilization was advantageous as it allows immobilized cells to tolerate a greater tyrosol concentration than free cells. The bioconversion yield reached 86% in the presence of 5 g L-1 of tyrosol when cells immobilized in alginate beads were carried out in single batches. Evaluation of kinetic parameters showed the maintenance of the same catalytic efficiency expressed as Kcat/Km for both free and immobilized cells. The use of immobilized cells in repeated batches demonstrated a notable activity stabilization since the biocatalyst reusability was extended for at least four batches with a molar yield greater than 85%.

  18. Calculation of the total electron excitation cross section in the Born approximation using Slater wave functions for the Li (2s yields 2p), Li (2s yields 3p), Na (3s yields 4p), Mg (3p yields 4s), Ca (4s yields 4p) and K (4s yields 4p) excitations. M.S. Thesis

    NASA Technical Reports Server (NTRS)

    Simsic, P. L.

    1974-01-01

    Excitation of neutral atoms by inelastic scattering of incident electrons in gaseous nebulae were investigated using Slater Wave functions to describe the initial and final states of the atom. Total cross sections using the Born Approximation are calculated for: Li(2s yields 2p), Na(3s yields 4p), k(4s yields 4p). The intensity of emitted radiation from gaseous nebulae is also calculated, and Maxwell distribution is employed to average the kinetic energy of electrons.

  19. 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.

  20. Reaction kinetics of the hydrothermal treatment of lignin.

    PubMed

    Zhang, Bo; Huang, Hua-Jiang; Ramaswamy, Shri

    2008-03-01

    Lignins derived from abundant and renewable resources are nontoxic and extremely versatile in performance, qualities that have made them increasingly important in many industrial applications. We have shown recently that liquefaction of lignin extracted from aspen wood resulted in a 90% yield of liquid. In this paper, the hydrothermal treatment of five types of lignin and biomass residues was studied: Kraft pine lignin provided by MeadWestvaco, Kraft pine lignin from Sigma-Aldrich, organosolv lignin extracted from oat hull, the residues of mixed southern hardwoods, and switchgrass after hydrolysis. The yields were found dependent on the composition or structure of the raw materials, which may result from different pretreatment processes. We propose a kinetic model to describe the hydrothermal treatment of Kraft pine lignin and compare it with another model from the literature. The kinetic parameters of the presented model were estimated, including the reaction constants, the pre-exponential factor, and the activation energy of the Arrhenius equations. Results show that the presented model is well in agreement with the experiments.

  1. 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.

  2. Kinetics study on biomass pyrolysis for fuel gas production.

    PubMed

    Chen, Guan-Yi; Fang, Meng-Xiang; Andries, J; Luo, Zhong-Yang; Spliethoff, H; Cen, Ke-Fa

    2003-01-01

    Kinetic knowledge is of great importance in achieving good control of the pyrolysis and gasification process and optimising system design. An overall kinetic pyrolysis scheme is therefore addressed here. The kinetic modelling incorporates the following basic steps: the degradation of the virgin biomass materials into primary products (tar, gas and semi-char), the decomposition of primary tar into secondary products and the continuous interaction between primary gas and char. The last step is disregarded completely by models in the literature. Analysis and comparison of predicted results from different kinetic schemes and experimental data on our fixed bed pyrolyser yielded very positive evidence to support our kinetic scheme.

  3. The effects of intensity on V̇O2 kinetics during incremental free swimming.

    PubMed

    de Jesus, Kelly; Sousa, Ana; de Jesus, Karla; Ribeiro, João; Machado, Leandro; Rodríguez, Ferran; Keskinen, Kari; Vilas-Boas, João Paulo; Fernandes, Ricardo J

    2015-09-01

    Swimming and training are carried out with wide variability in distances and intensities. However, oxygen uptake kinetics for the intensities seen in swimming has not been reported. The purpose of this study was to assess and compare the oxygen uptake kinetics throughout low-moderate to severe intensities during incremental swimming exercise. We hypothesized that the oxygen uptake kinetic parameters would be affected by swimming intensity. Twenty male trained swimmers completed an incremental protocol of seven 200-m crawl swims to exhaustion (0.05 m·s(-1) increments and 30-s intervals). Oxygen uptake was continuously measured by a portable gas analyzer connected to a respiratory snorkel and valve system. Oxygen uptake kinetics was assessed using a double exponential regression model that yielded both fast and slow components of the response of oxygen uptake to exercise. From low-moderate to severe swimming intensities changes occurred for the first and second oxygen uptake amplitudes (P ≤ 0.04), time constants (P = 0.01), and time delays (P ≤ 0.02). At the heavy and severe intensities, a notable oxygen uptake slow component (>255 mL·min(-1)) occurred in all swimmers. Oxygen uptake kinetics whilst swimming at different intensities offers relevant information regarding cardiorespiratory and metabolic stress that might be useful for appropriate performance diagnosis and training prescription.

  4. Kinetics of stress fibers

    NASA Astrophysics Data System (ADS)

    Stachowiak, Matthew R.; O'Shaughnessy, Ben

    2008-02-01

    Stress fibers are contractile cytoskeletal structures, tensile actomyosin bundles which allow sensing and production of force, provide cells with adjustable rigidity and participate in various processes such as wound healing. The stress fiber is possibly the best characterized and most accessible multiprotein cellular contractile machine. Here we develop a quantitative model of the structure and relaxation kinetics of stress fibers. The principal experimentally known features are incorporated. The fiber has a periodic sarcomeric structure similar to muscle fibers with myosin motor proteins exerting contractile force by pulling on actin filaments. In addition the fiber contains the giant spring-like protein titin. Actin is continuously renewed by exchange with the cytosol leading to a turnover time of several minutes. In order that steady state be possible, turnover must be regulated. Our model invokes simple turnover and regulation mechanisms: actin association and dissociation occur at filament ends, while actin filament overlap above a certain threshold in the myosin-containing regions augments depolymerization rates. We use the model to study stress fiber relaxation kinetics after stimulation, as observed in a recent experimental study where some fiber regions were contractile and others expansive. We find that two distinct episodes ensue after stimulation: the turnover-overlap system relaxes rapidly in seconds, followed by the slow relaxation of sarcomere lengths in minutes. For parameter values as they have been characterized experimentally, we find the long time relaxation of sarcomere length is set by the rate at which actin filaments can grow or shrink in response to the forces exerted by the elastic and contractile elements. Consequently, the stress fiber relaxation time scales inversely with both titin spring constant and the intrinsic actin turnover rate. The model's predicted sarcomere velocities and contraction-expansion kinetics are in good

  5. 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.