Science.gov

Sample records for yield kinetic parameters

  1. Estimation of yield, maintenance, and product formation kinetic parameters in anaerobic fermentations.

    PubMed

    Oner, M D; Erickson, L E; Yang, S S

    1984-12-01

    In many anaerobic fermentation processes, high energy bonds in adenosine triphosphate (ATP) are produced when available electrons are converted from organic substrate into extracellular organic products such as ethanol. The true growth yield and maintenance parameters are directly related to the product formation kinetic parameters for these anaerobic processes. Methods are presented which allow all of the experimental measurements to be used simultaneously to estimate these parameters. Results are presented for several different anaerobic fermentations. PMID:18551674

  2. A robust method for the joint estimation of yield coefficients and kinetic parameters in bioprocess models.

    PubMed

    Vastemans, V; Rooman, M; Bogaerts, Ph

    2009-01-01

    Bioprocess model structures that require nonlinear parameter estimation, thus initialization values, are often subject to poor identification performances because of the uncertainty on those initialization values. Under some conditions on the model structure, it is possible to partially circumvent this problem by an appropriate decoupling of the linear part of the model from the nonlinear part of it. This article provides a procedure to be followed when these structural conditions are not satisfied. An original method for decoupling two sets of parameters, namely, kinetic parameters from maximum growth, production, decay rates, and yield coefficients, is presented. It exhibits the advantage of requiring only initialization of the first subset of parameters. In comparison with a classical nonlinear estimation procedure, in which all the parameters are freed, results show enhanced robustness of model identification with regard to parameter initialization errors. This is illustrated by means of three simulation case studies: a fed-batch Human Embryo Kidney cell cultivation process using a macroscopic reaction scheme description, a process of cyclodextrin-glucanotransferase production by Bacillus circulans, and a process of simultaneous starch saccharification and glucose fermentation to lactic acid by Lactobacillus delbrückii, both based on a Luedeking-Piret model structure. Additionally, perspectives of the presented procedure in the context of systematic bioprocess modeling are promising. PMID:19455623

  3. Prediction of Microbial Growth Rate versus Biomass Yield by a Metabolic Network with Kinetic Parameters

    PubMed Central

    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. PMID:22792053

  4. 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)

  5. Spectroscopic determination of kinetic parameters for frequency sweeping Alfven eigenmodes

    SciTech Connect

    Lesur, M.; Idomura, Y.; Shinohara, K.; Garbet, X.

    2010-12-15

    A method for analyzing fundamental kinetic plasma parameters, such as linear drive and external damping rate, based on experimental observations of chirping Alfven eigenmodes, is presented. The method, which relies on new semiempirical laws for nonlinear chirping characteristics, consists of fitting procedures between the so-called Berk-Breizman model and the experiment in a quasiperiodic chirping regime. This approach is applied to the toroidicity induced Alfven eigenmode (TAE) on JT-60 Upgrade (JT-60U) [N. Oyama et al., Nucl. Fusion 49, 104007 (2009)], which yields an estimation of the kinetic parameters and suggests the existence of TAEs far from marginal stability. Two collision models are considered, and it is shown that dynamical friction and velocity-space diffusion are essential to reproduce nonlinear features observed in experiments. The results are validated by recovering measured growth and decay of perturbation amplitude and by estimating collision frequencies from experimental equilibrium data.

  6. Evaluation of objective functions for estimation of kinetic parameters

    SciTech Connect

    Muzic, Raymond F. Jr.; Christian, Bradley T.

    2006-02-15

    There is growing interest in quantitatively analyzing in vivo image data, as this facilitates objective comparisons and measurement of effect. In this regard, people increasingly turn to pharmacokinetic models and estimation of parameters of such models. In this work several parameter estimation methodologies were compared within the context of the most common pharmacokinetic model used in positron emission tomography imaging to describe glucose metabolism and receptor-ligand interactions at tracer concentrations. Simulated data were generated with 1000 realizations at each of 5 different noise levels. Estimates of the kinetic parameters were made for each realization using seven iterative, nonlinear estimation methodologies: ordinary least squares (OLS), weighted least squares (WLS), penalized weighted least squares (PWLS), iteratively reweighted least squares (IRLS), and variations of extended least squares (ELS0, ELS1, ELS3). Additionally, generalized linear least squares (GLLS) was also used. With relatively noise-free data, the iterative nonlinear estimation methods generally produced low-bias, high-precision parameter estimates, whereas with GLLS the bias was more prominent. Greater distinction between the estimation methods was seen at the higher, more realistic noise levels, with ELS and IRLS methods generally achieving better precision than the other methods. At the high noise levels WLS, GLLS, and PWLS yielded parameter estimates with large bias (>200%) for some kinetic parameters. In general, there are more favorable estimator methodologies than the frequently employed WLS. Methods that determine values of weights based on model output--IRLS, ELS0, ELS1 and ELS3--generally perform better than methods that determine values of weights based directly on the experimental data.

  7. Comments on extracting the resonance strength parameter from yield data

    NASA Astrophysics Data System (ADS)

    Croft, Stephen; Favalli, Andrea

    2015-10-01

    The F(α,n) reaction is the focus of on-going research in part because it is an important source of neutrons in the nuclear fuel cycle which can be exploited to assay nuclear materials, especially uranium in the form of UF6 [1,2]. At the present time there remains some considerable uncertainty (of the order of ±20%) in the thick target integrated over angle (α,n) yield from 19F (100% natural abundance) and its compounds as discussed in [3,4]. An important thin target cross-section measurement is that of Wrean and Kavanagh [5] who explore the region from below threshold (2.36 MeV) to approximately 3.1 MeV with fine energy resolution. Integration of their cross-section data over the slowing down history of a stopping α-particle allows the thick target yield to be calculated for incident energies up to 3.1 MeV. This trend can then be combined with data from other sources to obtain a thick target yield curve over the wider range of interest to the fuel cycle (roughly threshold to 10 MeV to include all relevant α-emitters). To estimate the thickness of the CaF2 target they used, Wrean and Kavanagh separately measured the integrated yield of the 6.129 MeV γ-rays from the resonance at 340.5 keV (laboratory α-particle kinetic energy) in the 19F(p,αγ) reaction. To interpret the data they adopted a resonance strength parameter of (22.3±0.8) eV based on a determination by Becker et al [6]. The value and its uncertainty directly affects the thickness estimate and the extracted (α,n) cross-section values. In their citation to Becker et al's work, Wrean and Kavanagh comment that they did not make use of an alternative value of (23.7±1.0) eV reported by Croft [7] because they were unable to reproduce the value from the data given in that paper. The value they calculated for the resonance strength from the thick target yield given by Croft was 21.4 eV. The purpose of this communication is to revisit the paper by Croft published in this journal and specifically to explain the origin of the reported resonance strength. Fortunately the original notes spanning the period 12 January 1988 to 16 January 1990 were available to consult. In hindsight there is certainly a case of excessive brevity to rectify. In essence the step requiring explanation is how to compute the resonance strength, ωγ, from the reported thick target resonance yield Y.

  8. New post-yield fracture toughness parameters for engineering materials

    SciTech Connect

    Wang, T.J.; Kuang, Z.B.

    1995-11-01

    Micromechanics approach is employed to investigate the constraint effect on post-yield fracture toughness. Relationships between the conventional post-yield fracture toughness values, J{sub lc} and {delta}{sub c}, and crack tip constraint characterized by the crack tip stress triaxiality are derived on the basis of an improved micromechanics criterion for ductile fracture. Then, new crack tip parameters J{sub mc} and {delta}{sub mc} (and associated new criteria for ductile fracture) are proposed, in which the effects of crack tip deformation and constraint are taken into account. Experiments show that both J{sub mc} and {delta}{sub mc} are material constant independent of stress state or specimen geometry. They can serve as new post-yield fracture toughness parameters to differentiate the fracture toughness of engineering materials, which provide new approaches for fracture assessments of engineering structures.

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

    PubMed

    Aceves-Lara, C A; Aguilar-Garnica, E; Alcaraz-Gonzlez, V; Gonzlez-Reynoso, O; Steyer, J P; Dominguez-Beltran, J L; Gonzlez-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. PMID:16180459

  10. Kinetic parameters of some tissue equivalent thermoluminescence materials

    NASA Astrophysics Data System (ADS)

    Kitis, G.; Furetta, C.; Prokic, M.; Prokic, V.

    2000-06-01

    The paper reports a study on the kinetic parameters of some thermoluminescent tissue equivalent materials recently prepared in Vinca Institute: Li2B4O7:Mn,Si, Li2B4O7:Cu, Li2B4O7:Cu,In and MgB4O7:Dy,Na. The kinetics parameters have been determined using several methods. The temperature lag effect, which could produce large errors in the parameters' determination when they are determined using high heating rates, has also been taken into consideration.

  11. 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. PMID:26551654

  12. 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

  13. Determining Kinetic Parameters for Isothermal Crystallization of Glasses

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  14. LDEF's map experiment foil perforations yield hypervelocity impact penetration parameters

    NASA Technical Reports Server (NTRS)

    Mcdonnell, J. A. M.

    1992-01-01

    The space exposure of LDEF for 5.75 years, forming a host target in low earth orbit (LEO) orbit to a wide distribution of hypervelocity particulates of varying dimensions and different impact velocities, has yielded a multiplicity of impact features. Although the projectile parameters are generally unknown and, in fact not identical for any two impacts on a target, the great number of impacts provides statistically meaningful basis for the valid comparison of the response of different targets. Given sufficient impacts for example, a comparison of impact features (even without knowledge of the project parameters) is possible between: (1) differing material types (for the same incident projectile distribution); (2) differing target configurations (e.g., thick and thin targets for the same material projectiles; and (3) different velocities (using LDEF's different faces). A comparison between different materials is presented for infinite targets of aluminum, Teflon, and brass in the same pointing direction; the maximum finite-target penetration (ballistic limit) is also compared to that of the penetration of similar materials comprising of a semi-infinite target. For comparison of impacts on similar materials at different velocities, use is made of the pointing direction relative to LDEF's orbital motion. First, however, care must be exercised to separate the effect of spatial flux anisotropies from those resulting from the spacecraft velocity through a geocentrically referenced dust distribution. Data comprising thick and thin target impacts, impacts on different materials, and in different pointing directions is presented; hypervelocity impact parameters are derived. Results are also shown for flux modeling codes developed to decode the relative fluxes of Earth orbital and unbound interplanetary components intercepting LDEF. Modeling shows the west and space pointing faces are dominated by interplanetary particles and yields a mean velocity of 23.5 km/s at LDEF, corresponding to a V(infinity) Earth approach velocity = 20.9 km/s. Normally resolved average impact velocities on LDEF's cardinal point faces are shown. As 'excess' flux on the east, north, and south faces is observed, compatible with an Earth orbital component below some 5 microns in particle diameter.

  15. Incremental parameter estimation of kinetic metabolic network models

    PubMed Central

    2012-01-01

    Background An efficient and reliable parameter estimation method is essential for the creation of biological models using ordinary differential equation (ODE). Most of the existing estimation methods involve finding the global minimum of data fitting residuals over the entire parameter space simultaneously. Unfortunately, the associated computational requirement often becomes prohibitively high due to the large number of parameters and the lack of complete parameter identifiability (i.e. not all parameters can be uniquely identified). Results In this work, an incremental approach was applied to the parameter estimation of ODE models from concentration time profiles. Particularly, the method was developed to address a commonly encountered circumstance in the modeling of metabolic networks, where the number of metabolic fluxes (reaction rates) exceeds that of metabolites (chemical species). Here, the minimization of model residuals was performed over a subset of the parameter space that is associated with the degrees of freedom in the dynamic flux estimation from the concentration time-slopes. The efficacy of this method was demonstrated using two generalized mass action (GMA) models, where the method significantly outperformed single-step estimations. In addition, an extension of the estimation method to handle missing data is also presented. Conclusions The proposed incremental estimation method is able to tackle the issue on the lack of complete parameter identifiability and to significantly reduce the computational efforts in estimating model parameters, which will facilitate kinetic modeling of genome-scale cellular metabolism in the future. PMID:23171810

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

    PubMed

    Anthon, Gordon E; Barrett, Diane M

    2002-07-01

    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. PMID:12083894

  17. Kinetics and yields of pesticide biodegradation at low substrate concentrations and under conditions restricting assimilable organic carbon.

    PubMed

    Helbling, Damian E; Hammes, Frederik; Egli, Thomas; Kohler, Hans-Peter E

    2014-02-01

    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

  18. 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

  19. Albite [yields] jadeite + quartz transformation in rock: Mechanism and kinetics

    SciTech Connect

    Bohlen, S.R.; Kirby, S.H. ); Hacker, B.R.

    1992-01-01

    Recent work on the calcite [yields] aragonite transformation using fully dense marble revealed significant differences from earlier experiments on powders and single-crystals. The reaction rate is retarded by a factor of > 1,000 and reaction mechanisms and resultant textures are considerably more complex. Stimulated by this, the authors conducted a study of the albite [yields] jadeite + quartz/coesite transformation in a fully dense albitite. Again the results are in marked contrast with previous powder-based studies of this archetypal metamorphic reaction. Solid cores of albitite were held at temperatures of 500-1,200 C and at pressure oversteps of 500 MPa into the jadeite + quartz stability field for 1--8 days in piston-cylinder apparatus. Samples that were dried in vacuum transformed appreciably only at temperatures in excess of 1,000 C. At all grain boundaries there is subequal transformation to micron-scale intergrowths of jadeite + quartz. Samples that were vacuum-impregnated with 1 wt% water contain jadeite + quartz to temperatures as low as 600 C. In contrast to the dried samples, transformation is much less homogeneous. The jadeite + quartz intergrowths do not form rows of subparallel crystals on grain boundaries, but rather are flower-shaped clusters that radiate outward from single nucleation sites at 3-grain edges and 4-grain corners. Compared to powders, pressure oversteps a factor of 10 greater are necessary to induce equivalent reaction in albitite. The sluggishness of this reaction has important implications for the evolution of the lower continental crust and subducting oceanic crust in terms of their (1) seismic velocity profiles, (2) petrological evolution, and (3) buoyancy forces, stresses and vertical crustal movements connected with densification and dilatational reactions.

  20. 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

    2015-05-01

    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. PMID:25723920

  1. [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+). PMID:26672292

  2. Cell population kinetic parameters for acute epidermal reactions in man

    SciTech Connect

    Cohen, L.

    1986-11-01

    Cell population kinetic parameters for acute reactions in squamous epithelium were estimated using available data on skin tolerance doses. Roughly equivalent doses for kilovoltage radiation delivered in equal daily fractions, as reported by F. Ellis (Br. J. Radiol. 15, 348-350 (1942)) and by R. Paterson (The Treatment of Malignant Disease by Radium and X-Rays. Edward Arnold, London, 1948), were combined with data for nonstandard fractionation at longer intervals of 1 or 2 weeks. By analyzing the combined data set, well-determined parameters could be derived. The data show that repopulation, with a potential cell doubling time of about 7 days, must occur in irradiated human skin, though this may possibly be limited to no more than seven doublings. The parameters derived are distinctly different from those associated with late-reacting dose-limiting tissues. The main difference is the steeper initial slope of the computed survival curve, that is a larger J parameter (multitarget model) or a larger alpha component (linear-quadratic model).

  3. 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.

  4. 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. PMID:16053157

  5. 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.

  6. Impact of sustaining a controlled residual growth on polyhydroxybutyrate yield and production kinetics in Cupriavidus necator.

    PubMed

    Grousseau, Estelle; Blanchet, Elise; Dlris, Stphane; Albuquerque, Maria G E; Paul, Etienne; Uribelarrea, Jean-Louis

    2013-11-01

    In this study a complementary modeling and experimental approach was used to explore how growth controls the NADPH generation and availability, and the resulting impact on PHB (polyhydroxybutyrate) yields and kinetics. The results show that the anabolic demand allowed the NADPH production through the Entner-Doudoroff (ED) pathway, leading to a high maximal theoretical PHB production yield of 0.89 C mole C mole(-1); whereas without biomass production, NADPH regeneration is only possible via the isocitrate dehydrogenase leading to a theoretical yield of 0.67 C mole C mole(-1). Furthermore, the maximum specific rate of NADPH produced at maximal growth rate (to fulfil biomass requirement) was found to be the maximum set in every conditions, which by consequence determines the maximal PHB production rate. These results imply that sustaining a controlled residual growth improves the PHB specific production rate without altering production yield. PMID:24035890

  7. Kinetic Parameters of Denitrification in a River Continuum†

    PubMed Central

    García-Ruiz, Roberto; Pattinson, Sarah N.; Whitton, Brian A.

    1998-01-01

    Kinetic parameters for nitrate reduction in intact sediment cores were investigated by using the acetylene blockage method at five sites along the Swale-Ouse river system in northeastern England, including a highly polluted tributary, R. Wiske. The denitrification rate in sediment containing added nitrate exhibited a Michaelis-Menten-type curve. The concentration of nitrate for half-maximal activity (Kmap) by denitrifying bacteria increased on passing downstream from 13.1 to 90.4 μM in the main river, but it was highest (640 μM) in the Wiske. The apparent maximal rate (Vmaxap) ranged between 35.8 and 324 μmol of N m−2 h−1 in the Swale-Ouse (increasing upstream to downstream), but it was highest in the Wiske (1,194 μmol N m−2 h−1). A study of nitrous oxide (N2O) production at the same time showed that rates ranged from below the detection limit (0.05 μmol of N2O-N m−2 h−1) at the headwater site to 27 μmol of N2O-N m−2 h−1 at the downstream site. In the Wiske the rate was up to 570 μmol of N2O-N m−2 h−1, accounting for up to 80% of total N gas production. PMID:9647826

  8. Evaluation of kinetic parameters of a sulfur-limestone autotrophic denitrification biofilm process.

    PubMed

    Zeng, Hui; Zhang, Tian C

    2005-12-01

    In this study, four kinetic parameters of autotrophic denitrifiers in fixed-bed sulfur-limestone autotrophic denitrification (SLAD) columns were evaluated. The curve-matching method was used by conducting 22 non-steady-state tests for estimation of half-velocity constant, K(s) and maximum specific substrate utilization rate, k. To estimate the bacteria yield coefficient, Y and the decay coefficient, k(d), two short term batch tests (before and after the starvation of the autotrophic denitrifiers) were conducted using a fixed-bed SLAD column where the biofilm was fully penetrated by nitrate-N. It was found that K(s) = 0.398 mg NO(3-)-N/l, k = 0.15 d(-1), k(d) = 0.09-0.12 d(-1), and Y = 0.85-1.11 g VSS/g NO(3-)-N. Our results are consistent with those obtained from SLAD biofilm processes, but different from those obtained from suspended-growth systems with thiosulfate or sulfur powders as the S source. The method developed in this study might be useful for estimation of four Monod-type kinetic parameters in other biofilm processes. However, cautions must be given when the estimated parameters are used because the measurements of the biomass and the biofilm thickness could be further improved, and the assumption of sulfur being a non-limiting substrate needs to be proved. PMID:16289671

  9. 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 475-500C 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. PMID:26407347

  10. The use of automated parameter searches to improve ion channel kinetics for neural modeling.

    PubMed

    Hendrickson, Eric B; Edgerton, Jeremy R; Jaeger, Dieter

    2011-10-01

    The voltage and time dependence of ion channels can be regulated, notably by phosphorylation, interaction with phospholipids, and binding to auxiliary subunits. Many parameter variation studies have set conductance densities free while leaving kinetic channel properties fixed as the experimental constraints on the latter are usually better than on the former. Because individual cells can tightly regulate their ion channel properties, we suggest that kinetic parameters may be profitably set free during model optimization in order to both improve matches to data and refine kinetic parameters. To this end, we analyzed the parameter optimization of reduced models of three electrophysiologically characterized and morphologically reconstructed globus pallidus neurons. We performed two automated searches with different types of free parameters. First, conductance density parameters were set free. Even the best resulting models exhibited unavoidable problems which were due to limitations in our channel kinetics. We next set channel kinetics free for the optimized density matches and obtained significantly improved model performance. Some kinetic parameters consistently shifted to similar new values in multiple runs across three models, suggesting the possibility for tailored improvements to channel models. These results suggest that optimized channel kinetics can improve model matches to experimental voltage traces, particularly for channels characterized under different experimental conditions than recorded data to be matched by a model. The resulting shifts in channel kinetics from the original template provide valuable guidance for future experimental efforts to determine the detailed kinetics of channel isoforms and possible modulated states in particular types of neurons. PMID:21243419

  11. Measurement of the asymmetry parameter for the decay {Lambda}{yields}p{pi}{sup +}

    SciTech Connect

    Ablikim, M.; Bai, J. Z.; Bai, Y.; Cai, X.; Chen, H. S.; Chen, H. X.; Chen, J. C.; Chen, Jin; Chen, Y. B.; Chu, Y. P.; Deng, Z. Y.; Du, S. X.; Fang, J.; Fu, C. D.; Gao, C. S.; Gu, S. D.; Guo, Y. N.; He, K. L.; Heng, Y. K.; Hu, H. M.

    2010-01-01

    Based on a sample of 58x10{sup 6}J/{psi} decays collected with the BESII detector at the BEPC, the {Lambda} decay parameter {alpha}{sub {Lambda}}for {Lambda}{yields}p{pi}{sup +} is measured using about 9000 J/{psi}{yields}{Lambda}{Lambda}{yields}pp{pi}{sup +{pi}-} decays. A fit to the joint angular distributions yields {alpha}{sub {Lambda}({Lambda}{yields}p{pi}{sup +})}=-0.755{+-}0.083{+-}0.063, where the first error is statistical, and the second systematic.

  12. Growth parameter and yield component response of field corn to simulated acid rain

    SciTech Connect

    Banwart, W.L.; Porter, P.M.; Ziegler, E.L.; Hassett, J.J.

    1988-01-01

    Acid rain occurs in the midwest. Studies to date have suggested minimal yield response of field corn to acid rain. However, small but significant reductions in yield have been shown for some cultivars under extreme conditions. To define further these yield changes the study examined the effect of simulated acid rain on parameters associated with corn yield. Cultivars B73 x Mo17 and Pioneer 3377 were shielded from ambient rain by two movable rain exclusion shelters. Six simulated rain treatments were applied biweekly within these shelters through the use of a nozzle distribution system. For the most part, growth and yield parameters were unaffected by simulated rain treatment. While the only significant yield reduction was a contrast of pH 3.0 and the average of all other treatments for B73 x Mo17, the reduction appears to be the result both of slightly fewer ears and slightly less successful ear fill.

  13. Kinetic and stoichiometric parameters estimation in a nitrifying bubble column through "in-situ" pulse respirometry.

    PubMed

    Ordaz, Alberto; Oliveira, Catarina S; Aguilar, Ricardo; Carrin, Manuel; Ferreira, Eugnio C; Alves, Madalena; Thalasso, Frdric

    2008-05-01

    This article proposes a simple "in-situ" pulse respirometric method for the estimation of four important kinetic and stoichiometric parameters. The method is validated in a suspended biomass nitrifying reactor for the determination of (i) maximum oxygen uptake rate (OUR(ex)max), (ii) oxidation yield (f(E)), (iii) biomass growth yield (f(S)), and (iv) affinity constant (K(S)). OUR(ex)max and f(E) were directly obtained from respirograms. In the presented case study, a minimum substrate pulse of 10 mgNH(4) (+)-N L(-1) was necessary to determine OUR(ex)max which was 61.15 +/- 4.09 mgO(2) L(-1) h(-1) (5 repetitions). A linear correlation (r(2) = 0.93) obtained between OUR(ex)max and the biomass concentration in the reactor suggests that biomass concentration can be estimated from respirometric experiments. The substrate oxidation yield, f(E), was determined along 60 days of continuous operation with an average error of 5.6%. The biomass growth yield was indirectly estimated from the substrate oxidation yield f(E). The average obtained value (0.10 +/- 0.04 mgCOD mg(-1)COD) was in accordance with the f(S) estimation by the traditional COD mass balance method under steady-state conditions (0.09 +/- 0.01). The affinity constant K(S) was indirectly estimated after fitting the ascending part of the respirogram to a theoretical model. An average value of 0.48 +/- 0.08 mgNH(4) (+)-N L(-1) was obtained, which is in the range of affinity constants reported in the literature for the nitrification process (0.16-2 mgNH(4) (+)-N L(-1)). PMID:18078297

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

    PubMed

    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

    2015-04-21

    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

  15. 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

  16. Identification of the catalytic mechanism and estimation of kinetic parameters for fumarase.

    PubMed

    Mescam, Muriel; Vinnakota, Kalyan C; Beard, Daniel A

    2011-06-17

    The enzyme fumarase catalyzes the reversible hydration of fumarate to malate. The reaction catalyzed by fumarase is critical for cellular energetics as a part of the tricarboxylic acid cycle, which produces reducing equivalents to drive oxidative ATP synthesis. A catalytic mechanism for the fumarase reaction that can account for the kinetic behavior of the enzyme observed in both isotope exchange studies and initial velocity studies has not yet been identified. In the present study, we develop an 11-state kinetic model of the enzyme based on the current consensus on its catalytic mechanism and design a series of experiments to estimate the model parameters and identify the major flux routes through the mechanism. The 11-state mechanism accounts for competitive binding of inhibitors and activation by different anions, including phosphate and fumarate. The model is identified from experimental time courses of the hydration of fumarate to malate obtained over a wide range of buffer and substrate concentrations. Further, the 11-state model is found to effectively reduce to a five-state model by lumping certain successive steps together to yield a mathematically less complex representation that is able to match the data. Analysis suggests the primary reaction route of the catalytic mechanism, with fumarate binding to the free unprotonated enzyme and a proton addition prior to malate release in the fumarate hydration reaction. In the reverse direction (malate dehydration), malate binds the protonated form of the enzyme, and a proton is generated before fumarate is released from the active site. PMID:21498518

  17. 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. PMID:12721476

  18. 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 6.24g/L, respectively in bioreactor with an overall PHB production rate of 0.75g/h. Bioreactor cultivation studies demonstrated that the specific biomass and PHB yield on sucrose was 0.37 and 0.29g/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. PMID:22915234

  19. Statistical analysis of nonlinear parameter estimation for Monod biodegradation kinetics using bivariate data.

    PubMed

    Knightes, C D; Peters, C A

    2000-07-20

    A nonlinear regression technique for estimating the Monod parameters describing biodegradation kinetics is presented and analyzed. Two model data sets were taken from a study of aerobic biodegradation of the polycyclic aromatic hydrocarbons (PAHs), naphthalene and 2-methylnaphthalene, as the growth-limiting substrates, where substrate and biomass concentrations were measured with time. For each PAH, the parameters estimated were: q(max), the maximum substrate utilization rate per unit biomass; K(S), the half-saturation coefficient; and Y, the stoichiometric yield coefficient. Estimating parameters when measurements have been made for two variables with different error structures requires a technique more rigorous than least squares regression. An optimization function is derived from the maximumlikelihood equation assuming an unknown, nondiagonal covariance matrix for the measured variables. Because the derivation is based on an assumption of normally distributed errors in the observations, the error structures of the regression variables were examined. Through residual analysis, the errors in the substrate concentration data were found to be distributed log-normally, demonstrating a need for log transformation of this variable. The covariance between ln C and X was found to be small but significantly nonzero at the 67% confidence level for NPH and at the 94% confidence level for 2MN. The nonlinear parameter estimation yielded unique values for q(max), K(S), and Y for naphthalene. Thus, despite the low concentrations of this sparingly soluble compound, the data contained sufficient information for parameter estimation. For 2-methylnaphthalene, the values of q(max) and K(S) could not be estimated uniquely; however, q(max)/K(S) was estimated. To assess the value of including the relatively imprecise biomass concentration data, the results from the bivariate method were compared with a univariate method using only the substrate concentration data. The results demonstrated that the bivariate data yielded a better confidence in the estimates and provided additional information about the model fit and model adequacy. The combination of the value of the bivariate data set and their nonzero covariance justifies the need for maximum likelihood estimation over the simpler nonlinear least squares regression. PMID:10861395

  20. 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

  1. 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…

  2. 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.

  3. Kinetics of the reaction O + ClO yields Cl + O2

    NASA Technical Reports Server (NTRS)

    Margitan, J. J.

    1984-01-01

    The kinetics of the reaction O + ClO yields Cl + O2 (k1) were studied by using resonance fluorescence to monitor the decay of O atoms which had been generated from the laser photolysis of ClO. A discharge flow system was used to generate the ClO and its concentration was measured directly by multipass absorption spectrometry. The results are k1(298) = (4.2 + or -0.8) x 10 to the -11th cu cm/s (including systematic errors) with E/R determined to lie in the range + or - 200 K. The literature data are reviewed and a composite value of k1(T) = 6.0 x 10 to the -11th exp-(100/T) is recommended for stratospheric modeling calculations. The atmospheric implications of the revised rate constant are discussed briefly.

  4. Rapid estimation of kinetic parameters for thermal decomposition of penicillins by modulated thermogravimetric analysis.

    PubMed

    Miller, Jonathan M; Kale, Uma J; Lau, Siu-Man Kelvin; Greene, Landon; Wang, Henry Y

    2004-04-01

    Modulated thermogravimetic analysis (MTGA) is evaluated for the rapid estimation of thermal stability using several penicillin antibiotics as model compounds. The MTGA technique utilizes an oscillatory temperature program to obtain Arrhenius kinetic parameters through a mass loss during thermal degradation. To evaluate the reliability of this technique, activation energies (E(a)), log pre-exponential factor (logZ), and log first order rate constants (logk) obtained by MTGA for the thermal decomposition of ampicillin anhydrous, ampicillin trihydrate, ampicillin sodium salt, and penicillin G potassium salt are compared to existing literature values. The logk values estimated by MTGA agreed well with literature values when the weight loss observed by MTGA was shown to be due to the first decomposition step of the compound. The E(a) and logZ values determined by MTGA did not consistently agree with literature values as these parameters increased with decreasing heating rate (beta). The increase in E(a) and logZ values with decreasing beta seemed to offset each other to some extent to yield a relatively consistent logk estimate regardless of beta. PMID:15030881

  5. 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 Pearsons correlation coefficient is over 0.6 for all countries. In contrast, on a grid scale, the correspondence is still high in most grids regardless of the countries. However, the model showed comparatively low reproducibility in the slope areas, such as around the Rocky Mountains in South Dakota, around the Great Xing'anling Mountains in Heilongjiang, and around the Brazilian Plateau. As there is a wide-ranging local climate conditions in the complex terrain, such as the slope of mountain, the GCM grid-scale weather inputs is likely one of major sources of error. The results of this study highlight the benefits of the perturbed-parameter ensemble method in simulating crop yield on a GCM grid scale: (1) the posterior PDF of parameter could quantify the uncertainty of parameter value of the crop model associated with the local crop production aspects; (2) the method can explicitly account for the uncertainty of parameter value in the crop model simulations; (3) the method achieve a Monte Carlo approximation of probability of sub-grid scale yield, accounting for the nonlinear response of crop yield to weather and management; (4) the method is therefore appropriate to aggregate the simulated sub-grid scale yields to a grid-scale yield and it may be a reason for high performance of the model in capturing inter-annual variation of yield.

  6. 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 extraction of polyphenols from honeysuckle and dynamic had not been reported. In this study, using cellulase to extract polyphenols from honeysuckle is first applied. Moreover, uniform design was used to optimize process and kinetic model of extraction was established to analyze the characteristics of enzymatic extraction, in order to improve the yield of polyphenols from honeysuckle and make maximum use of Lonicerae flos, which provide references for industrial production.

  7. 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

  8. 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…

  9. 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.

  10. 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.

  11. 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. PMID:11753918

  12. 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.

  13. 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. PMID:25063973

  14. 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

  15. The determination of pulsed reactor kinetic behavior based upon prepulse parameter measurements

    NASA Astrophysics Data System (ADS)

    Minnema, Douglas Martin

    This dissertation develops a method to allow the determination of the SPR III fast burst reactor's kinetic behavior based on pre-pulse measurements. The purpose is to reduce the vulnerability of pulse operations to human errors, and to improve understanding of the reactor's interactions with experiments. First, the operational history of SPR III over a wide range of experimental conditions was evaluated, looking for relationships among measured parameters. Second, the physical bases for the observed relationships were determined. Finally, the theoretical models were modified to account for the observed relationships. Computer simulations were utilized to validate the resulting models. Fast Burst Reactors (FBR) are a unique class of research reactors that generate high yield, self-terminated, short duration power pulses. Electromechanical shutdown mechanisms cannot respond quickly enough to truncate a pulse once it has been initiated, but can only mitigate post-pulse heat generation. These reactors are designed to accommodate a wide range of experimental conditions. Therefore, potential exists for an unintentional over-insertion of reactivity during a pulse operation, producing a yield capable of damaging the reactor. The safe operation of an FBR depends directly upon the knowledge, experience, skill, and judgment of the operating staff to compensate for the limitations of safety systems. This dissertation enhances the safety of these operations by identifying the mechanisms by which experiments influence the reactor's behavior, and improving the operating staff's ability to determine the impact of those influences on the reactor. Using pre-pulse reactivity measurements, this dissertation allows the operating staff to predict the change in the reactivity worth of the pulse element caused by the experiment before actually measuring it. It is also demonstrated that experiments neutronically behave as loosely-coupled reflectors, and the kinetic behavior of the reflected reactor during a pulse can be adequately modeled by treating the reflected neutrons in a manner analogous to additional delayed neutron groups. Observed changes in the reactor's negative temperature feedback coefficient due to experiments are also evaluated and explained.

  16. Sputtering Yields for C60 and Au3 Bombardment of Water Ice as a Function of Incident Kinetic Energy

    PubMed Central

    Russo, Michael F.; Szakal, Christopher; Kozole, Joseph; Winograd, Nicholas; Garrison, Barbara J.

    2008-01-01

    The total sputtering yields for water ice due to kiloelectronvolt cluster bombardment have been measured and compared to the predictions made by the mesoscale energy deposition footprint (MEDF) model. For C60 bombardment the experimental yield varies almost linearly from 820 water molecule equivalents at an incident kinetic energy of 10 keV to 10100 water molecule equivalents at a kinetic energy of 120 keV. For Au3 bombardment the experimental yield varies almost linearly from 630 water molecule equivalents at an incident energy of 10 keV and rises to 1200 water molecule equivalents at 25 keV. The MEDF model is used to calculate relative yield trends with respect to incident energy using short time molecular dynamics simulations. The results of these calculations indicate that the model can effectively predict the yield trends observed for these two clusters in experiments, although there is a consistent overestimate of the predicted induced C60 yield. It is hypothesized that this overestimate can be explained by the absence of reactions and ionization processes in the current simulations. Despite this omission experimental yield trends can be accurately predicted using relatively small amounts of computer time. The success of the model in predicting the yield of water from ice films using a variety of energies and projectiles suggests this approach may greatly aid in the optimization of experimental configurations. PMID:17503768

  17. 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

  18. 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)

  19. Describing protein structure: a general algorithm yielding complete helicoidal parameters and a unique overall axis.

    PubMed

    Sklenar, H; Etchebest, C; Lavery, R

    1989-01-01

    We present a general and mathematically rigorous algorithm which allows the helicoidal structure of a protein to be calculated starting from the atomic coordinates of its peptide backbone. This algorithm yields a unique curved axis which quantifies the folding of the backbone and a full set of helicoidal parameters describing the location of each peptide unit. The parameters obtained form a complete and independent set and can therefore be used for analyzing, comparing, or reconstructing protein backbone geometry. This algorithm has been implemented in a computer program named P-Curve. Several examples of its possible applications are discussed. PMID:2608659

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

    PubMed

    B?rzi?, Agris; Acti?, 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. PMID:24729295

  1. Thermochemical and kinetic parameters for hydrogen bonded clusters, derived from avalanche condensation flux measurements

    NASA Astrophysics Data System (ADS)

    Bauer, S. H.; Zhang, Yi-Xue; Wilcox, C. F.

    2000-06-01

    The kinetic molecular model (KMM) was applied to recently reported extensive measurements of condensation flux levels developed under homogeneous conditions from supersaturated vapors of water and n-pentanol, in inert gas carriers. These data span wide ranges in temperatures and critical supersaturations (css). The calculated fluxes reproduced those observed (defined: number of droplets generated per cm3-s) within a factor 2, utilizing a narrow range of adjustable parameters. From the derived kinetic and thermochemical parameters one may derive estimates of size-dependent entropies for clusters. Thus, the derived entropy per mole of a 13 unit cluster of water molecules, at 233 K, is 233 eu.

  2. Parameter estimations for the kinetics of de-hydriding reaction between zirconium-cobalt and hydrogen

    SciTech Connect

    Chang, M. H.; Cho, S.; Lee, E. S.; Ahn, M. Y.; Kim, D. H.; Jung, J. J.; Chung, H.; Shim, M.; Song, K. M.; Kim, D.; Yoshida, H.

    2008-07-15

    The de-hydriding reaction between ZrCo and hydrogen is the most important role of delivering hydrogen isotopes for fusion energies. Many researchers experimented in various conditions and estimated the relationship between ZrCo and hydrogen. In this study the kinetic approaches are performed using numerical simulations between ZrCo and hydrogen. Two kinds of parameter estimations are performed for the equilibrium pressure and the kinetics modeling and those are validated by the good agreement between predicted and experimental data. Based on the numerical simulation with obtained parameters, more rapid rates of de-hydriding reaction can be achieved with lower pressure and higher temperature. (authors)

  3. A comparative study of seed yield parameters in Arabidopsis thaliana mutants and transgenics.

    PubMed

    Van Daele, Inge; Gonzalez, Nathalie; Vercauteren, Ilse; de Smet, Lien; Inz, Dirk; Roldn-Ruiz, Isabel; Vuylsteke, Marnik

    2012-05-01

    Because seed yield is the major factor determining the commercial success of grain crop cultivars, there is a large interest to obtain more understanding of the genetic factors underlying this trait. Despite many studies, mainly in the model plant Arabidopsis thaliana, have reported transgenes and mutants with effects on seed number and/or seed size, knowledge about seed yield parameters remains fragmented. This study investigated the effect of 46 genes, either in gain- and/or loss-of-function situations, with a total of 64 Arabidopsis lines being examined for seed phenotypes such as seed size, seed number per silique, number of inflorescences, number of branches on the main inflorescence and number of siliques. Sixteen of the 46 genes, examined in 14 Arabidopsis lines, were reported earlier to directly affect in seed size and/or seed number or to indirectly affect seed yield by their involvement in biomass production. Other genes involved in vegetative growth, flower or inflorescence development or cell division were hypothesized to potentially affect the final seed size and seed number. Analysis of this comprehensive data set shows that of the 14 lines previously described to be affected in seed size or seed number, only nine showed a comparable effect. Overall, this study provides the community with a useful resource for identifying genes with effects on seed yield and candidate genes underlying seed QTL. In addition, this study highlights the need for more thorough analysis of genes affecting seed yield. PMID:22332878

  4. Interstitial insulin kinetic parameters for a 2-compartment insulin model with saturable clearance.

    PubMed

    Pretty, Christopher G; Le Compte, Aaron; Penning, Sophie; Fisk, Liam; Shaw, Geoffrey M; Desaive, Thomas; Chase, J Geoffrey

    2014-05-01

    Glucose-insulin system models are commonly used for identifying insulin sensitivity. With physiological, 2-compartment insulin kinetics models, accurate kinetic parameter values are required for reliable estimates of insulin sensitivity. This study uses data from 6 published microdialysis studies to determine the most appropriate parameter values for the transcapillary diffusion rate (n(I)) and cellular insulin clearance rate (n(C)). The 6 studies (12 data sets) used microdialysis techniques to simultaneously obtain interstitial and plasma insulin concentrations. The reported plasma insulin concentrations were used as input and interstitial insulin concentrations were simulated with the interstitial insulin kinetics sub-model. These simulated results were then compared to the reported interstitial measurements and the most appropriate set of parameter values was determined across the 12 data sets by combining the results. Interstitial insulin kinetic parameters values n(I)=n(C)=0.0060 min⁻¹ were shown to be the most appropriate. These parameter values are associated with an effective, interstitial insulin half-life, t(½)=58 min, within the range of 25-130 min reported by others. PMID:24548900

  5. 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. PMID:24065871

  6. A Comparison of Isoconversional and Model-Fitting Approaches to Kinetic Parameter Estimation and Application Predictions

    SciTech Connect

    Burnham, A K

    2006-05-17

    Chemical kinetic modeling has been used for many years in process optimization, estimating real-time material performance, and lifetime prediction. Chemists have tended towards developing detailed mechanistic models, while engineers have tended towards global or lumped models. Many, if not most, applications use global models by necessity, since it is impractical or impossible to develop a rigorous mechanistic model. Model fitting acquired a bad name in the thermal analysis community after that community realized a decade after other disciplines that deriving kinetic parameters for an assumed model from a single heating rate produced unreliable and sometimes nonsensical results. In its place, advanced isoconversional methods (1), which have their roots in the Friedman (2) and Ozawa-Flynn-Wall (3) methods of the 1960s, have become increasingly popular. In fact, as pointed out by the ICTAC kinetics project in 2000 (4), valid kinetic parameters can be derived by both isoconversional and model fitting methods as long as a diverse set of thermal histories are used to derive the kinetic parameters. The current paper extends the understanding from that project to give a better appreciation of the strengths and weaknesses of isoconversional and model-fitting approaches. Examples are given from a variety of sources, including the former and current ICTAC round-robin exercises, data sets for materials of interest, and simulated data sets.

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

    PubMed Central

    Haque, Mohammad Mahfuzul; Tejero, Jess; 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

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

    PubMed Central

    Satya, Eswari Jujjavarapu; Venkateswarlu, Chimmiri

    2013-01-01

    Abstract 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. PMID:24065871

  9. Determination of Kinetic Parameters within a Single Nonisothermal On-Flow Experiment by Nanoliter NMR Spectroscopy.

    PubMed

    Gomez, M Victoria; Rodriguez, Antonio M; de la Hoz, Antonio; Jimenez-Marquez, Francisco; Fratila, Raluca M; Barneveld, Peter A; Velders, Aldrik H

    2015-10-20

    Conventional methods to determine the kinetic parameters for a certain reaction require multiple, separate isothermal experiments, resulting in time- and material-consuming processes. Here, an approach to determine the kinetic information within a single nonisothermal on-flow experiment is presented, consuming less than 10 ?mol of reagents and having a total measuring time of typically 10 min. This approach makes use of a microfluidic NMR chip hyphenated to a continuous-flow microreactor and is based on the capabilities of the NMR chip to analyze subnanomole quantities of material in the 25 nL detection volume. Importantly, useful data are acquired from the microreactor platform in specific isothermal and nonisothermal frames. A model fitting the experimental data enables rapid determination of kinetic parameters, as demonstrated for a library of isoxazole and pyrazole derivatives. PMID:26383715

  10. 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. PMID:21520020

  11. Evaluation of kinetic parameters for water soluble crystals by thermo gravimetric analysis

    NASA Astrophysics Data System (ADS)

    Rama, S.; Surendra Dilip, C.; Perumal, Rajesh Narayana

    2015-01-01

    This work elevates the relevance of kinetic parameters of nucleation and thermal decomposition for water soluble crystals. The positive soluble Potassium Dihydrogen Phosphate (KDP) and negative soluble Lithium Sulfate Monohydrate (LSMH) materials were chosen for the kinetic evaluation. The results obtained from the classical nucleation theory are verified with the kinetic parameters which are evaluated from thermo gravimetric analysis. Nucleation parameters of a crystallization process such as interfacial energy (?), volume free energy (?Gv), critical energy barrier for nucleation (?G*), radius of the critical nucleus (r*) and nucleation rate (J) of the positive (KDP) and negative solubility (LSMH) crystals are determined from the classical nucleation theory of solubility-enthalpy relation. The kinetic parameters viz. the order of reaction, enthalpy, Gibbs free energy of activation, frequency factor, and entropy of activation are obtained from the TG based models viz. Horowitz-Metzger, Coats-Redfern and Piloyan-Novikova. The effect of varying temperature with relative variation on Gibbs free energy for both positive and negative solubility crystals is also discussed. The developed model holds good for both positive and negative solubility crystals.

  12. 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…

  13. 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

  14. Influence of predeformation and ageing of an Al-Zn-Mg alloy. 2: Modeling of precipitation kinetics and yield stress

    SciTech Connect

    Deschamps, A.; Brechet, Y.

    1998-12-11

    The authors present a model for precipitation kinetics integrating nucleation growth and coarsening. This model allows the description of competitive kinetics of heterogenous and homogeneous precipitation. The precipitation model is coupled to a model for structural hardening predicting the yield stress. This structural hardening model includes the possibility of taking into account the distribution of precipitate size and strength. The model is applied to experimental data on age hardening of Al-Zn-Mg alloys, and allows to describe the effect of a prestraining on the subsequent aging behavior.

  15. Parameters-related uncertainty in modeling sugar cane yield with an agro-Land Surface Model

    NASA Astrophysics Data System (ADS)

    Valade, A.; Ciais, P.; Vuichard, N.; Viovy, N.; Ruget, F.; Gabrielle, B.

    2012-12-01

    Agro-Land Surface Models (agro-LSM) have been developed from the coupling of specific crop models and large-scale generic vegetation models. They aim at accounting for the spatial distribution and variability of energy, water and carbon fluxes within soil-vegetation-atmosphere continuum with a particular emphasis on how crop phenology and agricultural management practice influence the turbulent fluxes exchanged with the atmosphere, and the underlying water and carbon pools. A part of the uncertainty in these models is related to the many parameters included in the models' equations. In this study, we quantify the parameter-based uncertainty in the simulation of sugar cane biomass production with the agro-LSM ORCHIDEE-STICS on a multi-regional approach with data from sites in Australia, La Reunion and Brazil. First, the main source of uncertainty for the output variables NPP, GPP, and sensible heat flux (SH) is determined through a screening of the main parameters of the model on a multi-site basis leading to the selection of a subset of most sensitive parameters causing most of the uncertainty. In a second step, a sensitivity analysis is carried out on the parameters selected from the screening analysis at a regional scale. For this, a Monte-Carlo sampling method associated with the calculation of Partial Ranked Correlation Coefficients is used. First, we quantify the sensitivity of the output variables to individual input parameters on a regional scale for two regions of intensive sugar cane cultivation in Australia and Brazil. Then, we quantify the overall uncertainty in the simulation's outputs propagated from the uncertainty in the input parameters. Seven parameters are identified by the screening procedure as driving most of the uncertainty in the agro-LSM ORCHIDEE-STICS model output at all sites. These parameters control photosynthesis (optimal temperature of photosynthesis, optimal carboxylation rate), radiation interception (extinction coefficient), root uptake of water (root profile), and transpiration and respiration (stomatal conductance, growth and maintenance respiration coefficients). We find that the optimal carboxylation rate and optimal photosynthesis temperature parameters contribute most to the uncertainty in NPP and GPP simulations whereas stomatal conductance is the most sensitive parameter controlling SH, followed by optimal photosynthesis temperature and optimal carboxylation rate. The spatial variation of the ranked correlation between input parameters and output variables is well explained by rain and temperature drivers, suggesting that climate mediated regionally different sensitivities of modeled sugarcane yield to the model parameters, for Australia and Brazil.

  16. 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

  17. Parameter estimation in stochastic chemical kinetic models using derivative free optimization and bootstrapping

    PubMed Central

    Srivastava, Rishi; Rawlings, James B.

    2014-01-01

    Recent years have seen increasing popularity of stochastic chemical kinetic models due to their ability to explain and model several critical biological phenomena. Several developments in high resolution fluorescence microscopy have enabled researchers to obtain protein and mRNA data on the single cell level. The availability of these data along with the knowledge that the system is governed by a stochastic chemical kinetic model leads to the problem of parameter estimation. This paper develops a new method of parameter estimation for stochastic chemical kinetic models. There are three components of the new method. First, we propose a new expression for likelihood of the experimental data. Second, we use sample path optimization along with UOBYQA-Fit, a variant of of Powells unconstrained optimization by quadratic approximation, for optimization. Third, we use a variant of Efrons percentile bootstrapping method to estimate the confidence regions for the parameter estimates. We apply the parameter estimation method in an RNA dynamics model of E. coli. We test the parameter estimates obtained and the confidence regions in this model. The testing of the parameter estimation method demonstrates the efficiency, reliability, and accuracy of the new method. PMID:24920866

  18. Genetic parameters of test-day milk yield in Guzer cattle under tropical conditions.

    PubMed

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

    2015-01-01

    The objective of this study was to estimate genetic parameters for test-day milk yield (TDMY) in Guzer 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 Guzer cattle. PMID:26535676

  19. Splitting parameter yield (SPY): A program for semiautomatic analysis of shear-wave splitting

    NASA Astrophysics Data System (ADS)

    Zaccarelli, Lucia; Bianco, Francesca; Zaccarelli, Riccardo

    2012-03-01

    SPY is a Matlab algorithm that analyzes seismic waveforms in a semiautomatic way, providing estimates of the two observables of the anisotropy: the shear-wave splitting parameters. We chose to exploit those computational processes that require less intervention by the user, gaining objectivity and reliability as a result. The algorithm joins the covariance matrix and the cross-correlation techniques, and all the computation steps are interspersed by several automatic checks intended to verify the reliability of the yields. The resulting semiautomation generates two new advantages in the field of anisotropy studies: handling a huge amount of data at the same time, and comparing different yields. From this perspective, SPY has been developed in the Matlab environment, which is widespread, versatile, and user-friendly. Our intention is to provide the scientific community with a new monitoring tool for tracking the temporal variations of the crustal stress field.

  20. Constraints on effective field theory parameters for the {Lambda}N{yields}NN transition

    SciTech Connect

    Perez-Obiol, Axel; Parreno, Assumpta; Julia-Diaz, Bruno

    2011-08-15

    The relation between the low-energy constants appearing in the effective field theory description of the {Lambda}N{yields}NN transition potential and the parameters of the one-meson-exchange model previously developed is obtained. We extract the relative importance of the different exchange mechanisms included in the meson picture by means of a comparison to the corresponding operational structures appearing in the effective approach. The ability of this procedure to obtain the weak baryon-baryon-meson couplings for a possible scalar exchange is also discussed.

  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. Comparison of gasification kinetics parameters of different types of nuclear graphite

    SciTech Connect

    El-Genk, M. S.; Tournier, J. M. P.

    2012-07-01

    A chemical-reaction kinetics model of nuclear graphite gasification has recently been developed and successfully validated with gasification rate measurements for nuclear graphite grades of IG-110, IG-430, NBG-18 and NBG-25. The model employs 4 elementary chemical reactions with applicable parameters, including the values and Gaussian-like distributions of the specific activation energies, the pre-exponential coefficients for adsorption of oxygen and desorption of CO and CO{sub 2} gases, and the surface area of free active sites. These parameters are determined from the reported measurements of the total gasification and transient weight loss using a multi-parameter optimization algorithm. The determined chemical kinetics parameters for IG-100 and NB-25 are nearly the same, but slightly different from those for NBG-18 and IG-430. The initial specific area of free active sites is inversely proportional to the square root of the mass or volume of the graphite specimens used in experiments. The recommended chemical kinetics parameters in this paper for these grades of nuclear graphite should be applicable to future safety analysis of high-temperature gas cooled reactors in the unlikely event of a massive air ingress accident. (authors)

  3. 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.

  4. 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

    2015-06-01

    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. We propose that synergy gains by such processes form a basis for further progress towards high efficiency and yield for a global project on artificial photosynthesis. Finally, we look at artificial photosynthesis research in The Netherlands and use this as an example of how an interdisciplinary approach is beneficial to artificial photosynthesis research. We conclude with some of the potential societal consequences of a large-scale roll out of artificial photosynthesis. PMID:26052428

  5. 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. We propose that synergy gains by such processes form a basis for further progress towards high efficiency and yield for a global project on artificial photosynthesis. Finally, we look at artificial photosynthesis research in The Netherlands and use this as an example of how an interdisciplinary approach is beneficial to artificial photosynthesis research. We conclude with some of the potential societal consequences of a large-scale roll out of artificial photosynthesis. PMID:26052428

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

    PubMed Central

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

    2015-01-01

    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 Legendres 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 Legendres 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. PMID:26323397

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

    PubMed

    Canaza-Cayo, Ali William; Lopes, Paulo Svio; 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. PMID:26323397

  8. Characterisation of sugar cane straw waste as pozzolanic material for construction: Calcining temperature and kinetic parameters

    SciTech Connect

    Frias, Moises

    2007-07-01

    This paper reports on the influence of calcining temperature (800 and 1000 deg. C) on the pozzolanic activation of sugar cane straw (SCS). The reaction kinetics of SCS ash-lime mixtures were inferred from physicochemical characteristics (X-ray diffraction patterns and thermogravimetry analysis. The fitting of a kinetic-diffusive model to the experimental data (fixed lime versus time) allowed the computing of the kinetic parameters (reaction rate constant) of the pozzolanic reaction. Results obtained confirm that the sugar cane straw ash (SCSA) calcined at 800 and 1000 deg. C have properties indicative of very high pozzolanic activity. No influence of calcining temperature on the pozzolanic activity was observed. Also, no crystalline compounds during the pozzolanic reaction were identified up to 90 days of reaction. Environmental durability and strength of the consequential mortars remain to be assessed.

  9. Thermoluminescence systems with two or more glow peaks described by anomalous kinetic parameters

    SciTech Connect

    Levy, P.W.

    1983-01-01

    The usual first and second order TL kinetic expressions are based on a number of assumptions, including the usually unstated assumption that charges released from one type of trap, giving rise to one glow peak, are not retrapped on other types of traps, associated with other glow peaks. Equations have been developed describing TL systems in which charges released from one type of trap may be retrapped in other types of traps. Called interactive kinetic equations, they are quite simple but have been studied by numerical methods. In particular, glow curves computed from the interactive kinetic equations have been regarded as data and analyzed by fitting them to the usual first and second order kinetic expressions. All of the anomalous features described above are reproduced. For example, usually the computed glow peaks are well fitted by the first and second order expressions over their upper 60 to 80% but not in the wings. This explains why the usual analysis methods, especially those utilizing peak temperature, full width, etc. appear to describe such peaks. Often unrealistic kinetic parameters are often obtained. Furthermore, the computed glow curves often reproduce the observed dependence on dose.

  10. Continuum theory of lumping approach to model hydrocracking kinetics for prediction of paraffins, naphthenes & aromatics (PNAs) yields

    SciTech Connect

    Narasimhan, C.S.L.; Verma, R.P.

    1995-12-31

    Modeling of hydrocracking kinetics capturing the chemistry of the process has been a continuous endeavor for the researchers. Very few approaches have been formulated so far, which either over simplify the problem or require large number of computation parameters for acceptable solution. The present paper proposes a novel and elegant approach based on continuum theory of lumping, which attempts to follow the process chemistry closely to model the complex hydrocracking kinetics for prediction of paraffins, naphthenes and aromatics (PNAs) in the product mixture. The model predictions match well with reported experimental results.

  11. Impact of initial conditions on extant microbial kinetic parameter estimates: application to chlorinated ethene dehalorespiration.

    PubMed

    Huang, Deyang; Lai, Yenjung; Becker, Jennifer G

    2014-03-01

    Monod kinetics are the foundation of mathematical models of many environmentally important biological processes, including the dehalorespiration of chlorinated ethene groundwater contaminants. The Monod parameters--qmax, the maximum specific substrate utilization rate, and KS, the half-saturation constant--are typically estimated in batch assays, which are superficially simple to prepare and maintain. However, if initial conditions in batch assays are not chosen carefully, it is unlikely that the estimated parameter values will be meaningful because they do not reflect microbial activity in the environmental system of interest, and/or they are not mathematically identifiable. The estimation of qmax and KS values that are highly correlated undoubtedly contributes significantly to the wide range in reported parameter values and may undermine efforts to use mathematical models to demonstrate the occurrence of natural attenuation or predict the performance of engineered bioremediation approaches. In this study, a series of experimental and theoretical batch kinetic assays were conducted using the tetrachloroethene-respirer Desulfuromonas michiganensis to systematically evaluate the effects of initial batch assay conditions, expressed as the initial substrate (S0)-to-initial biomass concentration (X0) ratio (S0/X0) and the S0/KS ratio on parameter correlation. An iterative approach to obtain meaningful Monod parameter estimates was developed and validated using three different strains and can be broadly applied to a range of other substrates and populations. While the S0/X0 ratio is critical to obtaining kinetic parameter estimates that reflect in situ microbial activity, this study shows that optimization of the S0/KS ratio is key to minimizing Monod parameter correlation. PMID:23963272

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

    PubMed

    Passala, 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%. PMID:22030272

  13. Kinetic Parameter Estimation Using a Closed-Form Expression via Integration-by-Parts

    PubMed Central

    Zeng, Gengsheng L.; Hernandez, Andrew; Kadrmas, Dan J.; Gullberg, Grant T.

    2012-01-01

    Dynamic emission computed tomographic imaging with compartment modeling can quantify in vivo physiologic processes, eliciting more information regarding underlying molecular disease processes than is obtained from static imaging. However, estimation of kinetic rate parameters for multi-compartment models can be computationally demanding and problematic due to local minima. A number of techniques for kinetic parameter estimation have been studied and are in use today, generally offering a tradeoff between computation time, robustness of fit, and flexibility with differing sets of assumptions. This paper presents a means to eliminate all differential operations by using the integration-by-parts method to provide closed-form formulas, so that the mathematical model is less sensitive to data sampling and noise. A family of closed-form formulas can be obtained. Computer simulations show that the proposed method is robust without having to specify the initial condition. PMID:22951326

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

    PubMed

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

    2016-04-01

    Kinetic models based on first principles are becoming common place in heterogeneous catalysis because of their ability to interpret experimental data, identify the rate-controlling step, guide experiments and predict novel materials. To overcome the tremendous computational cost of estimating parameters of complex networks on metal catalysts, approximate quantum mechanical calculations are employed that render models potentially inaccurate. Here, by introducing correlative global sensitivity analysis and uncertainty quantification, we show that neglecting correlations in the energies of species and reactions can lead to an incorrect identification of influential parameters and key reaction intermediates and reactions. We rationalize why models often underpredict reaction rates and show that, despite the uncertainty being large, the method can, in conjunction with experimental data, identify influential missing reaction pathways and provide insights into the catalyst active site and the kinetic reliability of a model. The method is demonstrated in ethanol steam reforming for hydrogen production for fuel cells. PMID:27001728

  15. Experimental determination of kinetic parameters for crystallizing amorphous NiTi thin films

    NASA Astrophysics Data System (ADS)

    Lee, Hoo-Jeong; Ni, Hai; Wu, David T.; Ramirez, Ainissa G.

    2005-09-01

    The crystallization of amorphous NiTi thin films was studied using in situ transmission electron microscopy (TEM) methods. Samples were subjected to heating conditions within the microscope and the microstructural development was monitored and recorded. The nucleation rate and the growth rate were determined experimentally by noting the number of new grains per frame and their change in size. These parameters were compared to the conventional method of kinetic analysis using the Johnson-Mehl-Avrami-Kolmogorov (JMAK) theory. In it, the amount transformed is related to fitting parameters that describe the overall crystallization rate. The individual kinetic rates found directly with the TEM methods have considerable agreement with the overall rate determined by the conventional JMAK analysis. This quantitative analysis provides the groundwork for the control of microstructures and properties in NiTi shape memory alloy thin films.

  16. 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. PMID:24583217

  17. The kinetic relationship between the C-550 absorbance change, the reduction of Q(delta A320) and the variable fluorescence yield change in chloroplasts at room temperature.

    PubMed

    Melis, A; Schreiber, U

    1979-07-10

    The light minus dark difference spectrum and the kinetics of the indicator pigment C-550 have been measured at room temperature in isolate, envelope-free chloroplasts in the presence of 3-(3' ,4'-dichlorophenyl)-1,1-dimethylurea (DCMU). The C-550 spectrum indicates a band shift with peaks at 540 and 550 nm and has an isobestic point at 545 nm. On the assumption of 400 chlorophyll molecules per electron transfer chain the differentaial extinction coefficient delta epsilon (540-550) is calculated to be approximately 5 mM-1 . CM-1. The kinetics of the C-550 absorbance change, occurring upin the onset of continuous illumination, are shown to be biphasic and strictly correlated with the kinetics of the complementary area measured from the fluorescence induction curve under identical cinditions and with those of the absorbance increase at 320 nm due to photoreduction of Q. The lighted-induced change in these three parameters can be described as a function of the variable fluorescence yield change occurring under the same conditions. Such functions are non-linear and reveal a heterogeneous dependence of the variable fluorescence yield on the fraction of closed System II reaction centers. It is concluded that for every molecule of the primary electron acceptor Q of Photosystem II that is photochemically reduced there corresponds an equivalent change in the absorbance of the indicator pigment C-550 and in the size of the complementary area. Ths, C-550 and area are two valid parameters for monitoring the primary photochemical activity of System II at the room temperature. PMID:465486

  18. Simultaneous segmentation, kinetic parameter estimation, and uncertainty visualization of dynamic PET images.

    PubMed

    Saad, Ahmed; Smith, Ben; Hamarneh, Ghassan; Mller, Torsten

    2007-01-01

    We develop a segmentation technique for dynamic PET incorporating the physiological parameters for different regions via kinetic modeling. We demonstrate the usefulness of our technique on fifteen [11C]Raclopride simulated PET images. We show qualitatively and quantitatively that the physiologically based algorithm outperforms two classical segmentation techniques. Further, we derive a formula to compute and visualize the uncertainty encountered during the segmentation. PMID:18044633

  19. Reaction kinetic parameters for ion transport from steady-state current-voltage curves.

    PubMed Central

    Gradmann, D; Klieber, H G; Hansen, U P

    1987-01-01

    This study demonstrates possible ways to estimate the rate constants of reaction kinetic models for ion transport from steady-state current-voltage data as measured at various substrate concentrations. This issue is treated theoretically by algebraic reduction and extension of a reaction kinetic four-state model for uniport. Furthermore, an example for application is given; current-voltage data from an open K+ selective channel (Schroeder, J.I., R. Hedrich, and J.M. Fernandez, 1984, Nature (Lond.), 312:361-362) supplemented by some new data have been evaluated. The analysis yields absolute numerical estimates of the 14 rate constants of a six-state model, which is discussed in a wider context. PMID:2437973

  20. 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.

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

    PubMed Central

    2014-01-01

    Background A major challenge in mathematical modeling of biological systems is to determine how model parameters contribute to systems dynamics. As biological processes are often complex in nature, it is desirable to address this issue using a systematic approach. Here, we propose a simple methodology that first performs an enrichment test to find patterns in the values of globally profiled kinetic parameters with which a model can produce the required system dynamics; this is then followed by a statistical test to elucidate the association between individual parameters and different parts of the systems dynamics. Results We demonstrate our methodology on a prototype biological system of perfect adaptation dynamics, namely the chemotaxis model for Escherichia coli. Our results agreed well with those derived from experimental data and theoretical studies in the literature. Using this model system, we showed that there are motifs in kinetic parameters and that these motifs are governed by constraints of the specified system dynamics. Conclusions A systematic approach based on enrichment statistical tests has been developed to elucidate the relationships between model parameters and the roles they play in affecting system dynamics of a prototype biological network. The proposed approach is generally applicable and therefore can find wide use in systems biology modeling research. PMID:24428922

  2. Effects of parameters affecting biomass yield and thermal behaviour of Chlorella vulgaris.

    PubMed

    Bhola, Virthie; Desikan, Ramesh; Santosh, Sheena Kumari; Subburamu, Karthikeyan; Sanniyasi, Elumalai; Bux, Faizal

    2011-03-01

    Conventional fossil fuels are facing a global challenge which lead scientists to explore alternative fuel production from biological sources. The algae-based fuels are gaining rapid attention as it has potential to replace petroleum-based fuels. An indigenous high lipid producing microalgae was isolated from a freshwater pond in the KwaZulu-Natal province of South Africa. The isolate was later identified as Chlorella vulgaris, based on partial 28S large subunit ribosomal RNA gene sequence. The growth kinetics, pyrolytic characteristics and photosynthetic efficiency of Chlorella was evaluated in vitro. The optimized conditions for higher biomass yield of the selected strain were at 4% CO(2), 0.5 g l(-1) NO(3) and 0.04 g l(-1) PO(4), respectively. The pulse amplitude modulation results indicated that C. vulgaris could withstand a light intensity ranging from 150 to 350 ?mol photons m(-2)s(-1). Further increase in light intensity resulted in a decline of the electron transport rate. Carbon fixation rate, lipid content and calorific value of C. vulgaris was 6.17 mg l(-1)h(-1), 21% and 17.44 kJ g(-1), respectively. The pyrolitic studies under inert atmosphere at different heating rates of 15, 30, 40 and 50C min(-1) from ambient temperature to 800C showed that the overall final weight loss recorded for the four different heating rates was in the range of 78.9-81%. These studies could be useful to appraise the biofuel potential of the isolated C. vulgaris strain, which can later be taken for pilot scale production. PMID:21185776

  3. Reaction-kinetic parameters of glycidamide as determinants of mutagenic potency.

    PubMed

    Silvari, V; Haglund, J; Jenssen, D; Golding, B T; Ehrenberg, L; Trnqvist, M

    2005-02-01

    Values for reaction-kinetic parameters of electrophiles can be used to predict mutagenic potency. One approach employs the Swain-Scott relationship for comparative kinetic studies of electrophilic agents reacting with nucleophiles. In this way glycidamide (GA), the putatively mutagenic/carcinogenic metabolite of acrylamide, was assessed by determining the rates of reaction with different nucleophiles. The rate constants (kNu) were determined using the "supernucleophile" cob(I)alamin [Cbl(I)] as an analytical tool. The Swain-Scott parameters for GA were compared with those of ethylene oxide (EO). The substrate constants, s values, for GA and for EO were found to be 1.0 and 0.93, respectively. The reaction rates at low values of nucleophilic strength (n=1-3), corresponding to oxygens in DNA, were determined to be 2-3.5 times higher for GA compared to EO. GA was also more reactive than EO towards other nucleophiles (n=0-6.4). The mutagenic potency of GA was determined in Chinese hamster ovary cells (hprt mutations in CHO-AA8 cells per dose unit with gamma-radiation as reference standard). The potency of GA was estimated to be about three mutations per 10(5) cells and mMh corresponding to about 40 rad-equ./mMh. A preliminary comparison of the mutagenic potency (per mMh and as rad-equivalents) of GA and EO shows an approximately seven times higher potency for GA. A higher mutagenic potency of GA compared to EO is compatible with expectation from reaction-kinetic data of the two compounds. The data confirmed that GA is not a strong mutagen, which is in line with what is expected for simple oxiranes. The present study shows the value of cob(I)alamin for the determination of reaction-kinetic parameters and their use for prediction of mutagenic potency. PMID:15668111

  4. 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 (?S() ?=?-30 to -25?eu) suggested that the transition structure was stabilized by multiple intramolecular interactions. PMID:24863621

  5. Thermoluminescence kinetic parameters of different amount La-doped ZnB?O?.

    PubMed

    Kucuk, Nil; Gozel, Aziz Halit; Yksel, 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 200C and a shoulder peak at around 315C with a constant heating rate of 5C/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. PMID:26186155

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

    NASA Astrophysics Data System (ADS)

    Chaudhry, Q. A.

    2014-12-01

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

  7. Identification of the crystallization kinetic parameters of a semi-crystalline polymer by using PVT? measurement

    NASA Astrophysics Data System (ADS)

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

    2011-05-01

    Injection molding is the most widely used process in the plastic industry. In the case of semi-crystalline polymer, crystallization kinetics impacts directly the quality of the piece, both on dimensional and mechanical aspects. The characterization of these kinetics is therefore of primary importance to model the process, in particular during the cooling phase. To be representative, this characterization must be carried out under conditions as close as possible to those encountered in the process: high pressure, high cooling rate, shearing, and potential presence of fibers. However, conventional apparatus such as the differential scanning calorimeter do not allow to reach these conditions. A PVT? apparatus, initially developed in the laboratory for the characterization of thermoset composites, was adapted to identify the crystallization kinetics. The aim of the presented study is to demonstrate the feasibility of the identification. This device allows the molding of a circular sample of 40 mm diameter and 6 mm thick by controlling the applied pressure on the sample and the temperature field on its surfaces. This mold is designed such as heat transfer is 1D within the thickness of the sample. It is equipped with two heat flux sensors to determine the average crystallization rate through the thickness and a displacement sensor for the determination of the volume change. The heat transfer problem between the polymer and the molding cavity is modeled by using a 1D conduction problem with a moving boundary, in which the control volume is a uniform temperature disk with a variable volume, and coupled to a crystallization kinetic model. An inverse method is used to identify the parameters of the crystallization kinetic model by minimizing an objective function based on the difference between the evolutions of the experimental and computed volume of the sample. The first validation of this methodology was to compare the kinetic parameters identified with this apparatus with those obtained from DSC experiments, i.e. without additional pressure and at low cooling rates. A good agreement was obtained between both methods. A second validation was to compare experimental and computed temperatures at the center of the plastic part. In this case also, a very good agreement was found. The feasibility of the methodology is now demonstrated. The device is being adapted to increase the level of applied pressure as well as the cooling rate to achieve injection conditions.

  8. Kinetic Parameter Extraction of Square Wave Voltammograms from DNA-Modified Gold Electrodes

    NASA Astrophysics Data System (ADS)

    McWilliams, Marc; Wohlgamuth, Chris; Slinker, Jason

    2012-10-01

    The field of surface bound electrochemistry is important in a variety of applications specifically sensing. A fundamental understanding of the processes involved could help to improve detection limits, optimize rates of detection and direct changes in device design. Accurate extraction of electrochemical kinetic parameters such as the rate constant k and charge transfer coefficient α from cyclic voltammograms can be challenging when confronted with large background currents and relatively weak signals. The commonly used technique of Laviron analysis is both time consuming and somewhat subjective. Square wave voltammetry (SWV) is therefore an ideal alternative method given that it maximizes signal while minimizing capacitive effects. In this experiment kinetic parameters of DNA-modified gold electrodes are obtained from SWV curves through background subtraction followed by nonlinear least squares fitting using a first order quasi-reversible surface process model. The fitting is accomplished using the Nelder-Mead simplex algorithm with standard parameters and a convergence condition of less than 0.0001%. General agreement with experimental data is shown with varying levels of confidence. Difficulties specific to this experiment are discussed as well as the possible benefits of utilizing the Bayesian statistical approach of nested sampling when confronted with multiple peaks of interest and the background source is well defined.

  9. 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

  10. 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-Galle; Vian, Maryline; Fine, Frdric; Joffre, Florent; Carr, 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

  11. 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...

  12. 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.

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

    SciTech Connect

    Kiedrowski, Brian C; Brown, Forrest B; Wilson, Paul

    2009-01-01

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

  14. Applicability of fluorescence-based sensors to the determination of kinetic parameters for O? in oxygenases.

    PubMed

    Di Russo, Natali V; Bruner, Steven D; Roitberg, Adrian E

    2015-04-15

    Optical methods for O2 determination based on dynamic fluorescence quenching have been applied to measure oxygen uptake rates in cell culture and to determine intracellular oxygen levels. Here we demonstrate the applicability of fluorescence-based probes in determining kinetic parameters for O2 using as an example catalysis by a cofactor-independent oxygenase (DpgC). Fluorescence-based sensors provide a direct assessment of enzyme-catalyzed O2 consumption using commercially available, low-cost instrumentation that is easily customizable and, thus, constitutes a convenient alternative to the widely used Clark-type electrode, especially in cases where chemical interference is expected to be problematic. PMID:25637681

  15. 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.

  16. Kinetics of the effect of ara C on chromosome aberration yield in irradiated human lymphocytes.

    TOXLINE Toxicology Bibliographic Information

    Virsik-Peuckert RP; Harder D

    1986-01-01

    In unstimulated lymphocytes the enhancing effect of ara C on the yield of X-ray-induced dicentric aberrations was maximal if ara C was added immediately or up to 2 h after irradiation. When ara C was added later the enhancing effect decreased and practically vanished by 5 h. In stimulated lymphocytes the ara C effect declined faster and practically vanished by 3 h. If ara C was added for 1 h immediately after irradiation, then the aberration yield observed in G0, early G1 and late G1 cells was similar whereas it increased significantly from G0 to late G1 cells without ara C post-treatment. The results are discussed in relation to the classical model of aberration formation.

  17. 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

  18. Determination of kinetic parameters specific for a given source rock: optim method

    SciTech Connect

    Ungerer, P.; Chenet, P.

    1987-05-01

    The OPTIM method consists of processing pyrolysis data in order to obtain an optimized set of kinetic parameters which account for the kinetics of hydrocarbon formation from the specific source rock considered. The basic principles of the underlying kinetic model are the same as the Tissot and Espitalie model, in which the number of parallel reactions has been increased. The first way to use the OPTIM program is to use Rock-Eval pyrolysis data from a unique immature kerogen sample at various heating rates. Additional data obtained from autoclave pyrolysis may be integrated optionally. This way is particularly adapted to early stages of basin exploration, when the source rock is already identified but not sampled in the oil formation zone. As shown in case where the predictions could be checked against well data, the model optimized by this way is applicable to natural conditions with a reasonable accuracy. The second way to use the program is to integrate pyrolysis data from several immature and mature samples of the type considered, together with the thermal history of each sample. Such a use of the program is possible only when the basin is already well explored and when the paleotemperatures do not suffer high uncertainties. The advantage of the method is then to account explicitly for the natural maturation process. Several application examples are presented which show very important differences of behavior between various source rocks, from a kinetic as well as from a quantitative viewpoint. Their method provides the industry with an operational and relatively rapid tool in order to account for these differences.

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

    PubMed

    Nieto, Juan Azorin; 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 (280C) 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. PMID:26656428

  20. Sparsity Constrained Mixture Modeling for the Estimation of Kinetic Parameters in Dynamic PET

    PubMed Central

    Lin, Yanguang; Haldar, Justin P.; Li, Quanzheng; Conti, Peter S.; Leahy, Richard M.

    2013-01-01

    The estimation and analysis of kinetic parameters in dynamic PET is frequently confounded by tissue heterogeneity and partial volume effects. We propose a new constrained model of dynamic PET to address these limitations. The proposed formulation incorporates an explicit mixture model in which each image voxel is represented as a mixture of different pure tissue types with distinct temporal dynamics. We use Cramr-Rao lower bounds to demonstrate that the use of prior information is important to stabilize parameter estimation with this model. As a result, we propose a constrained formulation of the estimation problem that we solve using a two-stage algorithm. In the first stage, a sparse signal processing method is applied to estimate the rate parameters for the different tissue compartments from the noisy PET time series. In the second stage, tissue fractions and the linear parameters of different time activity curves are estimated using a combination of spatial-regularity and fractional mixture constraints. A block coordinate descent algorithm is combined with a manifold search to robustly estimate these parameters. The method is evaluated with both simulated and experimental dynamic PET data. PMID:24216681

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

    PubMed

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

    2012-11-21

    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. PMID:23181288

  2. 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.

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

    PubMed

    Bozkoyunlu, Gaye; Takaç, Serpil

    2014-01-01

    Olive mill wastewater (OMW) with total phenol (TP) concentration range of 300-1200 mg/L was treated with alginate-immobilized Rhodotorula glutinis cells in batch system. The effects of pellet properties (diameter, alginate concentration and cell loading (CL)) and operational parameters (initial TP concentration, agitation rate and reusability of pellets) on dephenolization of OMW were studied. Up to 87% dephenolization was obtained after 120 h biodegradations. The utilization number of pellets increased with the addition of calcium ions into the biodegradation medium. The overall effectiveness factors calculated for different conditions showed that diffusional limitations arising from pellet size and pellet composition could be neglected. Mass transfer limitations appeared to be more effective at high substrate concentrations and low agitation rates. The parameters of logistic model for growth kinetics of R. glutinis in OMW were estimated at different initial phenol concentrations of OMW by curve-fitting of experimental data with the model. PMID:25244135

  4. Kinetic parameters of the conversion of methane precursors to methane in a hypereutrophic lake sediment.

    PubMed

    Strayer, R F; Tiedje, J M

    1978-08-01

    The kinetic parameters K(m), V(max), T(t) (turnover time), and v (natural velocity) were determined for H(2) and acetate conversion to methane by Wintergreen Lake sediment, using short-term (a few hours) methods and incubation temperatures of 10 to 14 degrees C. Estimates of the Michaelis-Menten constant, K(m), for both the consumption of hydrogen and the conversion of hydrogen to methane by sediment microflora averaged about 0.024 mumol g of dry sediment. The maximal velocity, V(max), averaged 4.8 mumol of H(2) g h for hydrogen consumption and 0.64 mumol of CH(4) g h for the conversion of hydrogen to methane during the winter. Estimated natural rates of hydrogen consumption and hydrogen conversion to methane could be calculated from the Michaelis-Menten equation and estimates of K(m), V(max), and the in situ dissolved-hydrogen concentration. These results indicate that methane may not be the only fate of hydrogen in the sediment. Among several potential hydrogen donors tested, only formate stimulated the rate of sediment methanogenesis. Formate conversion to methane was so rapid that an accurate estimate of kinetic parameters was not possible. Kinetic experiments using [2-C]acetate and sediments collected in the summer indicated that acetate was being converted to methane at or near the maximal rate. A minimum natural rate of acetate conversion to methane was estimated to be about 110 nmol of CH(4) g h, which was 66% of the V(max) (163 nmol of CH(4) g h). A 15-min preincubation of sediment with 5.0 x 10 atm of hydrogen had a pronounced effect on the kinetic parameters for the conversion of acetate to methane. The acetate pool size, expressed as the term K(m) + S(n) (S(n) is in situ substrate concentration), decreased by 37% and T(t) decreased by 43%. The V(max) remained relatively constant. A preincubation with hydrogen also caused a 37% decrease in the amount of labeled carbon dioxide produced from the metabolism of [U-C]valine by sediment heterotrophs. PMID:16345312

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

    PubMed

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

    2015-07-01

    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

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

    PubMed Central

    Franco, R; Gavald, 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

  7. The photocycle of the chloride pump halorhodopsin. II: Quantum yields and a kinetic model.

    PubMed

    Oesterhelt, D; Hegemann, P; Tittor, J

    1985-09-01

    The quantum yield of the primary photoreaction of HR478 was determined as phi(green) = 0.34 +/- 0.02 and that of the photochemical reconversion of HRL410 into HR578 as phi(blue) = 0.01 +/- 0.004. From steady-state illumination and flash-photolysis experiments, a quantitative description of HRL410 formation and decay was made leading to a model of the photocycle in isolated, light-adapted HR. This model satisfies all known facts about HR including its photochronic behaviour. PMID:15938054

  8. A State Space Transformation Can Yield Identifiable Models for Tracer Kinetic Studies with Enrichment Data

    PubMed Central

    Ramakrishnan, Rajasekhar; Ramakrishnan, Janak D.

    2012-01-01

    Tracer studies are analyzed almost universally by multicompartmental models where the state variables are tracer amounts or activities in the different pools. The model parameters are rate constants, defined naturally by expressing fluxes as fractions of the source pools. We consider an alternative state space with tracer enrichments or specific activities as the state variables, with the rate constants redefined by expressing fluxes as fractions of the destination pools. Although the redefinition may seem unphysiological, the commonly computed fractional synthetic rate actually expresses synthetic flux as a fraction of the product mass (destination pool). We show that, for a variety of structures, provided the structure is linear and stationary, the model in the enrichment state space has fewer parameters than that in the activities state space, and is hence better both to study identifiability and to estimate parameters. The superiority of enrichment modeling is shown for structures where activity model unidentifiability is caused by multiple exit pathways; on the other hand, with a single exit pathway but with multiple untraced entry pathways, activity modeling is shown to be superior. With the present-day emphasis on mass isotopes, the tracer in human studies is often of a precursor, labeling most or all entry pathways. It is shown that for these tracer studies, models in the activities state space are always unidentifiable when there are multiple exit pathways, even if the enrichment in every pool is observed; on the other hand, the corresponding models in the enrichment state space have fewer parameters and are more often identifiable. Our results suggest that studies with labeled precursors are modeled best with enrichments. PMID:20195911

  9. Kinetics of the reaction O + ClO yields Cl + O2

    NASA Technical Reports Server (NTRS)

    Leu, M.-T.

    1984-01-01

    The bimolecular rate constant for the reaction O + ClO yields Cl + O2 has been measured over the temperature range 236-422 K in a discharge flow system using atomic oxygen resonance fluorescence at 130 nm to monitor the decay of O in an excess of ClO. The results are found to be independent of the method used to produce the ClO radical. At 296 K, the rate constant is given by (3.6 + or - 0.7) x 10 to the -11th cu cm/sec and the temperature dependence expressed in Arrhenius form by k2 = (5.0 + or - 1.0) x 10 to the -11th exp-(96 + or - 20)/T cu cm/sec. The results are compared with earlier values, and the implications for stratospheric chemistry are discussed briefly.

  10. 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.

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

    SciTech Connect

    Jantzen, C M

    1988-01-01

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

  12. 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%.

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

    PubMed

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

    2010-01-01

    Composting is a feasible biological treatment for the recycling of wastewater sludge as a soil amendment. The process can be optimized by selecting an initial compost recipe with physical properties that enhance microbial activity. The present study measured the microbial O(2) uptake rate (OUR) in 16 sludge and wood residue mixtures to estimate the kinetics parameters of maximum growth rate mu(m) and rate of organic matter hydrolysis K(h), as well as the initial biodegradable organic matter fractions present. The starting mixtures consisted of a wide range of moisture content (MC), waste to bulking agent (BA) ratio (W/BA ratio) and BA particle size, which were placed in a laboratory respirometry apparatus to measure their OUR over 4 weeks. A microbial model based on the activated sludge process was used to calculate the kinetic parameters and was found to adequately reproduced OUR curves over time, except for the lag phase and peak OUR, which was not represented and generally over-estimated, respectively. The maximum growth rate mu(m), was found to have a quadratic relationship with MC and a negative association with BA particle size. As a result, increasing MC up to 50% and using a smaller BA particle size of 8-12 mm was seen to maximize mu(m). The rate of hydrolysis K(h) was found to have a linear association with both MC and BA particle size. The model also estimated the initial readily biodegradable organic matter fraction, MB(0), and the slower biodegradable matter requiring hydrolysis, MH(0). The sum of MB(0) and MH(0) was associated with MC, W/BA ratio and the interaction between these two parameters, suggesting that O(2) availability was a key factor in determining the value of these two fractions. The study reinforced the idea that optimization of the physical characteristics of a compost mixture requires a holistic approach. PMID:20395122

  14. {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.

  15. Optimization of kinetic parameters for thermal degradation of kerogen: A Pascal program

    NASA Astrophysics Data System (ADS)

    Bastow, M. A.

    1995-11-01

    Kinetic parameters for the thermal degradation of kerogens are derived both from isothermal and nonisothermal heating experiments and from field observations, and the data used in computer-aided basin modeling to simulate the maturation of source rocks and the timing of hydrocarbon generation and expulsion. A Pascal program for determination of kinetic parameters is presented, together with a simplified application. Thermal degradation of kerogen is modeled as a set of parallel, independent, irreversible first-order chemical reactions. The parameters for optimization are the fractional contributions of the parallel reactions, each characterized by a discrete activation energy level, and a single, global preexponential frequency (Arrhenius) factor. For a given frequency factor, determination of the reaction proportions reduces to least-squares regression analysis of an overdetermined set of linear equations, subject to nonnegativity and closure (sum to unity) constraints, solved using an active set method. The error function (mean-squared residual) then is a nonlinear function of the frequency factor and is minimized by one-dimensional interval reduction and line-searching techniques (minimum bracketing, golden section search, and inverse quadratic interpolation). The modular program operates in a UCSD Pascal P-system environment on a 640K IBM-compatible PC. Several sets of data may be combined, including simultaneous optimization of reaction rate and cumulative evolution (or transformation ratio) data. The number of parallel reactions, distribution of activation energies, and initial estimate for the frequency factor may all be changed. The program includes a procedure for fitting data to a single, first-order reaction, requiring optimization of one activation energy and the frequency factor. A mean-squared residual objective function is minimized using a multidimensional direction set method.

  16. 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.

  17. 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.

  18. Determination of kinetic parameters of Phlomis bovei de No 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 No. PMID:26276095

  19. Characterization of dupont photopolymer: determination of kinetic parameters in a diffusion model.

    PubMed

    Moreau, Vincent; Renotte, Yvon; Lion, Yves

    2002-06-10

    We investigate the recording dynamics of Omnidex photopolymer film from DuPont. We use a reviewed version of the diffusion model proposed by Zhao and Mouroulis [J. Mod. Opt. 41, 1929 (1994)] in order to describe the recording response that combined photopolymerization and free-monomer diffusion process. Two different experiments are detailed that lead to the determination of material kinetic parameters. These values are introduced in the numerical model to provide quantitative simulations of a grating formation under various holographic exposures. Theoretical results are experimentally checked as a validation of the model. We extend its applications to several secondary investigations, such as volume-shrinkage influence on refractive-index distribution and spectral selectivity of reflection gratings. This study improves the understanding of the recording process and consequently allows to build more accurate holographic components in this material to be built. PMID:12074514

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

    SciTech Connect

    Albano, C.; Freitas, E.

    1996-12-31

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

  1. Estimates of genetic parameters for Holstein cows for test-day yield traits with a random regression cubic spline model

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Genetic parameters were estimated with REML for individual test-day milk, fat, and protein yields and SCS with a random regression cubic spline model. Test-day records of Holstein cows that calved from 1994 through early 1999 were obtained from Dairy Records Management Systems in Raleigh, North Car...

  2. ESTIMATES OF GENETIC PARAMETERS FOR FIRST LACTATION TEST-DAY YIELDS OF HOLSTEIN COWS WITH A CUBIC SPLINE MODEL

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The objective was to estimate genetic parameters for individual test-day milk, fat, and protein yields with a cubic spline model. A total of 196,687 test-day records in the first 305-d of 38,172 first lactation Holstein cows that calved between 1994 and early 1999 were obtained from Dairy Records Ma...

  3. 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 -?H, adsorption/desorption rate constants Ka and Kd, active-site number per unit mass N' and surface coverage ?, 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 -?H. To achieve more sensing-sites, KIT-5 mesoporous-silica with higher surface-area is assessed, resulting in good sensitivity but too high -?H 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 -?H, Ka, Kd, N' and ?, 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. PMID:25732312

  4. Interactions of viruses in Cowpea: effects on growth and yield parameters

    PubMed Central

    Kareem, KT; Taiwo, MA

    2007-01-01

    The study was carried out to investigate the effects of inoculating three cowpea cultivars: "OLO II", "OLOYIN" and IT86D-719 with three unrelated viruses: Cowpea aphid-borne mosaic virus (CABMV), genus Potyvirus, Cowpea mottle virus (CMeV), genus Carmovirus and Southern bean mosaic virus (SBMV), genus Sobemovirus singly and in mixture on growth and yield of cultivars at 10 and 30 days after planting (DAP). Generally, the growth and yield of the buffer inoculated control plants were significantly higher than those of the virus inoculated plants. Inoculation of plants at an early age of 10 DAP resulted in more severe effect than inoculations at a later stage of 30 DAP. The average values of plant height and number of leaves produced by plants inoculated 30 DAP were higher than those produced by plants inoculated 10 DAP. Most of the plants inoculated 10 DAP died and did not produce seeds. However, " OLOYIN" cultivar was most tolerant and produced reasonable yields when infected 30 DAP. The effect of single viruses on growth and yield of cultivars showed that CABMV caused more severe effects in IT86D-719, SBMV had the greatest effect on "OLO II" while CMeV induced the greatest effect on "OLOYIN". Yield was greatly reduced in double infections involving CABMV in combination with either CMeV or SBMV in "OLOYIN" and "OLO II", however, there was complete loss in yield of IT86D-719. Triple infection led to complete yield loss in all the three cultivars. PMID:17286870

  5. Aqueous oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Kinetics and SOA yields

    NASA Astrophysics Data System (ADS)

    Richards-Henderson, Nicole K.; Hansel, Amie K.; Valsaraj, Kalliat T.; Anastasio, Cort

    2014-10-01

    Green leaf volatiles (GLVs) are a class of oxygenated hydrocarbons released from vegetation, especially during mechanical stress or damage. The potential for GLVs to form secondary organic aerosol (SOA) via aqueous-phase reactions is not known. Fog events over vegetation will lead to the uptake of GLVs into water droplets, followed by aqueous-phase reactions with photooxidants such as the hydroxyl radical (OH). In order to determine if the aqueous oxidation of GLVs by OH can be a significant source of secondary organic aerosol, we studied the partitioning and reaction of five GLVs: cis-3-hexen-1-ol, cis-3-hexenyl acetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol. For each GLV we measured the kinetics of aqueous oxidation by OH, and the corresponding SOA mass yield. The second-order rate constants for GLVs with OH were all near diffusion controlled, (5.4-8.6) 109 M-1 s-1 at 298 K, and showed a small temperature dependence, with an average activation energy of 9.3 kJ mol-1 Aqueous-phase SOA mass yields ranged from 10 to 88%, although some of the smaller values were not statistically different from zero. Methyl jasmonate was the most effective aqueous-phase SOA precursor due to its larger Henry's law constant and high SOA mass yield (68 8%). While we calculate that the aqueous-phase SOA formation from the five GLVs is a minor source of aqueous-phase SOA, the availability of other GLVs, other oxidants, and interfacial reactions suggest that GLVs overall might be a significant source of SOA via aqueous reactions.

  6. Determination of kinetics parameters of glass transition in glassy Se and glassy Se98M2 alloys using DSC technique

    NASA Astrophysics Data System (ADS)

    Dohare, C.; Mehta, N.

    2014-02-01

    Glassy Se and Se98M2 (M = Ag, Cd, Zn) alloys are obtained by the melt quenching technique. Differential Scanning Calorimetry (DSC) technique (under non-isothermal conditions) has been applied to see the effects of Ag, Cd, and Zn additives on the glass transition kinetics of Se-rich glassy alloys at different heating rates. The variation of glass transition temperature, T g with the heating rate, ? has been used to investigate the glass transition kinetics. The values of various kinetic parameters such as glass transition temperature, activation energy of glass transition, overall mean bond energy < E>, heat of atomization H S , bond strength (Se-M) have also been calculated.

  7. Estimating kinetic parameter maps from dynamic contrast-enhanced MRI using spatial prior knowledge.

    PubMed

    Kelm, Bernd Michael; Menze, Bjoern H; Nix, Oliver; Zechmann, Christian M; Hamprecht, Fred A

    2009-10-01

    Dynamic contrast-enhanced magnetic resonance (DCE-MR) imaging can be used to study microvascular structure in vivo by monitoring the abundance of an injected diffusible contrast agent over time. The resulting spatially resolved intensity-time curves are usually interpreted in terms of kinetic parameters obtained by fitting a pharmacokinetic model to the observed data. Least squares estimates of the highly nonlinear model parameters, however, can exhibit high variance and can be severely biased. As a remedy, we bring to bear spatial prior knowledge by means of a generalized Gaussian Markov random field (GGMRF). By using information from neighboring voxels and computing the maximum a posteriori solution for entire parameter maps at once, both bias and variance of the parameter estimates can be reduced thus leading to smaller root mean square error (RMSE). Since the number of variables gets very big for common image resolutions, sparse solvers have to be employed. To this end, we propose a generalized iterated conditional modes (ICM) algorithm operating on blocks instead of sites which is shown to converge considerably faster than the conventional ICM algorithm. Results on simulated DCE-MR images show a clear reduction of RMSE and variance as well as, in some cases, reduced estimation bias. The mean residual bias (MRB) is reduced on the simulated data as well as for all 37 patients of a prostate DCE-MRI dataset. Using the proposed algorithm, average computation times only increase by a factor of 1.18 (871 ms per voxel) for a Gaussian prior and 1.51 (1.12 s per voxel) for an edge-preserving prior compared to the single voxel approach (740 ms per voxel). PMID:19369150

  8. Estimation methods and parameter assessment for ethanol yields from total soluble solids of sweet sorghum

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Estimation methods and evaluation of ethanol yield from sweet sorghum (Sorghum bicolor (L.) Moench.) based on agronomic production traits and juice characteristics is important for developing parents and inbred lines of sweet sorghum that can be used by the bio-ethanol industry. The objectives of th...

  9. 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 be investigated and its impact on tropospheric ozone distribution will be shown.

  10. Genetic Parameters And Selection Response For Yield Traits In Bread Wheat Under Irrigated And Rainfed Environments

    NASA Astrophysics Data System (ADS)

    Khalil, Iftikhar Hussain; at-ur-Rahman, Hiday; Khan, Imran

    2008-01-01

    A set of 22 F5:7 experimental wheat lines along with four check cultivars (Dera-98, Fakhr-e-Sarhad, Ghaznavi-98 and Tatara) were evaluated as independent experiments under irrigated and rainfed environments using a randomized complete block design at NWFP Agricultural University, Peshawar during 2004-05. The two environments were statistically different for days to heading and spike length only. Highly significant genetic variability existed among the wheat lines (P<0.01) in the combined analysis across environments for all traits. Genotype×environment interactions were non-significant for all traits except 1000-grain weight indicating consistent performance of wheat genotypes across the two environments. Wheat lines and check cultivars were 2 to 5 days early in heading under rainfed environment compared to the irrigated. Plant height, spike length, 1000-grain weight, biological and grain yields were generally reduced under rainfed environment. Genetic variances were of greater magnitude than environmental variances for most of the traits in both environments. The heritability estimates were of higher magnitude (0.74 to 0.96) for days to heading, plant height, spike length, biological and grain yield, while medium (0.31 to 0.51) for 1000-grain weight. Selection differentials were negative for heading (-7.3 days in irrigated vs -9.4 days in rainfed) and plant height (-9.0 cm in irrigated vs -8.7 cm in rainfed) indicating possibility of selecting wheat genotypes with early heading and short plant stature. Positive selection differentials of 1.3 vs 1.6 cm for spike length, 3.8 vs 3.4 g for 1000-grain weight, 2488.2 vs 3139.7 kg ha-1 for biological yield and 691.6 vs 565.4 kg ha-1 for grain yield at 20% selection intensity were observed under irrigated and rainfed environments, respectively. Expected selection responses were 7.98 vs 8.91 days for heading, 8.20 vs 9.52 cm for plant height, 1.01 vs 1.61 cm for spike length, 2.12 vs 1.15 g for 1000-grain weight, 1655.8 vs 2317.2 kg ha-1 for biological yield and 691.6 vs 565.4 kg ha-1 for grain yield under the two test environments, respectively. The differential heritability and selection responses for yield and related traits suggest the simultaneous evaluation and selection of wheat lines under the two environments.

  11. Phase transitions in a two-parameter model of opinion dynamics with random kinetic exchanges

    NASA Astrophysics Data System (ADS)

    Sen, Parongama

    2011-01-01

    Recently, a model of opinion formation with kinetic exchanges has been proposed in which a spontaneous symmetry-breaking transition was reported [M. Lallouache, A. S. Chakrabarti, A. Chakraborti, and B. K. Chakrabarti, Phys. Rev. EPLEEE81539-375510.1103/PhysRevE.82.056112 82, 056112 (2010)]. We generalize the model to incorporate two parameters: ?, to represent conviction, and ?, to represent the influencing ability of individuals. A phase boundary given by ?=1-?/2 is obtained separating the symmetric and symmetry broken phases: The effect of the influencing term enhances the possibility of reaching a consensus in the society. The time scale diverges near the phase boundary in a power-law manner. The order parameter and the condensate also show power-law growth close to the phase boundary albeit with different exponents. The exponents in general change along the phase boundary, indicating a nonuniversality. The relaxation times, however, become constant with increasing system size near the phase boundary, indicating the absence of any diverging length scale. Consistently, the fluctuations remain finite but show strong dependence on the trajectory along which it is estimated.

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

    PubMed

    Aguirre, Juan S; de Fernando, Gonzalo Garca; Hierro, Eva; Hospital, Xavier F; Ordez, Juan A; Fernndez, Manuela

    2015-06-01

    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 (?max) 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 ?max of the survivors and the inactivation achieved. The ?max 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. PMID:25755081

  13. Turbulence intensity and turbulent kinetic energy parameters over a heterogeneous terrain of Loess Plateau

    NASA Astrophysics Data System (ADS)

    Yue, Ping; Zhang, Qiang; Wang, Runyuan; Li, Yaohui; Wang, Sheng

    2015-09-01

    A deep understanding of turbulence structure is important for investigating the characteristics of the atmospheric boundary layer, especially over heterogeneous terrain. In the present study, turbulence intensity and turbulent kinetic energy (TKE) parameters are analyzed for different conditions with respect to stability, wind direction and wind speed over a valley region of the Loess Plateau of China during December 2003 and January 2004. The purpose of the study is to examine whether the observed turbulence intensity and TKE parameters satisfy Monin-Obukhov similarity theory (MOST), and analyze the wind shear effect on, and thermal buoyancy function of, the TKE, despite the terrain heterogeneity. The results demonstrate that the normalized intensity of turbulence follows MOST for all stability in the horizontal and vertical directions, as well as the normalized TKE in the horizontal direction. The shear effect of the wind speed in the Loess Plateau region is strong in winter and could enhance turbulence for all stability conditions. During daytime, the buoyancy and shear effect together constitute the generation of TKE under unstable conditions. At night, the contribution of buoyancy to TKE is relatively small, and mechanical shearing is the main production form of turbulence.

  14. 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. PMID:26299576

  15. Crop yield estimation model for Iowa using remote sensing and surface parameters

    NASA Astrophysics Data System (ADS)

    Prasad, Anup K.; Chai, Lim; Singh, Ramesh P.; Kafatos, Menas

    2006-01-01

    Numerous efforts have been made to develop various indices using remote sensing data such as normalized difference vegetation index (NDVI), vegetation condition index (VCI) and temperature condition index (TCI) for mapping and monitoring of drought and assessment of vegetation health and productivity. NDVI, soil moisture, surface temperature and rainfall are valuable sources of information for the estimation and prediction of crop conditions. In the present paper, we have considered NDVI, soil moisture, surface temperature and rainfall data of Iowa state, US, for 19 years for crop yield assessment and prediction using piecewise linear regression method with breakpoint. Crop production environment consists of inherent sources of heterogeneity and their non-linear behavior. A non-linear Quasi-Newton multi-variate optimization method is utilized, which reasonably minimizes inconsistency and errors in yield prediction. Minimization of least square loss function has been carried out through iterative convergence using pre-defined empirical equation that provided acceptable lower residual values with predicted values very close to observed ones ( R2 = 0.78) for Corn and Soybean crop ( R2 = 0.86) for Iowa state. The crop yield prediction model discussed in the present paper will further improve in future with the use of long period dataset. Similar model can be developed for different crops of other locations.

  16. Tris(2,2'-bipyridine)ruthenium(II)-sensitized photooxidation of phenols. Environmental effects on electron transfer yields and kinetics

    SciTech Connect

    Miedlar, K.; Das, P.K.

    1982-12-29

    Laser flash photolysis (337.1 nm) combined with kinetic absorption-emission spectrophotometry has been used to study the photoreduction of tris(2,2'-bipyridine)ruthenium(II) by phenols and the effects of solvent, temperature, and ionic strength on electron transfer kinetics and yields. The excited-state quenching rate constants (k/sub q/) are in the range 1 x 10/sup 6/-5 x 10/sup 9/ M/sup -1/s/sup -1/ for substituted phenolate ions (pH 12.7) and correlate well with Hammett sigma/sup +/ values and with oxidation potentials. The plot of RT in k'/sub q/ against E/sub ArO./ArO/sup -// has a slope of -0.56, k'/sub q/ being the quenching rate constant corrected for the initial diffusional process. Arrhenius plots for k/sub q/ in the cases of p-CH/sub 3/O-C/sub 6/H/sub 4/O/sup -/, C/sub 6/H/sub 5/O/sup -/, and p-COO/sup -/-C/sub 6/H/sub 4/O/sup -/ as quenchers in aqueous solutions are linear from 0 to 80/sup 0/C. With p-methoxyphenolate ion and p-methoxy-N,N-dimethylaniline as quenchers, k/sub q/ increases on changing solvent from water to 95% ethanol or 95% acetone; k/sub q/ goes through a minimum at intermediate solvent compositions. Electron transfer yields (eta) are 0.3 to 1.0 for various phenolate ions in aqueous solutions (pH 12.7). For p-methoxyphenolate ion and p-methoxy-N,N-dimethylaniline, eta exhibits an increasing trend at elevated temperatures, in aqueous solvent systems richer in the nonaqueous component (acetone or ethanol), and at lower ionic strengths. The excited-state absorption spectrum (triplet-triplet) or tris(2,2'-bipyridine)ruthenium(II) in aqueous solution (230 to 800 nm) shows small absorption at (500 to 800 nm) and prominent three-band feature at 240 to 400 nm.

  17. 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.

  18. 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-Vzquez, Aura Roxana; Corts Penagos, Consuelo de Jess; Corts-Martnez, Ral

    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 25C. 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

  19. 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)

  20. 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

    2014-10-01

    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. PMID:25220448

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

    NASA Astrophysics Data System (ADS)

    Bouillard, Jacques Xavier; Marchal, Philippe; Henry, Franois; 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.

  2. Rate Equations and Kinetic Parameters of the Reactions Involved in Pyrite Oxidation by Thiobacillus ferrooxidans

    PubMed Central

    Lizama, Hector M.; Suzuki, Isamu

    1989-01-01

    Rate equations and kinetic parameters were obtained for various reactions involved in the bacterial oxidation of pyrite. The rate constants were 3.5 ?M Fe2+ per min per FeS2 percent pulp density for the spontaneous pyrite dissolution, 10 ?M Fe2+ per min per mM Fe3+ for the indirect leaching with Fe3+, 90 ?M O2 per min per mg of wet cells per ml for the Thiobacillus ferrooxidans oxidation of washed pyrite, and 250 ?M O2 per min per mg of wet cells per ml for the T. ferrooxidans oxidation of unwashed pyrite. The Km values for pyrite concentration were similar and were 1.9, 2.5, and 2.75% pulp density for indirect leaching, washed pyrite oxidation by T. ferrooxidans, and unwashed pyrite oxidation by T. ferrooxidans, respectively. The last reaction was competitively inhibited by increasing concentrations of cells, with a Ki value of 0.13 mg of wet cells per ml. T. ferrooxidans cells also increased the rate of Fe2+ production from Fe3+ plus pyrite. PMID:16348054

  3. Isopeptidase activity of human transglutaminase 2: disconnection from transamidation and characterization by kinetic parameters.

    PubMed

    Kirly, Rbert; Thangaraju, Kiruphagaran; Nagy, Zsfia; Collighan, Russell; Nemes, Zoltn; Griffin, Martin; Fss, Lszl

    2016-01-01

    Transglutaminase 2 (TG2) is a multifunctional protein with diverse catalytic activities and biological roles. Its best studied function is the Ca(2+)-dependent transamidase activity leading to formation of ?-glutamyl-?-lysine isopeptide crosslinks between proteins and ?-glutamyl-amine derivatives. TG2 has a poorly studied isopeptidase activity cleaving these bonds. We have developed and characterised TG2 mutants which are significantly deficient in transamidase activity while have normal or increased isopeptidase activity (W332F) and vice versa (W278F). The W332F mutation led to significant changes of both the K m and the V max kinetic parameters of the isopeptidase reaction of TG2 while its calcium and GTP sensitivity was similar to the wild-type enzyme. The W278F mutation resulted in six times elevated amine incorporating transamidase activity demonstrating the regulatory significance of W278 and W332 in TG2 and that mutations can change opposed activities located at the same active site. The further application of our results in cellular systems may help to understand TG2-driven physiological and pathological processes better and lead to novel therapeutic approaches where an increased amount of crosslinked proteins correlates with the manifestation of degenerative disorders. PMID:26250429

  4. [Comparison of kinematic and kinetic parameters between the locomotion patterns in nordic walking, walking and running].

    PubMed

    Kleindienst, F I; Michel, K J; Schwarz, J; Krabbe, B

    2006-03-01

    Based on a higher cardio-pulmonary and cardio-vascular benefit and a promised reduction of mechanical load of the musculoskeletal system Nordic Walking (NW) shows an increased market potential. The present study should investigate whether there are biomechanical differences between the locomotion patterns NW, walking and running. Moreover possible resultant load differences should be determined. Eleven subjects, who were already experienced with the NW-technique, participated in this experiment. The kinematic data were collected using two high-speed camera systems from posterior and from lateral at the same time. Simultaneously the ground reaction forces were recorded. The kinematic and the kinetic data reveal differences between the three analyzed locomotion patterns. For NW as well as walking the mechanical load of the lower extremity is lower compared to running. None of the kinematic parameters suggest a "physiological benefit" of NW compared to walking. Moreover NW shows higher vertical and horizontal forces during landing. Exclusively the lower vertical force peak during push off indicates a lower mechanical load for NW in comparison to walking. Consequently it is questionable is NW -- based on its promised "biomechanical benefits" compared to walking -- should be still recommended for overweight people and for people with existing musculoskeletal problems of the lower limb. PMID:16544213

  5. Evaluation of reactor kinetic parameters without the need for perturbation codes.

    SciTech Connect

    Bretscher, M. M.

    1998-01-14

    The analysis of research reactor transients depends on the effective delayed neutron fraction (k{sub eff}), its family-dependent components ({beta}{sub eff,i}), the prompt neutron lifetime (l{sub p}), and the decay constants ({lambda}{sub i}) for each delayed neutron family. Beginning with ENDF/B-V data, methods are presented for accurately calculating these kinetic parameters within the framework of diffusion theory but without the need for a perturbation code. For heavy water systems these methods can be extended to include the delayed photoneutron component of {beta}{sub eff}. However, a separate calculation is needed to estimate the fractional loss of fission product gamma rays, energetic enough to dissociate the deuteron, from leakage, energy degradation and absorption in fuel and structural materials. These methods are illustrated for a light-water Oak Ridge Research Reactor (ORR) LEU core and for a heavy-water Georgia Tech Research Reactor (GTRR) HEU core where calculated and measured values of the prompt neutron decay constant ({beta}{sub eff}/l{sub p}) are compared.

  6. 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. PMID:25597679

  7. 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)

  8. Effect of Simulated Dasiops inedulis (Diptera: Lonchaeidae) Injury on Yield and Fruit Quality Parameters in Yellow Passionfruit.

    PubMed

    Salamanca, Leidy; Manzano, Maria R; Baena, Diosdado; Tovar, Diego; Wyckhuys, Kris A G

    2015-02-01

    Yellow passionfruit (Passiflora edulis f. flavicarpa O. Deg.) is a tropical fruit crop that is meeting increasing demand both in local and international markets in South America. The lance fly, Dasiops inedulis (Diptera: Lonchaeidae), affects P. edulis floral buds and flowers, and is thought to cause important yield losses in this crop. In Colombia, D. inedulis are commonly controlled through calendar-based applications of chemically synthesized insecticides, and no scientific criteria exist to guide pest management. In the present study, we simulated D. inedulis injury to passionfruit plants, over the course of three production cycles. We assessed the effect of seven different categories of flower bud removal (from 0% to 79.9%) on passionfruit yield and fruit quality parameters. Removal rates above 20% caused a significant reduction in the number of flowers, while yield levels were lowest at 50-79.9% bud removal. With increasing rates of flower bud removal, we observed higher initial production of buds and lower levels of natural abortion of floral and fruiting structures. For the three consecutive harvests, maximum yield levels were 7.575.51?kg (meanSD; with 0-9.9% damage), and minimum yield was 2.372.15?kg (60-69.9% damage) per plant. For fruit quality parameters, D. inedulis injury did not affect fruit pulp weight or the content of soluble solids (Brix). Our work provides insights into the impact of D. inedulis on yellow passionfruit production, and constitutes a basis for future integrated pest management programs for this pest. PMID:26470121

  9. The interrelationship of biological marker maturity parameters and molecular yields during contact metamorphism

    NASA Astrophysics Data System (ADS)

    Bishop, A. N.; Abbott, G. D.

    1993-08-01

    Jurassic siltstone samples were collected, on a centimetre scale, as a function of increasing distance from a dolerite dyke (Isle of Skye, northwest Scotland). The constant origin and type of the organic matter in this single lithological horizon is indicated by organic petrological observations as well as organic geochemical analyses. Therefore, changes in biological marker distributions, with distance from the dyke contact, can be unequivocally correlated with the thermal influence of the intrusion. The vitrinite reflectance ( R0 Average) values of these samples increase gradually from 0.35% to 3.60% as the dyke contact is approached. Four classical biological marker maturity parameters ( 20S/(20S + 20R), TA/(TA + MA), C 20/(C 20 + C 28) , and 22S/(22S + 22R)). have been measured from GCMS analyses of the sample extracts. Changes in these molecular parameters were compared with changes in the concentrations of the individual biological marker compounds, expressed relative to mass of rock extracted. This comparison revealed that these molecular parameters are not governed by the conventional productreactant relationships (chiral isomerisation, aromatisation or side-chain cracking reactions) operating solely in the free saturated or aromatic hydrocarbon structures. Release/formation from macromolecular and/or functionalised moieties (hydrocarbon or non-hydrocarbon) followed by compound loss provide an alternative paradigm in all four cases in this particular thermal regime. Direct chiral isomerisation in the free sterane or homohopane cannot, however, be completely ruled out as a contributor to an admixture of processes. Similarly, aromatisation in the free hydrocarbon fraction may account for a proportion of the triaromatic steroids.

  10. [Estimation of biological parameters and yield per recruitment for Coilia nasustaihuensis in Dianshan Lake, Shanghai, China].

    PubMed

    Gao, Chun-Xia; Tian, Si-Quan; Dai, Xiao-Jie

    2014-05-01

    Coilia nasustaihuensis is the most abundant species in Dianshan Lake and plays an important role in the lake ecosystem. From July 2010 to August 2011, a total of 3107 samples of C. nasustaihuensis were collected from Dianshan Lake. Based on length data of these samples, ELEFAN I technique was employed to estimate growth and mortality parameters, and the Beverton-Holt dynamic model was used to evaluate the population dynamics trend for C. nasustaihuensis. Growth of this species was described using avon Bertalanffy model, and the estimated parameters were Linfinity = 35.70 cm, k = 0.54, and t0 = -0.48 a. The turning point for body mass growth curve of the stock was situated at t = 1.37 a. Natural mortality coefficient M was then estimated using Pauly's empirical equation and found to be 0. 872. Length-converted catch curves were used to estimate the total mortality coefficient Z, which was found to be 2.121. Accordingly, the fishing mortality coefficient (F) was equal to 1.249, and the current exploitation rate was 0. 589, suggesting the stock was over-exploited. According to the Beverton-Holt dynamic model, the minimum capture size for C. nasustaihuensis should be 21.42 cm (age 1.22 years). PMID:25129955

  11. Two-parameter kinetic model based on a time-dependent activity coefficient accurately describes enzymatic cellulose digestion.

    PubMed

    Kostylev, Maxim; Wilson, David

    2013-08-20

    Lignocellulosic biomass is a potential source of renewable, low-carbon-footprint liquid fuels. Biomass recalcitrance and enzyme cost are key challenges associated with the large-scale production of cellulosic fuel. Kinetic modeling of enzymatic cellulose digestion has been complicated by the heterogeneous nature of the substrate and by the fact that a true steady state cannot be attained. We present a two-parameter kinetic model based on the Michaelis-Menten scheme ( Michaelis, L., and Menten, M. L. ( 1913 ) Biochem. Z. , 49 , 333 - 369 ) with a time-dependent activity coefficient analogous to fractal-like kinetics formulated by Kopelman ( Kopelman, R. ( 1988 ) Science 241 , 1620 - 1626 ). We provide a mathematical derivation and experimental support to show that one of the parameters is a total activity coefficient and the other is an intrinsic constant that reflects the ability of the cellulases to overcome substrate recalcitrance. The model is applicable to individual cellulases and their mixtures at low-to-medium enzyme loads. Using biomass degrading enzymes from cellulolytic bacterium Thermobifida fusca , we show that the model can be used for mechanistic studies of enzymatic cellulose digestion. We also demonstrate that it applies to the crude supernatant of the widely studied cellulolytic fungus Trichoderma reesei ; thus it can be used to compare cellulases from different organisms. The two parameters may serve a similar role to Vmax, KM, and kcat in classical kinetics. A similar approach may be applicable to other enzymes with heterogeneous substrates and where a steady state is not achievable. PMID:23837567

  12. 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 ?mol 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 ?mol CO2/g wet sediment/day). When inorganic nitrogen was added alone maximum rates of CO2 production measured were 4.25 0.91 ?mol 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 ?mol P/g wet sediment) maximum rates of measured CO2 production increased more than four-fold to 18.40 1.04 ?mol 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 ?mol/g wet sediment and 16.16 1.28 ?mol CO2/g wet sediment/day respectively. The corresponding values for P were 63 95 nmol/g wet sediment and 12.05 1.31 ?mol 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 were not limiting Ks and qmax for crude oil were 4.52 1.51 mg oil/g wet sediment and 16.89 1.25 ?mol CO2/g wet sediment/day. At concentrations of inorganic N above 45 ?mol/g wet sediment inhibition of CO2 production from hydrocarbon degradation was evident. Analysis of bacterial 16S rRNA genes indicated that Alcanivorax spp. were selected in these marine sediments with increasing inorganic nutrient concentration, whereas Cycloclasticus spp. were more prevalent at lower inorganic nutrient concentrations. These data suggest that simple empirical estimates of the proportion of nutrients added relative to crude oil concentrations may not be sufficient to guarantee successful crude oil bioremediation in oxic beach sediments. The data we present also help define the maximum rates and hence timescales required for bioremediation of beach sediments. PMID:24782848

  13. 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 ?mol 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 ?mol CO2/g wet sediment/day). When inorganic nitrogen was added alone maximum rates of CO2 production measured were 4.25 0.91 ?mol 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 ?mol P/g wet sediment) maximum rates of measured CO2 production increased more than four-fold to 18.40 1.04 ?mol 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 ?mol/g wet sediment and 16.16 1.28 ?mol CO2/g wet sediment/day respectively. The corresponding values for P were 63 95 nmol/g wet sediment and 12.05 1.31 ?mol 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 were not limiting Ks and qmax for crude oil were 4.52 1.51 mg oil/g wet sediment and 16.89 1.25 ?mol CO2/g wet sediment/day. At concentrations of inorganic N above 45 ?mol/g wet sediment inhibition of CO2 production from hydrocarbon degradation was evident. Analysis of bacterial 16S rRNA genes indicated that Alcanivorax spp. were selected in these marine sediments with increasing inorganic nutrient concentration, whereas Cycloclasticus spp. were more prevalent at lower inorganic nutrient concentrations. These data suggest that simple empirical estimates of the proportion of nutrients added relative to crude oil concentrations may not be sufficient to guarantee successful crude oil bioremediation in oxic beach sediments. The data we present also help define the maximum rates and hence timescales required for bioremediation of beach sediments. PMID:24782848

  14. 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.

  15. 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.

  16. Quantitative analysis of relationships between irradiation parameters and the reproducibility of cyclotron-produced (99m)Tc yields.

    PubMed

    Tanguay, J; Hou, X; Buckley, K; Schaffer, P; Bénard, F; Ruth, T J; Celler, A

    2015-05-21

    Cyclotron production of (99m)Tc through the (100)Mo(p,2n) (99m)Tc reaction channel is actively being investigated as an alternative to reactor-based (99)Mo generation by nuclear fission of (235)U. An exciting aspect of this approach is that it can be implemented using currently-existing cyclotron infrastructure to supplement, or potentially replace, conventional (99m)Tc production methods that are based on aging and increasingly unreliable nuclear reactors. Successful implementation will require consistent production of large quantities of high-radionuclidic-purity (99m)Tc. However, variations in proton beam currents and the thickness and isotopic composition of enriched (100)Mo targets, in addition to other irradiation parameters, may degrade reproducibility of both radionuclidic purity and absolute (99m)Tc yields. The purpose of this article is to present a method for quantifying relationships between random variations in production parameters, including (100)Mo target thicknesses and proton beam currents, and reproducibility of absolute (99m)Tc yields (defined as the end of bombardment (EOB) (99m)Tc activity). Using the concepts of linear error propagation and the theory of stochastic point processes, we derive a mathematical expression that quantifies the influence of variations in various irradiation parameters on yield reproducibility, quantified in terms of the coefficient of variation of the EOB (99m)Tc activity. The utility of the developed formalism is demonstrated with an example. We show that achieving less than 20% variability in (99m)Tc yields will require highly-reproducible target thicknesses and proton currents. These results are related to the service rate which is defined as the percentage of (99m)Tc production runs that meet the minimum daily requirement of one (or many) nuclear medicine departments. For example, we show that achieving service rates of 84.0%, 97.5% and 99.9% with 20% variations in target thicknesses requires producing on average 1.2, 1.5 and 1.9 times the minimum daily activity requirement. The irradiation parameters that would be required to achieve these service rates are described. We believe the developed formalism will aid in the development of quality-control criteria required to ensure consistent supply of large quantities of high-radionuclidic-purity cyclotron-produced (99m)Tc. PMID:25909462

  17. Quantitative analysis of relationships between irradiation parameters and the reproducibility of cyclotron-produced 99mTc yields

    NASA Astrophysics Data System (ADS)

    Tanguay, J.; Hou, X.; Buckley, K.; Schaffer, P.; Bénard, F.; Ruth, T. J.; Celler, A.

    2015-05-01

    Cyclotron production of 99mTc through the 100Mo(p,2n) 99mTc reaction channel is actively being investigated as an alternative to reactor-based 99Mo generation by nuclear fission of 235U. An exciting aspect of this approach is that it can be implemented using currently-existing cyclotron infrastructure to supplement, or potentially replace, conventional 99mTc production methods that are based on aging and increasingly unreliable nuclear reactors. Successful implementation will require consistent production of large quantities of high-radionuclidic-purity 99mTc. However, variations in proton beam currents and the thickness and isotopic composition of enriched 100Mo targets, in addition to other irradiation parameters, may degrade reproducibility of both radionuclidic purity and absolute 99mTc yields. The purpose of this article is to present a method for quantifying relationships between random variations in production parameters, including 100Mo target thicknesses and proton beam currents, and reproducibility of absolute 99mTc yields (defined as the end of bombardment (EOB) 99mTc activity). Using the concepts of linear error propagation and the theory of stochastic point processes, we derive a mathematical expression that quantifies the influence of variations in various irradiation parameters on yield reproducibility, quantified in terms of the coefficient of variation of the EOB 99mTc activity. The utility of the developed formalism is demonstrated with an example. We show that achieving less than 20% variability in 99mTc yields will require highly-reproducible target thicknesses and proton currents. These results are related to the service rate which is defined as the percentage of 99mTc production runs that meet the minimum daily requirement of one (or many) nuclear medicine departments. For example, we show that achieving service rates of 84.0%, 97.5% and 99.9% with 20% variations in target thicknesses requires producing on average 1.2, 1.5 and 1.9 times the minimum daily activity requirement. The irradiation parameters that would be required to achieve these service rates are described. We believe the developed formalism will aid in the development of quality-control criteria required to ensure consistent supply of large quantities of high-radionuclidic-purity cyclotron-produced 99mTc.

  18. Kinetic theory of turbulence modeling: smallness parameter, scaling and microscopic derivation of Smagorinsky model

    NASA Astrophysics Data System (ADS)

    Ansumali, Santosh; Karlin, Iliya V.; Succi, Sauro

    2004-07-01

    A mean-field approach (filtering out subgrid scales) is applied to the Boltzmann equation in order to derive a subgrid turbulence model based on kinetic theory. It is demonstrated that the only Smagorinsky type model which survives in the hydrodynamic limit on the viscosity time scale is the so-called tensor-diffusivity model. Scaling of the filter-width with Reynolds number and Knudsen number is established. This sets the first rigorous step in deriving turbulence models from kinetic theory.

  19. 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 ?m particles.

  20. Kinetic-energy-driven enhancement of secondary-electron yields of highly charged ions impinging on thin films of C60 on Au

    NASA Astrophysics Data System (ADS)

    Bodewits, E.; Hoekstra, R.; Dobes, K.; Aumayr, F.

    2012-12-01

    The secondary electron yields as a result of slow highly charged ions (Ar4+,Ar13+) impinging on clean Au(111), highly oriented pyrolitic graphite, and thin films of C60 on Au are presented. In order to investigate the dynamics of the neutralization of the highly charged ions in front of the surface, angular scans have been performed. The results give a clear indication that the observed increase in electron yield seen on C60 compared to Au stems from kinetic-energy-driven processes and not from processes driven by the potential energy carried by the highly charged ion.

  1. Antioxidative effects of melatonin on kinetics, microscopic and oxidative parameters of cryopreserved bull spermatozoa.

    PubMed

    Ashrafi, Iraj; Kohram, Hamid; Ardabili, Farhad Farrokhi

    2013-06-01

    Reactive oxygen species generated during the freeze-thawing process may reduce sperm quality. This study evaluates the effects of melatonin supplementation as an antioxidant in the semen extender on post-thaw parameters of bull spermatozoa. Melatonin was added to the citrate-egg yolk extender to yield six different final concentrations: 0, 0.1, 1, 2, 3 and 4mM. Ejaculates were collected from six proven Holstein bulls. Semen was diluted in the extender packaged in straws, which was frozen with liquid nitrogen. The semen extender supplemented with various doses of melatonin increased (p<0.05) total motility, progressive motility, linearity, sperm track straightness, lateral head displacement, viability, integrity of the sperm membrane and total normal morphology of sperm after the freeze-thawing process. The most effective concentration of melatonin in microscopic evaluations of the bull sperm freezing extender was 2mM. The highest (p<0.05) value of total antioxidant capacity (48.92.7) and the lowest value of lipid peroxidation (2.70.8) were achieved by inclusion of 3mM concentration of melatonin in the semen extender and the highest activity of catalase (0.70.1) was obtained by 2mM melatonin. Four millimolar concentration of melatonin were reduced (p<0.05) the progressive motility and straight linear velocity. In conclusion, supplementation of 2 or 3mM concentration of melatonin in the semen extender improved the quality of post-thawed semen, which may associate with a reduction in lipid peroxidation as well as an increase in the total antioxidant capacity and antioxidant enzyme activity. PMID:23664651

  2. Conjugation of highly reactive aflatoxin B1 exo-8,9-epoxide catalyzed by rat and human glutathione transferases: estimation of kinetic parameters.

    PubMed

    Johnson, W W; Ueng, Y F; Widersten, M; Mannervik, B; Hayes, J D; Sherratt, P J; Ketterer, B; Guengerich, F P

    1997-03-18

    Aflatoxin B1 (AFB1) exo-8,9-epoxide, the reactive product of the hepatocarcinogen AFB1, is stable in aprotic solvents but hydrolyzes rapidly in H2O at 25 degrees C and pH 7 (t1/2 = 1 s). However, it is also known that some glutathione (GSH) transferases can conjugate the epoxide with GSH to give the adduct in high yield. We developed an approach to estimating kinetic parameters for reactions involving this epoxide or other substrates that are unstable to H2O. Varying concentrations of the (anhydrous) epoxide and GSH transferase were mixed and the GSH conjugates were measured. The final concentrations of product were known for each set of the starting epoxide and enzyme concentrations in a modeling approach, where the competition with the hydrolysis reaction is considered with two variables, a K for binding of the enzyme and epoxide and a rate k2, which includes microscopic steps following complex formation and resulting in conjugate formation. The ratio k2/K, a measure of enzyme efficiency, varied among individual recombinant GSH transferases in the the order (rat) 10-10 > 3-3 > (human) M1-1 > T1-1 > A1-1 > P1-1 > A2-2, from 3 x 10(6) to 10 M(-1) s(-1). The high ratio of M1-1 among the human GSH transferase enzymes tested is consistent with other work in which GSH-AFB1 conjugates were not detected in hepatocytes with an M1 null polymorphism. This general kinetic approach should be applicable to estimation of kinetic parameters involved in the interaction of other unstable substrates with enzymes. PMID:9115980

  3. 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 content (0.122), and similar to that for protein content (0.275). Daily cheese yields showed heritability estimates similar to those of daily milk yield. The trait %CY(WATER) showed a highly positive genetic correlation with %CY(SOLIDS) (0.87), whereas their phenotypic correlation was moderate (0.37), and the fat and protein contents of milk showed high genetic correlations with %CY traits. The heritability estimates of REC(PROTEIN) and REC(FAT) were larger (0.490 and 0.208, respectively) than those obtained for the protein and fat contents of milk, and the genetic relationships between REC(PROTEIN) and REC(FAT) with milk protein and fat content were low or moderate; REC(PROTEIN) and REC(FAT) were moderately correlated with the %CY traits and highly correlated with REC(SOLIDS) and REC(ENERGY). Both REC(SOLIDS) and REC(ENERGY) were heritable (0.274 and 0.232), and showed high correlations with each other (0.96) and with the %CY traits (0.83 to 0.97). Together, these findings demonstrate the existence of economically important, genetically determined variability in cheese yield that does not depend solely upon the fat and protein contents of milk, but also relies on the ability of the coagulum to retain the highest possible proportions of the available protein, fat, and water. Exploitation of this interesting genetic variation does not seem to be feasible through direct measurement of the phenotype in cows at the population level. Instead, further research is warranted to examine possible means for indirect prediction, such as through assessing the mid-infrared spectra of milk samples. PMID:24094539

  4. 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 441.1cM, 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. PMID:23423654

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

    PubMed

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

    2016-02-01

    This study determines and compares the intrinsic kinetic parameters (Ks and Ki) of selected Thermococcus onnurineus NA1 strains (wild-type (WT), and mutants MC01, MC02, and WTC156T) using the substrate inhibition model. Ks and Ki values were used to find the optimum dissolved CO (CL) conditions inside the reactor. The results showed that in terms of the maximum specific CO consumption rates (qCO(max)) of WT, MC01, MC02, and WTC156T the optimum activities can be achieved by maintaining the CL levels at 0.56mM, 0.52mM, 0.58mM, and 0.75mM, respectively. The qCO(max) value of WTC156T at 0.75mM was found to be 1.5-fold higher than for the WT strain, confirming its superiority. Kinetic modeling was then used to predict the conditions required to maintain the optimum CL levels and high cell concentrations in the reactor, based on the kinetic parameters of the WTC156T strain. PMID:26638136

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

    PubMed

    Rdt, Matthias; Gillet, Florian; Heege, Stefanie; Hitzler, Julian; Kalbfuss, Bernd; Gulat, 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. PMID:26306913

  7. Confidence intervals for the parameters estimated from simulated O2 uptake kinetics: effects of different data treatments.

    PubMed

    Francescato, M P; Cettolo, V; Bellio, R

    2014-01-01

    The behaviour of pulmonary O2 uptake following a moderate-intensity step exercise increment is usually described by a first brief increase, followed by a second exponential time course reaching the new steady state (phase II). The parameters describing the phase II kinetics are investigated by applying different data treatments to the acquired O2 uptake data to reduce the effects of their noise before running a non-linear regression procedure. The effects of different data treatments (nothing, resampling at various time intervals or averaging of more repetitions) on the precision and/or accuracy of the kinetics parameters estimated by non-linear regression with a simple mono-exponential model were investigated by artificially generating 10(5) simulated responses with average breath duration of 3.5 s. The simulations showed that, whatever the explored data treatment, the average estimated parameters were close to the theoretical ones. Nevertheless, in all the explored conditions, the non-linear regression provided narrower asymptotic confidence intervals than the real ones. In particular, when the responses were resampled at 1 s time intervals, the width of the asymptotic confidence interval for the time constant was 50% of the real one, even after the averaging of more repetitions. The reasons for this discrepancy were investigated further, allowing us to identify some methods to obtain the correct confidence interval of the O2 uptake kinetics parameters. The simplest method to obtain an asymptotic confidence interval close to the real one is to average more responses resampled to a time interval slightly longer than the average breath duration. PMID:24121286

  8. Cationic metallocene olefin polymerization catalysts. Thermodynamic and kinetic parameters for ion pair formation, dissociation, and reorganization

    SciTech Connect

    Deck, P.A.; Marks, T.J.

    1995-06-07

    We report here the first detailed calorimetric thermodynamic and NMR spectroscopic kinetic study of a prototypical, structurally well-characterized metallocenium catalyst system, (1,2-Me{sub 2}C{sub 5}H{sub 3}){sub 2}MCH{sub 3}{sup +}CH{sub 3}B(C{sub 6}/F{sub 5}){sub 3}{sup -}(M = Zr, Hf). From the acquired data, it is possible to map out the reaction coordinate(s) for the aforementioned ion pair formation/reorganization processes and to quantify several striking metal and solvent effects thereupon. The present results provide the first quantitative information on the thermodynamics and kinetics of metallocenium ion pair formation, dissociation, and stereomutation. The quantitative data indicate that the stability of the ion pairs with respect to the constituent neutrals is metal-dependent (Zr > Hf) and that processes which loosen the ion pairing and invert the local dissymmetry are also highly metal- and solvent-dependent. These results convey significant implications for catalyst stability, activity, and stereoregulation kinetics of the sterically-sensitive olefin insertion process. 13 refs., 1 fig., 1 tab.

  9. Relations between climatic-geomorphological parameters and sediment yield in a mediterranean semi-arid area (Sicily, southern Italy)

    NASA Astrophysics Data System (ADS)

    Grauso, Sergio; Pagano, Andrea; Fattoruso, Grazia; de Bonis, Piero; Onori, Filippo; Regina, Pasquale; Tebano, Carlo

    2008-03-01

    In the present work on-going research is discussed whose primary goal is to test some statistical methods to estimate the average yearly area-specific sediment yield (SSY). Using geomorphological and climatic parameters various multiple regression formulae have been set up based on SSY observed data from 16 catchments of Sicily. Three distinct techniques were adopted to select the parameters to be used in the equations: simple correlation, stepwise regression analysis and a supervised geomorphological-statistical correlation. The comparison of the results showed the effectiveness of the stepwise analysis, which led to a regression equation with a coefficient of determination ( r 2) of 0.87. Nevertheless, even this methodology showed some elements of uncertainty that have caused, in some cases, appreciable differences between observed and predicted values (mean percentage error equal to 26%). These differences are likely either due to the hydraulic regime of most of Sicilian watercourses (typical of semi-arid regions) or to hidden factors (e.g., topography, human impact and concentrated erosion), which can greatly affect the processes of sediment production and transport. The study has pointed out the need to take into account a larger number of observations and to perform the analysis of relations between suitable variables and SSY at a more detailed time resolution.

  10. 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

  11. 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.

  12. Kinetics of the reaction OH (v equals 0) plus O3 yields HO2 plus O2

    NASA Technical Reports Server (NTRS)

    Anderson, J. G.; Kaufman, F.

    1973-01-01

    The rate constant (kl) of the reaction OH(v=o) + O3 yields HO2 + O2 measured over the temperature range 220 to 450 K at total pressures between 2 and 5 torr using ultraviolet fluorescent scattering for the detection of OH radicals. An Arrhenius expression was obtained, and the rate constant for the reaction HO2 + O3 yields OH + 2O2 was inferred to be less than 0.1 kl over the entire temperature interval.

  13. Extrapolation of biodegradability test data by use of growth kinetic parameters.

    PubMed

    Blok, J

    1994-04-01

    Formulas for extrapolation of test data on biodegradability to percentage removal in treatment plants and biological half-life time in surface water are derived from growth kinetics. A pseudo-first-order rate constant can be used provided that substance properties and microbial density in the environment are assessed independently. For comparison of kinetics at different concentration levels an extrapolation factor can be used that is based on the ratio between maximum growth rate and sludge age in a treatment plant. The specific microbial density is estimated on the basis of proportional growth on all degradable substances in a state of equilibrium after adaptation. As a consequence the percentage removal can be predicted on the basis of sludge age and influent concentration in combination with the substance properties. The formulas predict that the combination of sewage treatment and surface water gives an almost equal biological half-life time for all readily biodegradable substances in the surface water. The predicted removal percentages and biological half-life times are in agreement with observations. PMID:7519549

  14. Kinetic parameters of red pepper waste as biomass to solid biofuel.

    PubMed

    Maia, Amanda Alves Domingos; de Morais, Leandro Cardoso

    2016-03-01

    This work aimed to study the kinetic of thermal degradation of red pepper waste as solid biofuel to bioenergy production. The thermal degradation experiments were conducted at three heating rates, 5°C/min, 7.5°C/min and 10°C/min in a thermogravimetric analyzer and oxidative atmosphere. The kinetic analysis was carried out applying the isoconversional model of Ozawa-Flynn-Wall. The activation energy was considerate low and varied 29.49-147.25kJ/mol. The enthalpies revealed the energy difference between the reagent and the activated complex agreed with activation energies, the values of the pre-exponential factor indicated empirical first order reactions, Gibbs free energy varied from 71.77kJ/mol to 207.03kJ/mol and the changes of entropies had negative values, indicating that the degree of disorder of products formed through bond dissociations was lower than initial reactants. The calorific value was 19.5MJ/kg, considered a relevant result for bioenergy production. PMID:26773950

  15. 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

    2014-01-01

    Inverse Dynamic calculations are routinely used in joint moment and power estimates during gait with anthropometric data often taken from published sources. Many biomechanical analyses have highlighted the need to obtain subject-specific anthropometric data (e.g. Mass, Centre of Mass, Moments of Inertia) yet the types of imaging techniques required to achieve this are not always available in the clinical setting. Differences in anthropometric sets have been shown to affect the reactive force and moment calculations in normal subjects but the effect on a paediatric diplegic cerebral palsy group has not been investigated. The aim of this study was to investigate the effect of using different anthropometric sets on predicted sagittal plane moments during normal and diplegic cerebral palsy gait. Three published anthropometric sets were applied to the reactive force and moment calculations of 14 Cerebral Palsy and 14 Control subjects. Statistically significant differences were found when comparing the different anthropometric sets but variability in the resulting sagittal plane moment calculations between sets was low (0.01-0.07 Nm/kg). In addition, the GDI-Kinetic, used as an outcome variable to assess whether differences were clinically meaningful, indicated no clinically meaningful difference between sets. The results suggest that the effects of using different anthropometric sets on the kinetic profiles of normal and diplegic cerebral palsy subjects are clinically insignificant. PMID:24200337

  16. Indoor formaldehyde removal by thermal catalyst: kinetic characteristics, key parameters, and temperature influence.

    PubMed

    Xu, Qiujian; Zhang, Yinping; Mo, Jinhan; Li, Xinxiao

    2011-07-01

    Thermal catalytic oxidation (TCO) technology can continuously degrade formaldehyde at room temperature without added energy. However, there is very little knowledge on the TCO kinetic reaction mechanism, which is necessary in developing such air cleaners and in comparison with other air cleaning techniques. This paper addresses the problem of a novel TCO catalyst, Pt/MnO(x)-CeO(2). The experiments measuring the outlet concentrations of formaldehyde and other possible byproducts were conducted at temperatures of 25, 40, 60, 100, and 180 C and at a series of inlet formaldehyde concentrations (280-3000 ppb). To measure the concentrations precisely and real timely, proton transfer reaction-mass spectrometry (PTR-MS) was used. We found the following from the experimental results: (1) no byproducts were detected; (2) the bimolecular L-H kinetic model best described the catalytic reaction rate; (3) the activation energy of the oxidation was about 25.8 kJ mol(-1); (4) TCO is most energy efficient at room temperature without auxiliary heating; (5) compared with photocatalytic oxidation (PCO) which needs ultraviolet light radiation, the reaction area of TCO can be much larger for a given volume so that TCO can perform much better not only in formaldehyde removal efficiency but also in energy saving. PMID:21667968

  17. 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

  18. Kinetics and quantum yield of photoluminescence of EuFOD{sub 3} doped into a nanoporous glass with the help of supercritical CO{sub 2}

    SciTech Connect

    Bagratashvili, V N; Tsypina, S I; Chutko, E A; Gerasimova, V I; Gordienko, V M

    2008-08-31

    The kinetics of photoluminescence of a EuFOD{sub 3} metalloorganic compound doped into a nanoporous Vycor glass by the method of supercritical fluid impregnation is studied. The lifetime of luminescence of EuFOD{sub 3} molecules in pores excited by an excimer XeCl laser was 40 {mu}s, which is considerably smaller than this lifetime (150-890 {mu}s) in solutions. The quantum yield of luminescence of EuFOD{sub 3} was estimate as {approx}4x10{sup -4}. (laser applications and other topics in quantum electronics)

  19. 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.

  20. A novel bacterial expression method with optimized parameters for very high yield production of triple-labeled proteins.

    PubMed

    Murray, Victoria; Huang, Yuefei; Chen, Jianglei; Wang, Jianjun; Li, Qianqian

    2012-01-01

    The Gram-negative bacterium Escherichia coli offer a means for rapid, high-yield, and economical production of recombinant proteins. However, when preparing protein samples for NMR, high-level production of functional isotopically labeled proteins can be quite challenging. This is especially true for the preparation of triple-labeled protein samples in D(2)O ((2)H/(13)C/(15)N). The large expense and time-consuming nature of triple-labeled protein production for NMR led us to revisit the current bacterial protein expression protocols. Our goal was to develop an efficient bacterial expression method for very high-level production of triple-labeled proteins that could be routinely utilized in every NMR lab without changing expression vectors or requiring fermentation. We developed a novel high cell-density IPTG-induction bacterial expression method that combines tightly controlled traditional IPTG-induction expression with the high cell-density of auto-induction expression. In addition, we optimize several key experimental protocols and parameters to ensure that our new high cell-density bacterial expression method routinely produces 14-25 mg of triple-labeled proteins and 15-35 mg of unlabeled proteins from 50-mL bacterial cell cultures. PMID:22167665

  1. Kinetic parameters of radical reactions of 2-mercaptobenzothiazole with quinone imines

    NASA Astrophysics Data System (ADS)

    Varlamov, V. T.; Gadomska, A. V.

    2014-09-01

    The chain reaction of N, N'-diphenyl-1,4-benzoquinone diimine with 2-mercaptobenzothiazole was studied by two methods developed earlier for the nonchain reaction of N-phenyl-1,4-benzoquinone monoimine with 2-mercaptobenzothiazole. In the methods used, the kinetic scheme of the reaction is simplified by creating conditions under which the rates of all stages except radical generation and decay can be neglected. One of the methods was updated. For the nonchain reaction of N-phenyl-1,4-benzoquinone monoimine with 2-mercaptobenzothiazole, both methods gave close results; for the chain reaction of N, N'-diphenyl-1,4-phenylenediamine with 2-mercaptobenzothiazole, the results differed by approximately one order of magnitude.

  2. Crystallization kinetics of lithium niobate glass: determination of the Johnson-Mehl-Avrami-Kolmogorov parameters.

    PubMed

    Choi, H W; Kim, Y H; Rim, Y H; Yang, Y S

    2013-06-28

    The formation of crystalline LiNbO3 (LN) from LN glass has been studied by means of differential scanning calorimetry and in situ synchrotron X-ray diffraction. The LN glass with no glass former was prepared by the polymerized complex method. The isothermal kinetics of the crystallization process is described using the Johnson-Mehl-Avrami-Kolmogorov (JMAK) equation and the Avrami exponent n is found to be ~2.0, indicating that the crystallization mechanism is diffusion-controlled growth with a decreasing nucleation rate. The effective activation energy of crystallization calculated from isothermal measurements is 6.51 eV. It is found that the LN glass directly transforms into a rhombohedral LN crystal without any intermediate crystalline phase and most crystal grains are confined within the size of ~40 nm irrespective of different isothermal temperatures. Application of JMAK theory to the non-isothermal thermoanalytical study of crystallization of LN glass is discussed. PMID:23677338

  3. Estimation of kinetic parameters of transcription from temporal single-RNA measurements.

    PubMed

    Zimmer, Christoph; Hkkinen, Antti; Ribeiro, Andre S

    2016-01-01

    Gene expression dynamics in prokaryotes is largely controlled by the multi-step process of transcription initiation whose kinetics is subject to regulation. Since the number and duration of these steps cannot be currently measured in vivo, we propose a novel method for estimating them from time series of RNA numbers in individual cells. We demonstrate the method's applicability on measurements of fluorescence-tagged RNA molecules in Escherichia coli cells, and compare with a previous method. We show that the results of the two methods agree for equal data. We also show that, when incorporating additional data, the new method produces significantly different estimates, which are in closer agreement with qPCR measurements. Unlike the previous method, the new method requires no preprocessing of the RNA numbers, using maximal information from the RNA time series. In addition, it can use data outside of the observed RNA productions. Overall, the new method characterizes the transcription initiation process with enhanced detail. PMID:26522167

  4. 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

    2016-03-01

    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 [Formula: see text]. 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 [Formula: see text], [Formula: see text], [Formula: see text] and [Formula: see text], 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. PMID:26208491

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

    PubMed

    Ostrovski? KuM; Voskoboev, A I; Gorenshten?n, B I; Dosta, G A

    1979-09-01

    The molecula-kinetic parameters (Km, Ki) of three thiamine enzymes, e. g. thiamine pyrophosphokinase (EC 2.7.6.2), pyruvate dehydrogenase (EC 1.2.4.1) and transketolase (EC 2.2.1.1) with respect to the effects of the thiamine antimetabolite hydroxythiamine in the whole animal organism have been compared. It has been shown that only the first two enzymes, which interact competitively with the vitamin, antivitamin or their pyrophosphate ethers, obey the kinetic parameters obtained for the purified enzymes in vitro. The anticoenzymic effect of hydroxythiamine pyrophosphate with respect to transketolase is not observed in vivo at maximal concentration of the anticoenzyme in tissues due to the absence of competitive interactions with thiamine pyrophosphate. The incorporation of the true and false coenzymes into transketolase occurs only during de novo transketolase synthesis (the apoform is absent in tissues, with the exception of erythrocytes) and proceeds slowly with a half-life time equal to 24--30 hrs. After a single injection of hydroxythiamine at a large dose (70--400 mg/kg) the maximal inhibition of the transketolase activity in tissues (liver, heart, kidney, muscle, spleen, lungs adrenal grands) manifests itself by the 48th--72nd hour, when the concentration of free hydroxythiamine and its pyrophosphate is minimal and the whole anticoenzyme is tightly bound to the protein, forming the false holoenzyme. The use of hydroxythiamine for inhibition of pyruvate dehydrogenase or transketolase in animal organism is discussed. PMID:228770

  6. 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.

  7. Attenuation length in ion-induced kinetic electron emission: A key to an understanding of angular-dependent yields

    NASA Astrophysics Data System (ADS)

    Wittmaack, Klaus

    2015-03-01

    The mean attenuation length, , of electrons emitted from ion bombarded solids was derived from measured angular-dependent electron yields ?(?) in combination with Monte Carlo simulations of inelastic (electronic) energy deposition. The transport controlled contributions of excited electrons to the measured electron yields were derived as the integral gL over Seexp (-z /L ), where Se(? ,z ) is the electronic energy deposition and z the depth from the surface. The unknown attenuation length L ? reflects the average over the energy spectrum and the angular distribution of those internally excited electrons that can reach the solid-vacuum interface and overcome the surface barrier. To determine L , the ratios gL(? ) /gL(0 ) , calculated for 0 ?L ?10 nm , were compared with measured yield ratios ?(?)/?(0) for a wide variety of projectile-target combinations and impact energies between 1 and 50 keV (velocity-proportional electronic stopping). The procedure works well at angles at which Se(?,z ) decreases smoothly in the depth region between 1 and 3 nm. The result is =1.5 0.3 nm, a number basically in accordance with expectation based on estimated data for the inelastic mean free path of low-energy electrons (<25 eV) but a factor of 10 lower than the numbers recently advocated (10-15 nm) to rationalize "internal" electron yields observed with metal-insulator-metal sandwich structures.

  8. Methyl isocyanide isomerization kinetics: determination of collisional deactivation parameters following C-H overtone excitation

    SciTech Connect

    Snavely, D.L.; Zare, R.N.; Miller, J.A.; Chandler, D.W.

    1986-07-31

    The isomerization of methyl isocyanide (CH/sub 3/NC) to acetonitrile (CH/sub 3/CN) was studied by excitation of the 5nu/sub C-H/ (726.6 nm) and 6nu/sub C-H/ (621.4 nm) overtone states, which lie about 1 and 8 kcal/mol, respectively, above the isomerization barrier. Products yields were measured as a function of pressure and collision partner. A Stern-Volmer plot (yield/sup -1/ vs. pressure) shows that (1) deactivation by collision with pure CH/sub 3/NC is more rapid than with C/sub 3/H/sub 6/, SF/sub 6/, or Ar, (2) the collisional deactivation efficiencies decrease in going from C/sub 3/H/sub 6/ to SF/sub 6/ to Ar, and (3) the single-collision deactivation approximation (strong collider approximation) fails for both the 6nu/sub C-H/ and 5nu/sub C-H/ data. With the use of a master equation solution, assuming an exponential down energy-transfer function, the average energy transferred in a deactivating collision, -<..delta..E>/sub down/, is extracted from each data set, as well as the average energy transferred fer collision, -<..delta..E>. It is concluded that the isomerization yield depends markedly on the collision partner and on the average energy transferred per collision, -<..delta..E>, even though the single-collision deactivation approximation might have been expected to have its greatest validity in this energy regime.

  9. 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.

  10. Kinetic Modeling and Parameter Estimation in a Tower Bioreactor for Bioethanol Production

    NASA Astrophysics Data System (ADS)

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

    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.

  11. 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.

  12. Gender bias on the effects of instruction on kinematic and kinetic jump parameters of high-level athletes.

    PubMed

    Walsh, Mark S; Waters, Jeff; Kersting, Uwe G

    2007-01-01

    The purposes of this study were to examine gender differences during drop jumps, to evaluate the effect of a set of simple instructions on kinematic and kinetic parameters during a drop jump, and to determine if there are gender differences in the effects of instruction on those parameters. Twenty-five basketball players, 13 men and 12 women, performed drop jumps from a box (height 30.5 cm) after being asked to perform a land and jump movement as they normally would do when aiming at maximum jump height. The experimental group received a set of instructions designed to make them land softer. The measured parameters were impact force at landing, ground contact time, flight time, frontal plane knee angle, sagittal plane knee angle, and distance between the knees. When the groups were examined by gender, no differences in the parameters were seen in men after instruction, but in women the following significant differences were detected: an increase in contact time, a decrease in landing force, and a decrease in inward movement of the knees after landing. These data indicate that females respond differently to jumping/landing instructions. PMID:18158693

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

    PubMed

    Pitakpoolsil, Wipawan; Hunsom, Mali

    2014-01-15

    The possibility of using commercial chitosan flakes as an adsorbent for the removal of pollutants from biodiesel wastewater was evaluated. The effect of varying the adsorption time (0.5-5h), initial wastewater pH (2-8), adsorbent dose (0.5-5.5g/L) and mixing rate (120-350rpm) on the efficiency of pollutant removal was explored by univariate analysis. Under the derived optimal conditions, greater than 59.3%, 87.9% and 66.2% of the biological oxygen demand (BOD), chemical oxygen demand (COD) and oil & grease, respectively, was removed by a single adsorption. Nevertheless, the remaining BOD, COD and oil & grease were still higher than the acceptable Thai government limits for discharge into the environment. When the treatment was repeated, a greater than 93.6%, 97.6% and 95.8% removal of the BOD, COD and oil & grease, respectively, was obtained. The reusability of commercial chitosan following NaOH washing (0.05-0.2M) was not suitable, with less than 40% efficiency after just one recycling and declining rapidly thereafter. The adsorption kinetics of all pollutant types by the commercial chitosan flakes was controlled by a mixed process of diffusion and adsorption of the pollutants during the early treatment period (0-1.5h) and then solely controlled by adsorption after 2h. PMID:24412591

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

    PubMed

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

    2015-09-01

    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

  15. 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.

  16. Enhancing the heat stability and kinetic parameters of the maize endosperm ADP-glucose pyrophosphorylase using iterative saturation mutagenesis.

    PubMed

    Boehlein, Susan K; Shaw, Janine R; Stewart, Jon D; Sullivan, Bradford; Hannah, L Curtis

    2015-02-15

    Iterative saturation mutagenesis (ISM) has been used to improve the thermostability of maize endosperm ADP-glucose pyrophosphorylase (AGPase), a highly-regulated, rate-limiting and temperature-sensitive enzyme essential for starch biosynthesis. The thermo-sensitivity of heterotetrameric AGPase has been linked to grain loss in cereals and improving this property might therefore have direct impacts on grain yield. Nine amino acids were selected for site-saturation mutagenesis on the basis of elevated B-factors in the crystal structure of the closest available homolog (a small subunit homotetramer of potato AGPase). After each round of mutagenesis, iodine staining and antibody capture activity assays at varying temperatures were used to select the optimum positions and amino acid changes for the next rounds of mutagenesis. After three iterations, the signals from whole-colony iodine staining were saturated and a heat stable AGPase variant was obtained. Kinetic studies of the heat stable mutant showed that it also had an unexpected increased affinity for the activator, 3-PGA. This is particularly valuable as both the temperature stability and allosteric properties of AGPase significantly influence grain yield. PMID:25600571

  17. Robust parameter estimation during logistic modeling of batch and fed-batch culture kinetics.

    PubMed

    Goudar, Chetan T; Konstantinov, Konstantinov B; Piret, James M

    2009-01-01

    Methods for robust logistic modeling of batch and fed-batch mammalian cell cultures are presented in this study. Linearized forms of the logistic growth, logistic decline, and generalized logistic equation were derived to obtain initial estimates of the parameters by linear least squares. These initial estimates facilitated subsequent determination of refined values by nonlinear optimization using three different algorithms. Data from BHK, CHO, and hybridoma cells in batch or fed-batch cultures at volumes ranging from 100 mL-300 L were tested with the above approach and solution convergence was obtained for all three nonlinear optimization approaches for all data sets. This result, despite the sensitivity of logistic equations to parameter variation because of their exponential nature, demonstrated that robust estimation of logistic parameters was possible by this combination of linearization followed by nonlinear optimization. The approach is relatively simple and can be implemented in a spreadsheet to robustly model mammalian cell culture batch or fed-batch data. PMID:19496143

  18. Characterization of Nicotinamidases: Steady-State Kinetic Parameters, Class-wide Inhibition by Nicotinaldehydes and Catalytic Mechanism

    PubMed Central

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

    2010-01-01

    Nicotinamidases are metabolic enzymes that hydrolyze nicotinamide to nicotinic acid. These enzymes are widely distributed across biology, with examples found encoded in the genomes of Mycobacteria, Archaea, Eubacteria, Protozoa, yeast and invertebrates but there are none found in mammals. Although recent structural work has improved understanding of these enzymes, their catalytic mechanism is still not well understood. Recent data shows that nicotinamidases are required for growth and virulence of several pathogenic microbes. The enzymes of Saccharomyces cerevisiae, Drosophila melanogaster and Caenorhabditis elegans regulate lifespan in their respective organisms, consistent with proposed roles in the regulation of NAD+ metabolism and organismal aging. In this manuscript, the steady state kinetic parameters of nicotinamidase enzymes from C. elegans, S. cerevisiae, Streptococcus pneumoniae (a pathogen responsible for human pneumonia), Borrelia burgdorferi (the pathogen that causes Lyme Disease) and Plasmodium falciparum (responsible for most human malaria) are reported. Nicotinamidases are generally efficient catalysts with steady state kcat values typically exceeding 1 s?1. The Km values for nicotinamide are low and are in the range from 2 110 M. Nicotinaldehyde was determined to be a potent competitive inhibitor of these enzymes, binding in the low M to low nM range for all nicotinamidases tested. A variety of nicotinaldehyde derivatives were synthesized and evaluated as inhibitors in kinetic assays. Inhibitions are consistent with reaction of the universally conserved catalytic Cys on each enzyme with the aldehyde carbonyl carbon to form a thiohemiacetal complex which is stabilized by a conserved oxyanion hole. The S. pneumoniae nicotinamidase can catalyse exchange of 18O into the carboxy oxygens of nicotinic acid with 18O-water. The collected data, along with kinetic analysis of several mutants, allowed us to propose a catalytic mechanism that explains nicotinamidase and nicotinic acid 18O exchange chemistry for the S. pneumoniae enzyme involving key catalytic residues, a catalytic transition metal ion and the intermediacy of a thioester intermediate. PMID:20979384

  19. 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 avoiding integration, the developed technology is of great significance for a broad panel of applications, including transcription-factor-based induced cell fate conversion and controlled transfer of genetically encoded RNA- or protein-based drugs. PMID:25728583

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

    NASA Astrophysics Data System (ADS)

    Hageseth, Gaylord T.

    1982-02-01

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

  1. Optical absorption spectra and kinetic parameters of products of the radiolysis of sodium and potassium chlorates

    SciTech Connect

    Borisova, I.A.; Polganov, V.S.; Safanov, Y.N.; Trushnikov, V.N.

    1986-11-01

    The absorption spectra arising from the irradiation of single crystals of NaC10/sub 3/ and KC10/sub 3/ with nanosecond pulses of electrons were studied. The spectra were found to consist of the superposition of a large number of absorption bands. The overall spectra were broken down into components and the separated absorption bands identified. Spectrokinetic parameters of the transient centers were determined. Some characteristic features which are peculiar to this class of compounds when exposed to high-density pulsed radiation were identified.

  2. A deficiency of manganese ions in the presence of high sugar concentrations is the critical parameter for achieving high yields of itaconic acid by Aspergillus terreus.

    PubMed

    Karaffa, Levente; Daz, Rafael; Papp, Benedek; Fekete, Erzsbet; Sndor, Erzsbet; Kubicek, Christian P

    2015-10-01

    Itaconic acid (IA), an unsaturated dicarboxylic acid with a high potential as a platform for chemicals derived from sugars, is industrially produced by large-scale submerged fermentation by Aspergillus terreus. Although the biochemical pathway and the physiology leading to IA is almost the same as that leading to citric acid production in Aspergillus niger, published data for the volumetric (g L(-1)) and the specific yield (mol/mol carbon source) of IA are significantly lower than for citric acid. Citric acid is known to accumulate to high levels only when a number of nutritional parameters are carefully adjusted, of which the concentration of the carbon source and that of manganese ions in the medium are particularly important. We have therefore investigated whether a variation in these two parameters may enhance IA production and yield by A. terreus. We show that manganese ion concentrations?yields. Highest yields were also dependent on the concentration of the carbon source (D-glucose), and highest yields (0.9) were only obtained at concentrations of 12-20 % (w/v), thus allowing the accumulation of up to 130 g L(-1) IA. These findings perfectly mirror those obtained when these parameters are varied in citric acid production by A. niger, thus showing that the physiology of both processes is widely identical. Consequently, applying the fermentation technology established for citric acid production by A. niger citric acid production to A. terreus should lead to high yields of IA, too. PMID:26078111

  3. Use of a Plackett-Burman experimental design to examine the impact of extraction parameters on yields and compositions of pectins extracted from chicory roots (Chicorium intybus L.).

    PubMed

    Robert, Christelle; Devillers, Thierry; Wathelet, Bernard; Van Herck, Jean-Claude; Paquot, Michel

    2006-09-20

    Chicory root pectin was isolated by acid extraction followed by alcohol precipitation. Because the extraction conditions have important effects on the features of pectins, an experimental design was used to study the influence of 17 different extraction parameters on yield and composition of pectin: pH, temperature, time of extraction, solid/liquid ratio, and different pretreatments of the pulps before extraction. Twenty extractions were conducted and examined for their significance on yield and sugar content using the Plackett-Burman factorial design. The acid extraction of chicory roots resulted in an average yield of 11% containing 86% of sugars. It was found that extraction temperature, time, protease pretreatment, water purity, and water washing of pulps significantly affected yield and pectin composition with an increase of yield and purity of pectin in harsher extraction conditions. PMID:16968078

  4. 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. PMID:19911293

  5. Measurement of kinetic rate law parameters on a Na?Ca?Al borosilicate glass for low-activity waste

    NASA Astrophysics Data System (ADS)

    McGrail, B. P.; Ebert, W. L.; Bakel, A. J.; Peeler, D. K.

    1997-10-01

    The dissolution kinetics of a Na?Ca?Al borosilicate glass, being studied for immobilization of low-activity waste, were measured between 20 and 90C and solution pH between 6 and 12 using the single-pass flow-through method. Dissolution kinetics measurements are needed to parameterize a mechanistic model that is being used to compute the corrosion rate of the glass waste form as a function of temperature, pH, and the concentrations of the other glass components in water percolating through a proposed shallow-land disposal facility. The key factors that were found to influence the test results include test duration and background subtraction of the raw data. Background subtraction is shown to be important to prevent a non-physical increase in the computed rate with increasing flow rate, particularly in tests run at higher flow rates. Experimental factors that were found to have no detectable influence on the test results included the glass particle size and buffer type. We also illustrate how flow rate variations can be used to obtain information about the reaction order and equilibrium constant parameters in a conventional transition-state theory rate law.

  6. A method for conforming the pH dependence of the michaelis parameters of nonallosteric enzymes to four kinetic schemes.

    PubMed

    Vega-Catalan, F J

    1990-10-01

    A nonlinear regression program for the analysis of the effect of pH on enzyme activity has been developed for the IBM micro range and compatible machines. The program conforms the V and Km pH profiles to one of four commonly occurring kinetic schemes. By using multiple linear regression the program computes initial estimates for the nonlinear search which are thus not required from the user. Two nonlinear optimization methods are included in order to effectively handle the nonnegativity constraints on the parameters. The program is user-friendly and provides plots of the fit and residual plots to help the user decide on the goodness of fit obtained. The program was coded in Turbo Pascal version 4.0 and runs on IBM micros or close compatibles with four types of graphics cards. PMID:2225789

  7. 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. PMID:24929526

  8. 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.

  9. Interactive effects of elevated CO2 concentration and irrigation on photosynthetic parameters and yield of maize in Northeast China.

    PubMed

    Meng, Fanchao; Zhang, Jiahua; Yao, Fengmei; Hao, Cui

    2014-01-01

    Maize is one of the major cultivated crops of China, having a central role in ensuring the food security of the country. There has been a significant increase in studies of maize under interactive effects of elevated CO2 concentration ([CO2]) and other factors, yet the interactive effects of elevated [CO2] and increasing precipitation on maize has remained unclear. In this study, a manipulative experiment in Jinzhou, Liaoning province, Northeast China was performed so as to obtain reliable results concerning the later effects. The Open Top Chambers (OTCs) experiment was designed to control contrasting [CO2] i.e., 390, 450 and 550 molmol(-1), and the experiment with 15% increasing precipitation levels was also set based on the average monthly precipitation of 5-9 month from 1981 to 2010 and controlled by irrigation. Thus, six treatments, i.e. C550W+15%, C550W0, C450W+15%, C450W0, C390W+15% and C390W0 were included in this study. The results showed that the irrigation under elevated [CO2] levels increased the leaf net photosynthetic rate (Pn) and intercellular CO2 concentration (Ci) of maize. Similarly, the stomatal conductance (Gs) and transpiration rate (Tr) decreased with elevated [CO2], but irrigation have a positive effect on increased of them at each [CO2] level, resulting in the water use efficiency (WUE) higher in natural precipitation treatment than irrigation treatment at elevated [CO2] levels. Irradiance-response parameters, e.g., maximum net photosynthetic rate (Pnmax) and light saturation points (LSP) were increased under elevated [CO2] and irrigation, and dark respiration (Rd) was increased as well. The growth characteristics, e.g., plant height, leaf area and aboveground biomass were enhanced, resulting in an improved of yield and ear characteristics except axle diameter. The study concluded by reporting that, future elevated [CO2] may favor to maize when coupled with increasing amount of precipitation in Northeast China. PMID:24848097

  10. Interactive Effects of Elevated CO2 Concentration and Irrigation on Photosynthetic Parameters and Yield of Maize in Northeast China

    PubMed Central

    Meng, Fanchao; Zhang, Jiahua; Yao, Fengmei; Hao, Cui

    2014-01-01

    Maize is one of the major cultivated crops of China, having a central role in ensuring the food security of the country. There has been a significant increase in studies of maize under interactive effects of elevated CO2 concentration ([CO2]) and other factors, yet the interactive effects of elevated [CO2] and increasing precipitation on maize has remained unclear. In this study, a manipulative experiment in Jinzhou, Liaoning province, Northeast China was performed so as to obtain reliable results concerning the later effects. The Open Top Chambers (OTCs) experiment was designed to control contrasting [CO2] i.e., 390, 450 and 550 µmol·mol−1, and the experiment with 15% increasing precipitation levels was also set based on the average monthly precipitation of 5–9 month from 1981 to 2010 and controlled by irrigation. Thus, six treatments, i.e. C550W+15%, C550W0, C450W+15%, C450W0, C390W+15% and C390W0 were included in this study. The results showed that the irrigation under elevated [CO2] levels increased the leaf net photosynthetic rate (Pn) and intercellular CO2 concentration (Ci) of maize. Similarly, the stomatal conductance (Gs) and transpiration rate (Tr) decreased with elevated [CO2], but irrigation have a positive effect on increased of them at each [CO2] level, resulting in the water use efficiency (WUE) higher in natural precipitation treatment than irrigation treatment at elevated [CO2] levels. Irradiance-response parameters, e.g., maximum net photosynthetic rate (Pnmax) and light saturation points (LSP) were increased under elevated [CO2] and irrigation, and dark respiration (Rd) was increased as well. The growth characteristics, e.g., plant height, leaf area and aboveground biomass were enhanced, resulting in an improved of yield and ear characteristics except axle diameter. The study concluded by reporting that, future elevated [CO2] may favor to maize when coupled with increasing amount of precipitation in Northeast China. PMID:24848097

  11. Temperature dependence on hydration kinetic model parameters during rehydration of parboiled rice.

    PubMed

    Rafiq, Aasima; Chowdhary, Juri; Hazarika, Manuj Kumar; Makroo, Hilal Ahmad

    2015-09-01

    A study was carried out to relate the hydration behaviour with processing conditions of low amylose content parboiled rice which was dried at various temperatures (40, 50 and 60C). The rehydration characteristics of the parboiled rice (dehusked only) was then studied at various soaking temperatures (30, 40 and 50C) and time ( upto 3h at every 30min interval) and equilibrium moisture content of rehydration (EMC) was determined. The data were tested on three hydration equations viz., Peleg's, Exponential and Weibull equations. The experimental data were used to determine the model parameters. The goodness of fit for the models were evaluated by coefficient of determination (R(2)) and sum of square error (SSE). The results were indicated that the Weibull model fits better than the exponential model and Peleg's equation. Also, water transfer to paddy, was described by applying the Fick's diffusion model and the moisture diffusivity (D) was calculated. The Diffusivity values varied between 1.06 and 4??10(-11)m(2)/s. PMID:26345034

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

    PubMed

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

    2010-05-21

    Optimal experiment design for parameter estimation (OED/PE) has become a popular tool for efficient and accurate estimation of kinetic model parameters. When the kinetic model under study encloses multiple parameters, different optimization strategies can be constructed. The most straightforward approach is to estimate all parameters simultaneously from one optimal experiment (single OED/PE strategy). However, due to the complexity of the optimization problem or the stringent limitations on the system's dynamics, the experimental information can be limited and parameter estimation convergence problems can arise. As an alternative, we propose to reduce the optimization problem to a series of two-parameter estimation problems, i.e., an optimal experiment is designed for a combination of two parameters while presuming the other parameters known. Two different approaches can be followed: (i) all two-parameter optimal experiments are designed based on identical initial parameter estimates and parameters are estimated simultaneously from all resulting experimental data (global OED/PE strategy), and (ii) optimal experiments are calculated and implemented sequentially whereby the parameter values are updated intermediately (sequential OED/PE strategy). This work exploits OED/PE for the identification of the Cardinal Temperature Model with Inflection (CTMI) (Rosso et al., 1993). This kinetic model describes the effect of temperature on the microbial growth rate and encloses four parameters. The three OED/PE strategies are considered and the impact of the OED/PE design strategy on the accuracy of the CTMI parameter estimation is evaluated. Based on a simulation study, it is observed that the parameter values derived from the sequential approach deviate more from the true parameters than the single and global strategy estimates. The single and global OED/PE strategies are further compared based on experimental data obtained from design implementation in a bioreactor. Comparable estimates are obtained, but global OED/PE estimates are, in general, more accurate and reliable. PMID:20064532

  13. Kinetics of the reaction OH + HO2 yields H2O + O2 from 254 to 382 K

    NASA Technical Reports Server (NTRS)

    Keyser, Leon F.

    1988-01-01

    The discharge-flow resonance fluorescence technique has been used to determine the absolute rate constant for the reaction OH + HO2 yields H2O + O2 from 254 to 382 K at a total pressure of 1 Torr. Pseudo-=first-order conditions were used with HO2 in large excess over OH. The rate constant was obtained directly from observed decays of OH and measured concentrations of HO2. Since the observed rate constant was found to be very sensitive to small background concentrations of O and H atoms, NO2 was used to remove both atom species from the system. With added NO2 the result at 299 K is (1.1 + or - 0.3) x 10 to the -10th cu cm/molecule where the error limits are one standard deviation and include an estimate of overall experimental uncertainty. The temperature dependence expressed in Arrhenius form is (4.8 + or - 0.8) x 10 to the -11th exp (250 + or - 50)/T. The results are independent of the type of reactor surface and the precursor used to produce OH and HO2. The present results agree well with earlier measurements near 1-atm total pressure and suggest that this rate constant exhibits little or no pressure dependence between 1 and 1000 Torr.

  14. Computer-based gait analysis of dogs: evaluation of kinetic and kinematic parameters after cemented and cementless total hip replacement.

    PubMed

    Dren, S; Bddeker, J; Meyer-Lindenberg, A; Fehr, M; Nolte, I; Wefstaedt, P

    2012-01-01

    To date it is unclear whether cementless total hip replacement (THR) in dogs is of clinical advantage in comparison to cemented THR with regard to lameness improvement. Thus the aim of this study was to compare objectively the development of the gait pattern after cemented and cementless THR in dogs. For this purpose, 18 adult dogs with hip dysplasia underwent computer-based gait analysis on an instrumented treadmill prior to unilateral THR and then again ten days, four weeks and four months after surgery. Analysed kinetic parameters were symmetry indices (SI) of vertical ground reaction forces (GRF), which included peak vertical forces (PFz), mean vertical forces (MFz), vertical impulse (IFz), and vertical ground reaction forces of the arthroplasty limbs only. Analysed kinematic parameters were range-of-motion and the flexion and extension angles of hip, stifle and hock joints. The symmetry indice for PVF, MFz and IFz decreased to a value less than six in both THR groups four months after surgery, which is defined as not lame. Improvement in lameness of the arthroplasty limbs during the examination period of four months was not significantly different between the cemented and cementless groups. The results suggest that within a short-term observation period of four months after surgery, neither cementless nor cemented THR have a greater advantage with regard to lameness improvement. Additional studies with larger pools of subjects and longer time periods for follow-up examinations are necessary to verify these findings. PMID:22828804

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

    PubMed

    Sensz, 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. PMID:18068973

  16. 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.

  17. Effects of sulfate reduction on the bacterial community and kinetic parameters of a dechlorinating culture under chemostat growth conditions.

    PubMed

    Berggren, Dusty R V; Marshall, Ian P G; Azizian, Mohammad F; Spormann, Alfred M; Semprini, Lewis

    2013-02-19

    Results are presented from a chemostat study where the reductive dehalogenation of PCE was evaluated in the absence and presence of sulfate. Two chemostats inoculated with the Point Mugu culture, which contains strains of Dehalococcoides mccartyi, were operated at a 50 day HRT and fed PCE (1.12 mM) and lactate (4.3 mM). The control chemostat (PM-5L, no sulfate), achieved pseudo-steady-state transformation of PCE to ethene (98%) and VC (2%) at 2.4 nM of H(2). Batch kinetic tests with chemostat harvested cells showed the maximum rate (k(max)X) value for each dehalogenation step remained fairly constant, while hupL clone library analyses showed maintenance of a diverse D. mccartyi community. Sulfate (1 mM) was introduced to the second chemostat, PM-2L. Effective sulfate reduction was achieved 110 days later, resulting in 600 ?M of total sulfide. PCE dechlorination efficiency decreased following complete sulfate reduction, yielding ethene (25%), VC (67%), and cis-DCE (8%). VC dechlorination was most affected, with k(max)X values decreasing by a factor of 50. The decrease was associated with the enrichment of the Cornell group of D. mccartyi and decline of the Pinellas group. Long-term exposure to sulfides and/or competition for H(2) may have been responsible for the community shift. PMID:23316874

  18. 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 227nm, ZP+24.13mv 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. PMID:26783636

  19. 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.

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

    NASA Astrophysics Data System (ADS)

    Malln, 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 ( ?L) 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, also spread along less permeable pathways.

  1. 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 magnitudes of the genetic correlations suggest that indices that include both milk yield and mortality could be effective in identifying sires that would provide opportunities for minimizing death loss even when selecting for increased milk yield. PMID:24792794

  2. 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.

  3. 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: R01 CA136927.

  4. [Determination of enzyme kinetic parameters and differentiation between various mechanisms by means of a non-linear least squares method].

    PubMed

    Haerlin, R; Steinijans, V

    1978-01-01

    The effect produced by an inhibitor on an enzyme is characterized by the underlying mechanism and the molar inhibition coefficients Ki and Ki', respectively. The commonly used graphical estimation methods according to Lineweaver-Burk, Dixon and Cornish-Bowden do not always yield a differentiation between various possible mechanisms. According to our experience, a non-linear least-squares procedure allows a unique identification of the mechanism even in cases that are not at all, or not uniquely, solvable by graphical methods. The major advantages of this procedures and the used FORTRAN program are: 1. Fitting of the model equation itself-and not of a reciprocal conditional form-simultaneously to all measurements; 2. confidence limits for the parameter estimates; 3. residual plots to judge the goodness of fit; 4. parallel calculations and comparison of various mechanisms using the same set of data; 5. addition of further mechanisms as FORTRAN-subroutines. PMID:580396

  5. Parameter-induced uncertainty quantification of crop yields, soil N2O and CO2 emission for 8 arable sites across Europe using the LandscapeDNDC model

    NASA Astrophysics Data System (ADS)

    Santabarbara, Ignacio; Haas, Edwin; Kraus, David; Herrera, Saul; Klatt, Steffen; Kiese, Ralf

    2014-05-01

    When using biogeochemical models to estimate greenhouse gas emissions at site to regional/national levels, the assessment and quantification of the uncertainties of simulation results are of significant importance. The uncertainties in simulation results of process-based ecosystem models may result from uncertainties of the process parameters that describe the processes of the model, model structure inadequacy as well as uncertainties in the observations. Data for development and testing of uncertainty analisys were corp yield observations, measurements of soil fluxes of nitrous oxide (N2O) and carbon dioxide (CO2) from 8 arable sites across Europe. Using the process-based biogeochemical model LandscapeDNDC for simulating crop yields, N2O and CO2 emissions, our aim is to assess the simulation uncertainty by setting up a Bayesian framework based on Metropolis-Hastings algorithm. Using Gelman statistics convergence criteria and parallel computing techniques, enable multi Markov Chains to run independently in parallel and create a random walk to estimate the joint model parameter distribution. Through means distribution we limit the parameter space, get probabilities of parameter values and find the complex dependencies among them. With this parameter distribution that determines soil-atmosphere C and N exchange, we are able to obtain the parameter-induced uncertainty of simulation results and compare them with the measurements data.

  6. 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. PMID:26954309

  7. 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 1-5C 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 2.0C and 2.3C, 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

  8. 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 15C 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 2.0C and 2.3C, 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

  9. 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. PMID:25149017

  10. 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.

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

    PubMed

    Jussier, Delphine; Dub Morneau, Amlie; Mira de Ordua, Ramn

    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

  12. Study of kinetic parameters and development of a voltammetric sensor for the determination of butylated hydroxyanisole (BHA) in oil samples.

    PubMed

    Thomas, Divya; Rasheed, Zafna; Jagan, Jesny Siri; Kumar, Krishnapillai Girish

    2015-10-01

    Electrochemical behavior of artificial antioxidant, butylated hydroxyanisole (BHA), was investigated at a glassy carbon electrode modified with poly L- cysteine [poly (L- Cys/GCE)]. BHA exhibits a pair of well - defined redox peak on L- cysteine modified GCE with Epa?=?69mV and Epc?=?4mV. The modified electrode showed good electrocatalytic activity towards the oxidation of BHA under optimal conditions and exhibited a linear response in the range from 1.0??10(-5) to 1.0??10(-6)M with a correlation coefficient of 0.998. The limit of detection was found to be 4.1??10(-7)M. The kinetics parameters of the proposed sensor such as heterogeneous electron transfer rate, k s , and charge transfer coefficient,?, was calculated and found to be 1.20s(-1) and 0.575 respectively. The average surface concentration of BHA on the surface of poly (L- Cys/GCE) was calculated to be 3.18??10(-4)molcm(-2). The analytical utility of the proposed sensor was evaluated by the successful determination of BHA in coconut oil and sesame oil samples. PMID:26396421

  13. 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. PMID:26847838

  14. 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 30C and pH 5. The half-life of laccase is 87min at 60C 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. PMID:24547974

  15. Effects of ambient and elevated level of ozone on Brassica campestris L. with special reference to yield and oil quality parameters.

    PubMed

    Tripathi, Ruchika; Agrawal, S B

    2012-11-01

    Tropospheric ozone (O(3)) has become a serious threat to growth and yield of important agricultural crops over Asian regions including India. Effect of elevated O(3) (ambient+10ppb) was studied on Brassica campestris L. (cv. Sanjukta and Vardan) in open top chambers under natural field conditions. Eight hourly mean ambient O(3) concentration varied from 26.3ppb to 69.5ppb during the growth period. Plants under O(3) exposure showed reductions in photosynthetic rate, reproductive parameters, yield as well as seed and oil quality. Cultivar Sanjukta showed more reduction in photosynthetic characteristics, reproductive structures and seed and oil quality. However, total yield was more affected in Vardan. Exposure of O(3) increased the degree of unsaturation and level of PUFA, ?-6fatty acid, linolenic acid and erucic acid in oil indicating the deterioration of its quality. The study further confirmed that there is a correspondence between O(3) induced change in photosynthetic processes, reproductive development and yield and did not find any compensatory response in the final yield. PMID:22986091

  16. Measurement of CP violation observables and parameters for the decays B{sup {+-}}{yields}DK*{sup {+-}}

    SciTech Connect

    Aubert, B.; Karyotakis, Y.; Lees, J. P.; Poireau, V.; Prencipe, E.; Prudent, X.; Tisserand, V.; Martinelli, M.; Palano, A.; Pappagallo, M.; Eigen, G.; Stugu, B.; Sun, L.; Battaglia, M.; Brown, D. N.; Kerth, L. T.; Kolomensky, Yu. G.; Lynch, G.

    2009-11-01

    We study the decay B{sup -}{yields}DK*{sup -} using a sample of 379x10{sup 6} {upsilon}(4S){yields}BB events collected with the BABAR detector at the PEP-II B factory. We perform a Gronau-London-Wyler analysis where the D meson decays into either a CP-even (CP+) eigenstate (K{sup +}K{sup -}, {pi}{sup +}{pi}{sup -}), CP-odd (CP-) eigenstate (K{sub S}{sup 0}{pi}{sup 0}, K{sub S}{sup 0}{phi}, K{sub S}{sup 0}{omega}) or a non-CP state (K{sup -}{pi}{sup +}). We also analyze D meson decays into K{sup +}{pi}{sup -} from a Cabibbo-favored D{sup 0} decay or doubly suppressed D{sup 0} decay [Atwood-Dunietz-Soni (ADS) analysis]. We measure observables that are sensitive to the Cabibbo-Kobayashi-Maskawa angle {gamma}: the partial-rate charge asymmetries A{sub CP{+-}}, the ratios R{sub CP{+-}} of the B-decay branching fractions in CP{+-} and non-CP decay, the ratio R{sub ADS} of the charge-averaged branching fractions, and the charge asymmetry A{sub ADS} of the ADS decays: A{sub CP+}=0.09{+-}0.13{+-}0.06, A{sub CP-}=-0.23{+-}0.21{+-}0.07, R{sub CP+}=2.17{+-}0.35{+-}0.09, R{sub CP-}=1.03{+-}0.27{+-}0.13, R{sub ADS}=0.066{+-}0.031{+-}0.010, and A{sub ADS}=-0.34{+-}0.43{+-}0.16, where the first uncertainty is statistical and the second is systematic. Combining all the measurements and using a frequentist approach yields the magnitude of the ratio between the Cabibbo-suppressed and favored amplitudes, r{sub B}=0.31 with a one (two) sigma confidence level interval of [0.24, 0.38] ([0.17, 0.43]). The value r{sub B}=0 is excluded at the 3.3 sigma level. A similar analysis excludes values of {gamma} in the intervals [0, 7] deg., [55, 111] deg., and [175, 180] deg. ([85, 99] deg.) at the one (two) sigma confidence level.

  17. 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.

  18. 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.

  19. Kinetic study of the reaction CH (X 2Pi) + H2 yields CH2 (X 3B1) + H in the temperature range 372 to 675 K

    NASA Technical Reports Server (NTRS)

    Zabarnick, S.; Fleming, J. W.; Lin, M. C.

    1986-01-01

    The kinetics of the reversible reaction CH (X 2Pi) + H2 yields CH2 (X 3B1) + H at 372-675 K and total pressure 100 torr (mainly Ar) is investigated experimentally. The ground-state CH radicals are produced by photolysis of CHBr3 using 10-mJ 266-nm laser pulses (repetition rate 10 Hz) and monitored by measuring the fluorescence induced by a 429.8-nm dye laser, in the apparatus described by Berman et al. (1982) and Berman and Lin (1984). The results are presented in tables and graphs and characterized. The absolute rate constants for the forward and reverse reactions are determined, and their temperature dependence is given by Arrhenius expressions and formulas obtained in transition-state-theory calculations. The heat of formation of CH2 at 0 K is estimated (assuming that the recombination reaction CH2 + H has zero activation energy) as 92.6 + or - 0.5 kcal/mol.

  20. '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; Nep?rek, 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.

  1. Model of curing shrinkage and kinetic parameters of an acrylate-based ultraviolet-embossing resist based on free volume theory

    NASA Astrophysics Data System (ADS)

    Liu, Nan; Liu, Jingbei; Lin, Jie; Davies, Graham; Jin, Peng; Zhang, Dou

    2013-04-01

    Free volume theory and a model of polymerization kinetics are introduced to predict and analyze the curing shrinkage and kinetic parameters of an acrylate-based ultraviolet-embossing resist. Curing shrinkage tests have been designed and performed to verify the accuracy of the model. The experimental results are in good agreement with the simulated results of the conversion behavior. The reaction coefficients of polymerization predicted by this model are essentially correct when compared to the classical experimental values. Moreover, the dynamic shrinkage during polymerization determined experimentally matches the simulated result predicted by our model.

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

    PubMed

    Navarro, F; Harouna, S; Calvo, M; Prez, M D; Snchez, L

    2015-07-01

    Lactoferrin is a protein with important biological functions that can be obtained from milk and by-products derived from the dairy industry, such as whey. Although bovine lactoferrin has been extensively studied, ovine lactoferrin is not quite as well known. In the present study, the effect of several heat treatments in 3 different media, over a temperature range from 66 to 75C, has been studied on lactoferrin isolated from sheep milk. Denaturation of lactoferrin was determined by measuring its immunoreactivity with specific polyclonal antibodies. Kinetic and thermodynamic parameters obtained indicate that lactoferrin denatures by heat more rapidly in whey than in phosphate buffer or milk. The value of activation energy found for the denaturation process of lactoferrin when treated in whey is higher (390kJ/mol) than that obtained in milk (194kJ/mol) or phosphate buffer (179kJ/mol). This indicates that a great amount of energy is necessary to start denaturation of ovine lactoferrin, probably due to the interaction of this protein with other whey proteins. The changes in the hydrophobicity of lactoferrin after heat treatments were determined by fluorescence measurement using acrylamide. The decrease in the hydrophobicity constant was very small for the treatments from 66 to 75C, up to 20min, which indicates that lactoferrin conformation did not experienced a great change. The results obtained in this study permit the prediction of behavior of ovine lactoferrin under several heat treatments and show that high-temperature, short-time pasteurization (72C, 15 s) does not cause loss of its immunoreactivity and, consequently, would not affect its conformation and biological activity. PMID:25958286

  3. Release kinetics, quantal parameters and their modulation during short-term depression at a developing synapse in the rat CNS.

    PubMed

    Taschenberger, Holger; Scheuss, Volker; Neher, Erwin

    2005-10-15

    We have characterized developmental changes in the kinetics and quantal parameters of action potential (AP)-evoked neurotransmitter release during maturation of the calyx of Held synapse. Quantal size (q) and peak amplitudes of evoked EPSCs increased moderately, whereas the fraction of vesicles released by single APs decreased. During synaptic depression induced in postnatal day (P) 5-7 synapses by 10-100 Hz stimulation, q declined rapidly to 40-12% of its initial value. The decrease in q was generally smaller in more mature synapses (P12-14), but quite severe for frequencies > or = 300 Hz. The stronger decline of q in immature synapses resulted from a slower recovery from desensitization, presumably due to delayed glutamate clearance. Recovery from this desensitization followed an exponential time course with a time constant of approximately 480 ms in P5-7 synapses, and sped up > 20-fold during maturation. Deconvolution analysis of EPSCs revealed a significant acceleration of the release time course during development, which was accompanied by a 2-fold increase of the peak release rate. During long 100 Hz trains, more mature synapses were able to sustain average rates of 8-10 quanta s(-1) per active zone for phasic release. The rates of asynchronous vesicle release increased transiently > 35-fold immediately after such stimuli and decayed rapidly with an exponential time constant of approximately 50 ms to low resting levels of spontaneous release. However, even following extended periods of 100 Hz stimulation, the amount of asynchronous release was relatively minor with peak rates of less than 5% of the average rate of synchronous release measured at steady state during the tetani. Therefore, a multitude of mechanisms seems to converge on the generation of fast, temporally precise and reliable high-frequency transmission at the mature calyx of Held synapse. PMID:16096340

  4. Release kinetics, quantal parameters and their modulation during short-term depression at a developing synapse in the rat CNS

    PubMed Central

    Taschenberger, Holger; Scheuss, Volker; Neher, Erwin

    2005-01-01

    We have characterized developmental changes in the kinetics and quantal parameters of action potential (AP)-evoked neurotransmitter release during maturation of the calyx of Held synapse. Quantal size (q) and peak amplitudes of evoked EPSCs increased moderately, whereas the fraction of vesicles released by single APs decreased. During synaptic depression induced in postnatal day (P) 57 synapses by 10100 Hz stimulation, q declined rapidly to 4012% of its initial value. The decrease in q was generally smaller in more mature synapses (P1214), but quite severe for frequencies ? 300 Hz. The stronger decline of q in immature synapses resulted from a slower recovery from desensitization, presumably due to delayed glutamate clearance. Recovery from this desensitization followed an exponential time course with a time constant of ?480 ms in P57 synapses, and sped up > 20-fold during maturation. Deconvolution analysis of EPSCs revealed a significant acceleration of the release time course during development, which was accompanied by a 2-fold increase of the peak release rate. During long 100 Hz trains, more mature synapses were able to sustain average rates of 810 quanta s?1 per active zone for phasic release. The rates of asynchronous vesicle release increased transiently > 35-fold immediately after such stimuli and decayed rapidly with an exponential time constant of ?50 ms to low resting levels of spontaneous release. However, even following extended periods of 100 Hz stimulation, the amount of asynchronous release was relatively minor with peak rates of less than 5% of the average rate of synchronous release measured at steady state during the tetani. Therefore, a multitude of mechanisms seems to converge on the generation of fast, temporally precise and reliable high-frequency transmission at the mature calyx of Held synapse. PMID:16096340

  5. 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. PMID:25727642

  6. 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.

  7. Effect of Tannin-Binding Agents (Polyethylene Glycol and Polyvinylpyrrolidone) Supplementation on In Vitro Gas Production Kinetics of Some Grape Yield Byproducts

    PubMed Central

    Besharati, Maghsoud; Taghizadeh, Akbar

    2011-01-01

    The effects of polyethylene glycol (PEG) and polyvinylpyrrolidone (PVP) on in vitro gas production characteristics, organic matter digestibility (OMD), and metabolizable energy (ME) contents of some grape yield byproducts were investigated. The gas production was recorded after 2, 4, 6, 8, 12, 16, 24, 36, and 48?h of incubation. The gas production profiles in triplicate fitted with equation Y = A (1 e?ct). The data was analyzed using completely randomized design. Total phenol (TP) and total tannin (TT) contents were highest for raisin waste (RW). The TP content (g/kg DM) ranged from 30.1 in grape pomace (GP) to 96.3 in RW, which also had the higher TT (72.1?g/kg DM). The potential gas production (a + b) of DGB, GP, and RW were 239.43, 263.49, and 208.22?mL/g DM, respectively. In the absence of PEG and PVP, rate constant of gas production (c) for GP was highest among the feedstuffs (0.1073?mL/h), but in presence of PEG or PVP, RW had highest fraction (c) among the feedstuffs. Addition of PEG and PVP inactivated effects of tannins and increased gas production, ME, NE1, OMD, and VFA in grape yield byproducts. Addition of PEG and PVP could overcome adverse effects of tannins on nutrient availability as indicated by gas production parameters. PMID:23738107

  8. Erbium hydride decomposition kinetics.

    SciTech Connect

    Ferrizz, Robert Matthew

    2006-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2007-03-01

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

  10. 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.

  11. 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. PMID:24036164

  12. Systematics of Fission-Product Yields

    SciTech Connect

    A.C. Wahl

    2002-05-01

    Empirical equations representing systematics of fission-product yields have been derived from experimental data. The systematics give some insight into nuclear-structure effects on yields, and the equations allow estimation of yields from fission of any nuclide with atomic number Z{sub F} = 90 thru 98, mass number A{sub F} = 230 thru 252, and precursor excitation energy (projectile kinetic plus binding energies) PE = 0 thru {approx}200 MeV--the ranges of these quantities for the fissioning nuclei investigated. Calculations can be made with the computer program CYFP. Estimates of uncertainties in the yield estimates are given by equations, also in CYFP, and range from {approx} 15% for the highest yield values to several orders of magnitude for very small yield values. A summation method is used to calculate weighted average parameter values for fast-neutron ({approx} fission spectrum) induced fission reactions.

  13. Spectra, Emission Yields, Cross Sections, and Kinetic Energy Distributions of Hydrogen Atoms from H2 X 1Eg+-d 3IIu Excitation by Electron Impact

    NASA Astrophysics Data System (ADS)

    Liu, Xianming; Shemansky, Donald E.; Yoshii, Jean; Johnson, Paul V.; Malone, Charles P.; Ajello, Joseph M.

    2016-02-01

    Electron-impact excitation of H2 triplet states plays an important role in the heating of outer planet upper thermospheres. The {d}3{{{\\Pi }}}u state is the third ungerade triplet state, and the {d}3{{{\\Pi }}}u–a{}3{{{Σ }}}g+ emission is the largest cascade channel for the a{}3{{{Σ }}}g+ state. Accurate energies of the d{}3{{{\\Pi }}}u-(v, J) levels are calculated from an ab initio potential energy curve. Radiative lifetimes of the {d}3{{{\\Pi }}}u(v, J) levels are obtained by an accurate evaluation of the {d}3{{{\\Pi }}}u–a{}3{{{Σ }}}g+ transition probabilities. The emission yields are determined from experimental lifetimes and calculated radiative lifetimes and are further verified by comparing experimental and synthetic {d}3{{{\\Pi }}}u–a{}3{{{Σ }}}g+ spectra at 20 eV impact energy. Spectral analysis revealed that multipolar components beyond the dipolar term are required to model the {X}1{{{Σ }}}g+–{d}3{{{\\Pi }}}u excitation, and significant cascade excitation occurs at the {d}3{{{\\Pi }}}u(v = 0,1) levels. Kinetic energy (Ek) distributions of H atoms produced via predissociation of the {d}3{{{\\Pi }}}u state and the {d}3{{{\\Pi }}}u‑a{}3{{{Σ }}}g+‑b{}3{{{Σ }}}u+ cascade dissociative emission are obtained. Predissociation of the {d}3{{{\\Pi }}}u state produces H atoms with an average Ek of 2.3 ± 0.4 eV/atom, while the Ek distribution of the {d}3{{{\\Pi }}}u‑a{}3{{{Σ }}}g+‑b{}3{{{Σ }}}u+ channel is similar to that of the {X}1{{{Σ }}}g+–a{}3{{{Σ }}}g+‑b{}3{{{Σ }}}u+ channel and produces H(1s) atoms with an average Ek of 1.15 ± 0.05 eV/atom. On average, each H2 excited to the {d}3{{{\\Pi }}}u state in an H2-dominated atmosphere deposits 3.3 ± 0.4 eV into the atmosphere, while each H2 directly excited to the a{}3{{{Σ }}}g+ state gives 2.2–2.3 eV to the atmosphere. The spectral distribution of the calculated a{}3{{{Σ }}}g+ –b{}3{{{Σ }}}u+ continuum emission due to the {X}1{{{Σ }}}g+–{d}3{{{\\Pi }}}u excitation is significantly different from that of direct a{}3{{{Σ }}}g+ excitation.

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

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

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

  15. 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. PMID:23644019

  16. 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

    Agro-Land Surface Models (agro-LSM) have been developed from the integration of specific crop processes into large-scale generic land surface models that allow calculating the spatial distribution and variability of energy, water and carbon fluxes within the soil-vegetation-atmosphere continuum. When developing agro-LSM models, a particular attention must be given to the effects of crop phenology and management on the turbulent fluxes exchanged with the atmosphere, and the underlying water and carbon pools. A part of the uncertainty of Agro-LSM models is related to their usually large number of parameters. In this study, we quantify the parameter-values uncertainty in the simulation of sugar cane biomass production with the agro-LSM ORCHIDEE-STICS, using a multi-regional approach with data from sites in Australia, La Réunion and Brazil. In ORCHIDEE-STICS, two models are chained: STICS, an agronomy model that calculates phenology and management, and ORCHIDEE, a land surface model that calculates biomass and other ecosystem variables forced by STICS' phenology. First, the parameters that dominate the uncertainty of simulated biomass at harvest date are determined through a screening of 67 different parameters of both STICS and ORCHIDEE on a multi-site basis. Secondly, the uncertainty of harvested biomass attributable to those most sensitive parameters is quantified and specifically attributed to either STICS (phenology, management) or to ORCHIDEE (other ecosystem variables including biomass) through distinct Monte-Carlo runs. The uncertainty on parameter values is constrained using observations by calibrating the model independently at seven sites. In a third step, a sensitivity analysis is carried out by varying the most sensitive parameters to investigate their effects at continental scale. A Monte-Carlo sampling method associated with the calculation of Partial Ranked Correlation Coefficients is used to quantify the sensitivity of harvested biomass to input 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.

  17. 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.; Martin, J.-F.

    2014-06-01

    Agro-land surface models (agro-LSM) have been developed from the integration of specific crop processes into large-scale generic land surface models that allow calculating the spatial distribution and variability of energy, water and carbon fluxes within the soil-vegetation-atmosphere continuum. When developing agro-LSM models, particular attention must be given to the effects of crop phenology and management on the turbulent fluxes exchanged with the atmosphere, and the underlying water and carbon pools. A part of the uncertainty of agro-LSM models is related to their usually large number of parameters. In this study, we quantify the parameter-values uncertainty in the simulation of sugarcane biomass production with the agro-LSM ORCHIDEE-STICS, using a multi-regional approach with data from sites in Australia, La Runion and Brazil. In ORCHIDEE-STICS, two models are chained: STICS, an agronomy model that calculates phenology and management, and ORCHIDEE, a land surface model that calculates biomass and other ecosystem variables forced by STICS phenology. First, the parameters that dominate the uncertainty of simulated biomass at harvest date are determined through a screening of 67 different parameters of both STICS and ORCHIDEE on a multi-site basis. Secondly, the uncertainty of harvested biomass attributable to those most sensitive parameters is quantified and specifically attributed to either STICS (phenology, management) or to ORCHIDEE (other ecosystem variables including biomass) through distinct Monte Carlo runs. The uncertainty on parameter values is constrained using observations by calibrating the model independently at seven sites. In a third step, a sensitivity analysis is carried out by varying the most sensitive parameters to investigate their effects at continental scale. A Monte Carlo sampling method associated with the calculation of partial ranked correlation coefficients is used to quantify the sensitivity of harvested biomass to input 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.

  18. A comparative study of dried apple using hot air, intermittent and continuous microwave: evaluation of kinetic parameters and physicochemical quality attributes.

    PubMed

    Aghilinategh, Nahid; Rafiee, Shahin; Gholikhani, Abolfazl; Hosseinpur, Soleiman; Omid, Mahmoud; Mohtasebi, Seyed S; Maleki, Neda

    2015-11-01

    In the study, the effectiveness of intermittent (IMWD) and continuous (CMWD) microwave drying and hot air drying (HAD) treatments on apple slices were compared in terms of drying kinetics (moisture diffusivity and activation energy) and critical physicochemical quality attributes (color change, rehydration ratio, bulk density, and total phenol content (TPC) of the final dried product. The temperature, microwave power, air velocity, and pulse ratio (PR) applied in the experiments were 40-80C, 200-600W, 0.5-2m/s, and 2-6, respectively. Results showed that IMWD and CMWD more effective than HAD in kinetic parameters and physicochemical quality attributes. Also, results indicated CMWD had the lowest and highest drying time and effective diffusivity. The exponential model for estimating IMWD activation energy, considering absolute power (1/P) and pulse ratio were also represented. The color change in apple slices dried by HAD showed the highest change. PMID:26788293

  19. 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; Menndez-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 antagonism between production and tolerance to heat stress demonstrated by the negative genetic correlation between these components (-0.23). Monitoring trends of the genetic component of heat stress would be a reasonable measure to avoid deterioration in one of the main traits of Zebu cattle (i.e., high tolerance to heat stress). On the basis of current genetic trends, the need for future genetic evaluation of dairy Zebu animals for tolerance to heat stress cannot be ruled out. PMID:26476953

  20. The use of the logarithmic transformation in the calculation of the transport parameters of a system that obeys Michaelis–Menten kinetics

    PubMed Central

    Barber, H. E.; Welch, B. L.; Mackay, D.

    1967-01-01

    1. A logarithmic method is described for the calculation of the transport parameters, Km and Vmax.' of a biological system obeying Michaelis–Menten kinetics. 2. This logarithmic method leads to a way of estimating the transport parameters that has not apparently been used previously. It allows the separation of variance due to Vmax. from other variance, and so reduces the fiducial limits that can be placed on an estimation of Km. 3. The results of studies on the transport of l-histidine and l-monoiodohistidine by rat intestinal sacs in vitro have been used to illustrate the application of the new method. Estimates of the transport parameters have also been made by two alternative procedures. The relative merits of the three methods are discussed. PMID:6033766

  1. 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. PMID:24229649

  2. 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. PMID:21071143

  3. 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 defined, as in challenge 2. Importantly, we found that aggregating independent parameter predictions and network topology across submissions creates a solution that can be better than the one from the best-performing submission. PMID:24507381

  4. Temperature impact on thermodynamical parameters of DNA:DNA hybridization kinetics as quantified by Surface Plasmon Resonance Imaging (SPRI) system

    NASA Astrophysics Data System (ADS)

    Hottin, Jrome; Moreau, Julien; Canva, Michael

    2009-02-01

    Surface plasmon resonance imaging optical biochips have shown promising applications in the field of genetic diagnosis due to their ability to record hundred of different biomolecular interactions without any label and in real time. Single nucleotide polymorphisms can be detected using this technique. To improve the accuracy and the reliability of biochips a quantitative study on the impact of temperature on DNA hybridization and secondary structures is shown for various oligonucleotides sequences. In this proceeding we focus on the impact of temperature T on the binding rate kinetic ?, using the model case of DNA:DNA interactions. We show that SPRI can quantify such characteristics as ?(T) and that they follow the Langmuir model variation law.

  5. Errors in Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) kinetic temperature caused by non-local-thermodynamic-equilibrium model parameters

    NASA Astrophysics Data System (ADS)

    GarcA-Comas, M.; Lpez-Puertas, M.; Marshall, B. T.; Wintersteiner, P. P.; Funke, B.; Bermejo-Pantalen, D.; Mertens, C. J.; Remsberg, E. E.; Gordley, L. L.; Mlynczak, M. G.; Russell, J. M.

    2008-12-01

    The vast set of near-global and continuous atmospheric measurements made by the Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument since 2002, including daytime and nighttime kinetic temperature (Tk) from 20 to 105 km, is available to the scientific community. The temperature is retrieved from SABER measurements of the atmospheric 15 ?m 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(?2) by N2, O2 and O, and the CO2(?2) vibrational-vibrational exchange to estimate their impact on SABER Tk for different atmospheric conditions. The Tk is more sensitive to the uncertainty in the latter two, and their effects depend on altitude. The Tk 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 favorable polar summer conditions. For strong temperature inversion layers, the errors reach 3 K at 82 km and 8 K at 90 km. This particularly affects tide amplitude estimates, with errors of up to 3 K.

  6. 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.

  7. Extracting kinetic parameters for homogeneous [Os(bpy)2ClPyCOOH]+ mediated enzyme reactions from cyclic voltammetry and simulations.

    PubMed

    Flexer, V; Ielmini, M V; Calvo, E J; Bartlett, P N

    2008-11-01

    The homogeneous reaction between glucose oxidase and osmium bipyridine-pyridine carboxylic acid in the presence of glucose has been studied in detail by cyclic voltammetry and digital simulation. Combination of the analytical equations that describe the dependence of the amperometric response on enzyme, substrate and co-substrate concentrations for the limiting cases with digital simulation of the coupled enzyme reaction diffusion problem allows us to extract kinetic parameters for the substrate-enzyme reaction: K(MS)=10.8 mM, k(cat)=254 s(-1) and for the redox mediator-enzyme reaction, k=2.2x10(5) M(-1) s(-1). The accurate determination of the kinetic parameters at low substrate concentrations (<7 mM) is limited by depletion of the substrate close to the electrode surface. At high substrate concentrations (>20 mM) inactivation of the reduced form of glucose oxidase in the bulk solution must be taken into account in the analysis of the results. PMID:18824418

  8. 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.

  9. Dynamic contrast-enhanced CT of head and neck tumors: Perfusion measurements using a distributed-parameter tracer kinetic model

    NASA Astrophysics Data System (ADS)

    Bisdas, Sotirios; Cheong, Dennis L. H.; Lazakidou, Athina; Tan, Markus C. K.; San Koh, Tong; Vogl, Thomas J.; Baghi, Mehran

    2006-12-01

    Functional imaging has the potential to be a practical and widely available method of studying the pathphysiology of disease using modern CT technologies. With the high temporal resolution achievable by these technologies, a two-compartment distributed-parameter model, which more accurately represents the tracer concentration within the vascular space, was applied on five patients' data with extracranial head and neck tumors. The parametric maps successfully generated were more informative than the current commercial software packages and the commonly used lumped-parameter compartmental models.

  10. 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.

  11. 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.

  12. Rationalization and prediction of in vivo metabolite exposures: The role of metabolite kinetics, clearance predictions and in vitro parameters

    PubMed Central

    Lutz, Justin D.; Fujioka, Yasushi; Isoherranen, Nina

    2010-01-01

    Importance of the field Due to growing concerns over toxic or active metabolites, significant efforts have been focused on qualitative identification of potential in vivo metabolites from in vitro data. However, limited tools are available to quantitatively predict their human exposures. Areas covered in this review Theory of clearance predictions and metabolite kinetics is reviewed together with supporting experimental data. In vitro and in vivo data of known circulating metabolites and their parent drugs was collected and the predictions of in vivo exposures of the metabolites were evaluated. What the reader will gain The theory and data reviewed will be useful in early identification of human metabolites that will circulate at significant levels in vivo and help in designing in vivo studies that focus on characterization of metabolites. It will also assist in rationalization of metabolite-to-parent ratios used as markers of specific enzyme activity. Take home message The relative importance of a metabolite in comparison to the parent compound as well as other metabolites in vivo can only be predicted using the metabolites in vitro formation and elimination clearances, and the in vivo disposition of a metabolite can only be rationalized when the elimination pathways of that metabolite are known. PMID:20557268

  13. A protocol for the measurement of all the parameters of the mass transfer kinetics in columns used in liquid chromatography

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2010-01-01

    Band broadening in chromatography results from the combination of the dispersive effects that are associated with the different steps involved in the migration of compound bands along the column. These steps include longitudinal diffusion, trans-particle mass transfer, external film mass transfer, overall eddy diffusion, including trans-column, short-range inter-channel, trans-channel eddy diffusion, and the possible, additional mass transfer contributions arising from heat friction and the thermal heterogeneity of the column. We describe a series of experiments that provide the data needed to determine the coefficients of the contributions to band broadening of each one of these individual mass transfer steps. This specifically designed protocol can provide key information regarding the kinetic performance of columns used in liquid chromatography and explain why different columns behave so differently. The limitations, accuracy and precision of these methods are discussed. Further avenues of research that could improve the characterization of the mass transfer mechanisms in chromatographic columns, possibly contributing to the development of better columns, are suggested.

  14. 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.

  15. Performance evaluation of the non-linear and linear estimation methods for determining kinetic parameters in dynamic FDG-PET study

    NASA Astrophysics Data System (ADS)

    Dai, Xiaoqian; Tian, Jie; Chen, Zhe

    2010-03-01

    Dynamic positron emission tomography (PET) is a promising diagnostic tool to quantitatively predict biological and physiological changes in vivo through estimation of kinetic parameters. In this work, several popular linear and non-linear estimation methods for determining kinetic parameters using PET imaging with Fluorine-18 fluorodeoxyglucose ([18F]FDG) are compared and evaluated. The simulation studies are presented. The linear estimation methods include linear least squares (LLS), generalized linear least squares (GLLS) and total least squares (TLS), while the non-linear estimation methods include non-linear least squares (NLS), weighted nonlinear least squares using noisy tissue time activity data (WNLS-N), weighted non-linear least squares using noise-free tissue time activity data (WNLS-NF) and iteratively re-weighted non-linear least squares (IRWNLS). There are several findings: 1. Compared with non-linear estimation methods, GLLS performs well when noise level is low, but worse especially in determining k3 and k4 when noise level is high. What's more, GLLS does not show obvious advantage in running time. 2. The choice of weights plays an important role in nonlinear estimation methods. Weighting using noisy data should be avoided. WNLS-NF and IRWNLS perform best. Since the noise-free data can not be obtained in clinical and IRWNLS is time-consuming, NLS is most recommended. 3. Non-linear estimation methods are prone to produce lower-biased, higher-precision parameter estimates, however, also more easily affected by noise. Linear estimation methods are prone to be more biased, however, much more computational efficient and noise robust.

  16. 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 (?), 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 (?C), 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 ? (P = 0.022) and vI (P = 0.010), and WX-ETK-model-derived ?C (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

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

    PubMed

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

    2015-11-15

    In view of understanding colour instability of pasteurised orange juice during storage, to the best of our knowledge, this study reports for the first time in a systematic and quantitative way on a range of changes in specific quality parameters as a function of time and as well as temperature (20-42 °C). A zero-order (°Brix, fructose, glucose), a first-order (vitamin C), a second-order (sucrose) and a fractional conversion model (oxygen) were selected to model the evolution of the parameters between parentheses. Activation energies ranged from 22 to 136 kJ mol(-1), HMF formation being the most temperature sensitive. High correlations were found between sugars, ascorbic acid, their degradation products (furfural and HMF) and total colour difference (ΔE(∗)). Based on PLS regression, the importance of the quality parameters for colour degradation was ranked relatively among each other: the acid-catalysed degradation of sugars and ascorbic acid degradation reactions appeared to be important for browning development in pasteurised orange juice during ambient storage. PMID:25977009

  18. Regulators of Calcium Homeostasis Identified by Inference of Kinetic Model Parameters from Live Single Cells Perturbed by siRNA

    PubMed Central

    Bandara, Samuel; Malmersjö, Seth; Meyer, Tobias

    2013-01-01

    Assigning molecular functions and revealing dynamic connections between large numbers of partially characterized proteins in regulatory networks are challenges in systems biology. We showed that functions of signaling proteins can be discovered with a differential equations model of the underlying signaling process to extract specific molecular parameter values from single-cell, time-course measurements. By analyzing the effects of 250 small interfering RNAs on Ca2+ signals in single cells over time, we identified parameters that were specifically altered in the Ca2+ regulatory system. Analysis of the screen confirmed known functions of the Ca2+ sensors STIM1 (stromal interaction molecule 1) and calmodulin and of Ca2+ channels and pumps localized in the endoplasmic reticulum (ER) or plasma membrane. Furthermore, we showed that the Alzheimer’s disease–linked protein presenilin-2 and the channel protein ORAI2 prevented overload of ER Ca2+ and that feedback from Ca2+ to phosphatidylinositol 4-kinase and PLCδ (phospholipase Cδ) may regulate the abundance of the plasma membrane lipid PI(4,5)P2 (phosphatidylinositol 4,5-bisphosphate) to control Ca2+ extrusion. Thus, functions of signaling proteins and dynamic regulatory connections can be identified by extracting molecular parameter values from single-cell, time-course data. PMID:23838183

  19. Non-Isothermal Kinetics.

    ERIC Educational Resources Information Center

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

    1978-01-01

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

  20. Self-emulsifying pellets: relations between kinetic parameters of drug release and emulsion reconstitution-influence of formulation variables.

    PubMed

    Nikolakakis, Ioannis; Malamataris, Stavros

    2014-05-01

    The effects of surfactant type and content on the kinetics of emulsion reconstitution and release of drugs differing in lipophilicity from self-emulsifying microcrystalline cellulose pellets were studied. Furosemide and propranolol were the drugs, medium-chain triglyceride was the oil, and Cremophors ELP, RH40, and RH60 were the surfactants. Pellets were prepared by extrusion/spheronization with emulsions (75% water and 25%, w/w, oil/surfactant/drug). Stability of the emulsions was evaluated from changes in the back-scattered light, and re-emulsification and drug release from light transmittance and UV spectroscopy, respectively. Emulsion stability increased because of the incorporation of the drugs. Re-emulsification depended only on the surfactant content and was expressed by a simple power equation (Ra2 > 0.945, Q(2) > 0.752). Drug release was expressed by two biexponential equations (Ra2 > 0.989, Q(2) > 0.699 and Ra2 > 0.947, Q(2) > 0.693) implying initial burst and terminal slow release phase and by the linear form (Lineweaver-Burke) of Michaelis-Menten equation (Ra2 > 0.726, Q(2) > 0.397). Relationships exist between the rate constants of the equations describing emulsion reconstitution and drug release, for propranolol compositions (R(2) = 0.915), and for compositions of both drugs with less hydrophilic ELP and RH40 (R(2) = 0.511), and also, among dissolution efficiency, drug solubility in oil/surfactant, and emulsion reconstitution ability, indicating the importance of drug solubilization in oil/surfactant and re-emulsification ability on drug release. PMID:24596121

  1. 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 ?-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 ?-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 312C under 2Gy ?-excitation and 284C for low energy diagnostic X-ray irradiation and 271C 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. PMID:26562181

  2. 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.

  3. Langmuir probe plasma parameters and kinetic rates in a Ar-SiH4-H2 plasma during nc-Si films deposition for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Moiseev, T.; Isella, G.; Chrastina, D.; Cavallotti, C.

    2009-11-01

    An assessment of main electron-impact and secondary (homogeneous) gas-phase reaction rates of silane in an argon-silane-hydrogen plasma during nano-crystalline silicon deposition is presented. Radially resolved Langmuir probe plasma parameters (electron temperature and density) and electron energy distribution functions (eedfs) have been evaluated for Ar, Ar-H2 and Ar-SiH4-H2 plasma in a low-energy plasma-enhanced chemical vapour deposition reactor. Input flow rates of 50 sccm Ar, 10 sccm SiH4 and 0-50 sccm H2 have been used for a reactor pressure range 1-4 Pa. The eedfs are used to evaluate kinetic rate constants for electron-impact dissociative processes of SiH4 and H2 and to infer the amount of atomic H available for the silane-hydrogen gas-phase reaction, observing trends with an increase in H2 input flow. The evolution of silane kinetic rates with an increase in H2 input indicates that conditions corresponding to nc-Si deposition are characterized by a dominance of silane-hydrogen gas-phase rates over electron-impact dissociation rates up to about two orders of magnitude.

  4. 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. PMID:25588557

  5. 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 20kHz and liquid bulk temperature of 30°C in the following range of experimental conditions: EP concentration 250-1250μg/L, ultrasound (US) density 20-60W/L, reaction time up to 120min, 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. PMID:26964924

  6. 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

  7. Photolysis of 2,3-pentanedione and 2,3-hexanedione: Kinetics, quantum yields, and product study in a simulation chamber

    NASA Astrophysics Data System (ADS)

    Bouzidi, H.; Fittschen, C.; Coddeville, P.; Tomas, A.

    2014-01-01

    The gas phase photolysis of two ?-diketones, 2,3-pentanedione (PTD) and 2,3-hexanedione (HEX), has been studied in a Teflon simulation chamber using UV lamps in the 330-480 nm wavelength range. Photolysis rates have been determined at room temperature and atmospheric pressure. Using NO2 actinometry allows estimating the lifetime of PTD and HEX in the atmosphere to be about 2.5 h, assessing the dominance of the photolysis loss process over the OH reaction for such ?-dicarbonyl compounds. Effective quantum yields for PTD and HEX have also been calculated over the whole wavelength range: ?PTD = 0.20 0.02 and ?HEx = 0.18 0.03, consistent with literature values on ?-dicarbonyls. Various end-products from the photolysis of PTD and HEX have been identified and quantified. For PTD, CH2O and CH3CHO have been detected with molar yields of (48 0.5)% and (41 0.7)%, respectively. For HEX, CH2O and C2H5CHO have been detected with molar yields of (45 1.1)% and (37 0.8)%, respectively. Small amounts of CO have also been observed, with yields of about 2%, as well as organic acids. Experiments performed in the absence of OH-radical scavengers showed significantly faster photolysis rates and higher CO yields (7%), indicating clear formation of OH radicals in the chemical systems. A reaction mechanism was developed for PTD and HEX photolysis based on the product observations, which allowed simulating the reactant and product time profiles with very good agreement. The present work represents the first study of 2,3-pentanedione and 2,3-hexanedione photolysis, to our knowledge, and may contribute to a better understanding of the photolysis of the ?-diketones in the troposphere.

  8. REPLY: Reply to Comments on 'Effect of heating rate on kinetic parameters of ?-irradiated Li2B4O7:Cu,Ag,P in TSL measurements'

    NASA Astrophysics Data System (ADS)

    Ege, A. Turkler; Tekin, E. Ekdal; Karali, T.; Can, N.; Proki?, M.

    2009-05-01

    We appreciate the opportunity to respond to comments regarding the paper published by Ege et al (2007 Effect of heating rate on kinetic parameters of ?-irradiated Li2B4O7:Cu,Ag,P in TSL measurements Meas. Sci. Technol. 18 889). We would like to thank the authors for taking the time to tell us about their opinion, but unfortunately we do not agree with them completely. In the article presented by Kumar and Chourasiya some comment is advanced to the analysis of the glow curves measured with different heating rates, presented in our recent study. According to our study, the area under the glow curve decreases with increasing heating rate in TL-temperature plots due to the quenching effects. Contrary to this, Kumar and Chourasiya suggest that this decrease is due to the normalization process. Here we hope to clarify any confusion regarding our published study.

  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. PMID:15117200

  10. Rates of reactions catalysed by a dimeric enzyme. Effects of the reaction scheme and the kinetic parameters on co-operativity.

    PubMed Central

    Ishikawa, H; Ogino, H; Oshida, H

    1991-01-01

    For the reaction S in equilibrium P catalysed by a dimeric enzyme, the reaction schemes are considered on the basis of the KNF model. For each of the ten possible schemes, the rate equation is derived on the basis of the combined steady-state and rapid-equilibrium assumptions. The curves of the plots of initial velocity v versus the substrate concentration [S] and the Hill coefficients h calculated from the rate equations depend strongly on the reaction scheme and the parameter X1. This parameter is defined by log (KS2/KS1) and is a measure of the relative affinities of the first and second protomers for the substrate. When X1 less than 0, v-[S] curves for some schemes exhibit negative co-operativity (h less than 1.0) and v-[S] curves for other schemes are similar to that of the Michaelis-Menten scheme, indicating that, even if there is interaction between the distinct protomers, sigmoidal rate behaviour is not necessarily observed. When X1 greater than 0, all the reaction schemes except one, which shows substrate-inhibition kinetic behaviour, exhibit sigmoidal kinetic behaviour (h greater than 1.0), and at the limit of X1 much greater than 0 the Hill coefficients attain the maximum possible value of 2.0. Furthermore, we have found that, even if X1 = 0, the v-[S] curve for almost all the schemes considered in the present work does not necessarily agree with that for the Michaelis-Menten scheme. This means that the deviation of the v-[S] curve from a hyperbola can be observed even if there is no interaction between the distinct protomers. PMID:1741741

  11. Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions: Part 1 - general equations, parameters, and terminology

    NASA Astrophysics Data System (ADS)

    Pschl, U.; Rudich, Y.; Ammann, M.

    2005-04-01

    Aerosols and clouds play central roles in atmospheric chemistry and physics, climate, air pollution, and public health. The mechanistic understanding and predictability of aerosol and cloud properties, interactions, transformations, and effects are, however, still very limited. This is due not only to the limited availability of measurement data, but also to the limited applicability and compatibility of model formalisms used for the analysis, interpretation, and description of heterogeneous and multiphase processes. To support the investigation and elucidation of atmospheric aerosol and cloud surface chemistry and gas-particle interactions, we present a comprehensive kinetic model framework with consistent and unambiguous terminology and universally applicable rate equations and parameters. It allows to describe mass transport and chemical reactions at the gas-particle interface and to link aerosol and cloud surface processes with gas phase and particle bulk processes in systems with multiple chemical components and competing physicochemical processes. The key elements and essential aspects of the presented framework are: a simple and descriptive double-layer surface model (sorption layer and quasi-static layer); straightforward flux-based mass balance and rate equations; clear separation of mass transport and chemical reactions; well-defined rate parameters (uptake and accommodation coefficients, reaction and transport rate coefficients); clear distinction between gas phase, gas-surface, and surface-bulk transport (gas phase diffusion correction, surface and bulk accommodation); clear distinction between gas-surface, surface layer, and surface-bulk reactions (Langmuir-Hinshelwood and Eley-Rideal mechanisms); mechanistic description of concentration and time dependencies; flexible inclusion/omission of chemical species and physicochemical processes; flexible convolution/deconvolution of species and processes; and full compatibility with traditional resistor model formulations. Exemplary practical applications and model calculations illustrating the relevance of the above aspects will be presented in a companion paper (Ammann and Pschl, 2005). We expect that the presented model framework will serve as a useful tool and basis for experimental and theoretical studies investigating and describing atmospheric aerosol and cloud surface chemistry and gas-particle interactions. In particular, it is meant to support the planning and design of laboratory experiments for the elucidation and determination of kinetic parameters; the establishment, evaluation, and quality assurance of comprehensive and self-consistent collections of rate parameters; and the development of detailed master mechanisms for process models and the derivation of simplified but yet realistic parameterizations for atmospheric and climate models.

  12. Kinetic model for the oxidative chlorination of ethane yielding vinyl chloride. III. Formation and transformation of 1,1-dichloroethane and 1,1,2-trichloroethane

    SciTech Connect

    Gel'perin, E.I.; Bakshi, Yu.M.; Avetisov, A.K.; Gel'bshtein, A.I.

    1983-05-01

    A study was carried out on the oxidative chlorination of 1,1-dichloroethane at 350-450/sup 0/C and of 1,1,2-trichloroethane at 375-450/sup 0/C on an aged CuCl/sub 2/-KCl catalyst. The rates of transformation of both these chloroethanes is proportional to their partial pressures. In addition, the rate of transformation of 1,1,2-trichloroethane depends on the partial pressure of chlorine to the 0.5 power. Vinyl chloride is formed in the oxidative chlorination of ethane from 1,1- and 1,2-dichloroethanes. The single pathway for the reaction of vinyl chloride is its additive chlorination to yield 1,1,2-trichloroethane. The results obtained were used to describe the transformations of ethyl chloride to yield ethylene and dichloroethanes. 3 figures, 4 tables.

  13. Modeling of the shape of polyethylene oxide single crystals and determination of the kinetic crystallization parameters: Theoretical and experimental approaches

    NASA Astrophysics Data System (ADS)

    Shcherbina, M. A.; Chvalun, S. N.; Ungar, G.

    2012-11-01

    The curvature of faces of polymer single crystals is described by the system of Mansfield equations, which is based on the Frank-Seto growth model. This model assumes the velocity of nucleus steps to be the same for their propagation to the right and left and is valid only for symmetric crystallographic planes. To describe the shape of polyethylene oxide single crystals grown from melt and limited by the {100} and {120} folding planes, it is assumed that the layer velocities to the right and left are different on {120} faces. This approach allows modeling, with a high accuracy, of the observed shapes of polymer single crystals grown at different temperatures, which makes it possible to determine unambiguously the fundamental crystallization parameters: the dimensionless ratio of the secondary homogeneous nucleation rate to the average velocities of nuclei along the crystallization planes and the ratio of nucleus velocities to the right and left. In addition, it was found that a known macroscopic single-crystal growth rate can be used to determine the absolute values of the secondary homogeneous nucleation rate and the velocities of nuclei along the growth plane.

  14. 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. PMID:25549903

  15. 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. PMID:19646039

  16. Isotopic discrimination and kinetic parameters of RubisCO from the marine bloom-forming diatom, Skeletonema costatum.

    PubMed

    Boller, A J; Thomas, P J; Cavanaugh, C M; Scott, K M

    2015-01-01

    The cosmopolitan, bloom-forming diatom, Skeletonema costatum, is a prominent primary producer in coastal oceans, fixing CO2 with ribulose 1,5-bisphosphate carboxylase/oxygenase (RubisCO) that is phylogenetically distinct from terrestrial plant RubisCO. RubisCOs are subdivided into groups based on sequence similarity of their large subunits (IA-ID, II, and III). ID is present in several major oceanic primary producers, including diatoms such as S. costatum, coccolithophores, and some dinoflagellates, and differs substantially in amino acid sequence from the well-studied IB enzymes present in most cyanobacteria and in green algae and plants. Despite this sequence divergence, and differences in isotopic discrimination apparent in other RubisCO enzymes, stable carbon isotope compositions of diatoms and other marine phytoplankton are generally interpreted assuming enzymatic isotopic discrimination similar to spinach RubisCO (IB). To interpret phytoplankton ?(13) C values, S. costatum RubisCO was characterized via sequence analysis, and measurement of its KCO2 and Vmax , and degree of isotopic discrimination. The sequence of this enzyme placed it among other diatom ID RubisCOs. Michaelis-Menten parameters were similar to other ID enzymes (KCO2 = 48.9 2.8 ?m; Vmax = 165.1 6.3 nmol min(-1 ) mg(-1) ). However, isotopic discrimination (? = [(12) k/(13) k - 1] 1000) was low (18.5; 17.0-19.9, 95% CI) when compared to IA and IB RubisCOs (22-29), though not as low as ID from coccolithophore, Emiliania huxleyi (11.1). Variability in ?-values among RubisCOs from primary producers is likely reflected in ?(13) C values of oceanic biomass. Currently, ?(13) C variability is ascribed to physical or chemical factors (e.g. illumination, nutrient availability) and physiological responses to these factors (e.g. carbon-concentrating mechanisms). Estimating the importance of these factors from ?(13) C measurements requires an accurate ?-value, and a mass-balance model using the ?-value for S. costatum RubisCO is presented. Clearly, appropriate ?-values must be included in interpreting ?(13) C values of environmental samples. PMID:25302659

  17. Direct kinetic study of radical transformation reaction Me sub 2 COH + Ph sub 2 CO yields Me sub 2 CO + Ph sub 2 COH

    SciTech Connect

    Demeter, A.; Berces, T. )

    1991-02-07

    Reaction Me{sub 2}COH + Ph{sub 2}CO {yields} Me{sub 2}CO + Ph{sub 2}COH (5) was studied by laser flash photolysis under such experimental conditions where the changes in the concentrations of ketyl radicals with reaction time were controlled by this radical transformation process. Diphenylketyl radical concentration profiles were obtained by monitoring transient absorption at 540 nm and the rate coefficient k{sub 5} was extracted from that part of the concentration trajectory which was determined solely by reaction 5. Thus, k{sub 5} = (3.6 {plus minus} 0.6) {times} 10{sup 5} dm{sup 3} mol{sup {minus}1} s{sup {minus}1} was determined at 298 K in acetonitrile, which is higher than the two recently reported values derived from quantum yields measured under steady-state conditions. A reaction mechanism for the radical transformation process (5) is proposed in which hydrogen-bonded species formed from ketyl radical and benzophenone participate.

  18. 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. PMID:25772368

  19. Analysis of the kinetics and yields of OH radical production from the CH3OCH2 + O2 reaction in the temperature range 195-650 K: an experimental and computational study.

    PubMed

    Eskola, A J; Carr, S A; Shannon, R J; Wang, B; Blitz, M A; Pilling, M J; Seakins, P W; Robertson, S H

    2014-08-28

    The methoxymethyl radical, CH3OCH2, is an important intermediate in the low temperature combustion of dimethyl ether. The kinetics and yields of OH from the reaction of the methoxymethyl radical with O2 have been measured over the temperature and pressure ranges of 195-650 K and 5-500 Torr by detecting the hydroxyl radical using laser-induced fluorescence following the excimer laser photolysis (248 nm) of CH3OCH2Br. The reaction proceeds via the formation of an energized CH3OCH2O2 adduct, which either dissociates to OH + 2 H2CO or is collisionally stabilized by the buffer gas. At temperatures above 550 K, a secondary source of OH was observed consistent with thermal decomposition of stabilized CH3OCH2O2 radicals. In order to quantify OH production from the CH3OCH2 + O2 reaction, extensive relative and absolute OH yield measurements were performed over the same (T, P) conditions as the kinetic experiments. The reaction was studied at sufficiently low radical concentrations (?10(11) cm(-3)) that secondary (radical + radical) reactions were unimportant and the rate coefficients could be extracted from simple bi- or triexponential analysis. Ab initio (CBS-GB3)/master equation calculations (using the program MESMER) of the CH3OCH2 + O2 system were also performed to better understand this combustion-related reaction as well as be able to extrapolate experimental results to higher temperatures and pressures. To obtain agreement with experimental results (both kinetics and yield data), energies of the key transition states were substantially reduced (by 20-40 kJ mol(-1)) from their ab initio values and the effect of hindered rotations in the CH3OCH2 and CH3OCH2OO intermediates were taken into account. The optimized master equation model was used to generate a set of pressure and temperature dependent rate coefficients for the component nine phenomenological reactions that describe the CH3OCH2 + O2 system, including four well-skipping reactions. The rate coefficients were fitted to Chebyshev polynomials over the temperature and density ranges 200 to 1000 K and 1 10(17) to 1 10(23) molecules cm(-3) respectively for both N2 and He bath gases. Comparisons with an existing autoignition mechanism show that the well-skipping reactions are important at a pressure of 1 bar but are not significant at 10 bar. The main differences derive from the calculated rate coefficient for the CH3OCH2OO ? CH2OCH2OOH reaction, which leads to a faster rate of formation of O2CH2OCH2OOH. PMID:25069059

  20. Fundamental electrode kinetics

    NASA Technical Reports Server (NTRS)

    Elder, J. P.

    1968-01-01

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

  1. 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.

  2. 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

  3. Kinetic model framework for aerosol and cloud surface chemistry and gas-particle interactions - Part 1: General equations, parameters, and terminology

    NASA Astrophysics Data System (ADS)

    Pschl, U.; Rudich, Y.; Ammann, M.

    2007-12-01

    Aerosols and clouds play central roles in atmospheric chemistry and physics, climate, air pollution, and public health. The mechanistic understanding and predictability of aerosol and cloud properties, interactions, transformations, and effects are, however, still very limited. This is due not only to the limited availability of measurement data, but also to the limited applicability and compatibility of model formalisms used for the analysis, interpretation, and description of heterogeneous and multiphase processes. To support the investigation and elucidation of atmospheric aerosol and cloud surface chemistry and gas-particle interactions, we present a comprehensive kinetic model framework with consistent and unambiguous terminology and universally applicable rate equations and parameters. It enables a detailed description of mass transport and chemical reactions at the gas-particle interface, and it allows linking aerosol and cloud surface processes with gas phase and particle bulk processes in systems with multiple chemical components and competing physicochemical processes. The key elements and essential aspects of the presented framework are: a simple and descriptive double-layer surface model (sorption layer and quasi-static layer); straightforward flux-based mass balance and rate equations; clear separation of mass transport and chemical reactions; well-defined and consistent rate parameters (uptake and accommodation coefficients, reaction and transport rate coefficients); clear distinction between gas phase, gas-surface, and surface-bulk transport (gas phase diffusion, surface and bulk accommodation); clear distinction between gas-surface, surface layer, and surface-bulk reactions (Langmuir-Hinshelwood and Eley-Rideal mechanisms); mechanistic description of concentration and time dependences (transient and steady-state conditions); flexible addition of unlimited numbers of chemical species and physicochemical processes; optional aggregation or resolution of intermediate species, sequential processes, and surface layers; and full compatibility with traditional resistor model formulations. The outlined double-layer surface concept and formalisms represent a minimum of model complexity required for a consistent description of the non-linear concentration and time dependences observed in experimental studies of atmospheric multiphase processes (competitive co-adsorption and surface saturation effects, etc.). Exemplary practical applications and model calculations illustrating the relevance of the above aspects are presented in a companion paper (Ammann and Pschl, 2007). We expect that the presented model framework will serve as a useful tool and basis for experimental and theoretical studies investigating and describing atmospheric aerosol and cloud surface chemistry and gas-particle interactions. It shall help to end the "Babylonian confusion" that seems to inhibit scientific progress in the understanding of heterogeneous chemical reactions and other multiphase processes in aerosols and clouds. In particular, it shall support the planning and design of laboratory experiments for the elucidation and determination of fundamental kinetic parameters; the establishment, evaluation, and quality assurance of comprehensive and self-consistent collections of rate parameters; and the development of detailed master mechanisms for process models and derivation of simplified but yet realistic parameterizations for atmospheric and climate models.

  4. "a" interfacial parameter in Nicolais-Narkis model for yield strength of polymer particulate nanocomposites as a function of material and interphase properties.

    PubMed

    Zare, Yasser

    2016-05-15

    In this paper, "a" interfacial parameter in Nicolais-Narkis model is expressed by thickness "ri" and strength "σi" of interphase between polymer and nanoparticles as well as material properties. "a" parameter is connected to "B1" interfacial parameter in modified Pukanszky model and the effects of "ri" and "σi" on "a" are explained. The negligible difference between "a" values calculated by fitting the experimental results to Nicolais-Narkis model and also, by "B1" results confirms the accurateness of the suggested relation between "a" and "B1" parameters. Additionally, an inverse relation is found between "a" and "B1" parameters for nanocomposites containing spherical nanoparticles. The results demonstrate that the slight levels of "ri" and "σi" data give a large value of "a" which indicates the poor interfacial adhesion. PMID:26955000

  5. Assessment of total- and partial-body irradiation in a baboon model: preliminary results of a kinetic study including clinical, physical, and biological parameters.

    PubMed

    Hrodin, Francis; Richard, Sandrine; Grenier, Nancy; Arvers, Philippe; Grome, Patrick; Baug, Stphane; Denis, Josiane; Chaussard, Herv; Gouard, Stphane; Mayol, Jean-Franois; 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. PMID:22951472

  6. Kinetics and activation parameters of the reaction of cyanide with free aquocobalamin and aquocobalamin bound to a haptocorrin from chicken serum.

    PubMed

    Marques, H M; Brown, K L; Jacobsen, D W

    1988-09-01

    The kinetics of the reaction of cyanide with free aquocobalamin (H2OCbl) and with aquocobalamin bound to a vitamin B12-binding protein (haptocorrin) from chicken serum (HC-H2OCbl) have been investigated as a function of temperature and pH. The mechanism of replacement of H2O from protein-bound and free H2OCbl is apparently the same and involves attack of both CN- (k1) and HCN (k2). The reactions with HC-H2OCbl are somewhat slower than those with free H2OCbl, k1 being 22-fold smaller and k2 7-fold smaller at 25 degrees C. The relatively small effect of the protein on the rate constants supports the view that the metal in HC-H2OCbl is readily accessible to solvent. Activation parameters suggest that the transition states for ligand substitution are stabilized by nucleophilic participation (at least by CN-) and that ligand substitution on the protein-bound cobalamin proceeds through more ordered, concerted transition states. The latter effect suggests that the Co-O bond of H2OCbl is strengthened upon binding to the haptocorrin. PMID:2842331

  7. Estimating kinetic parameters for single channels with simulation. A general method that resolves the missed event problem and accounts for noise.

    PubMed Central

    Magleby, K L; Weiss, D S

    1990-01-01

    Analysis of currents recorded from single channels is complicated by the limited time resolution (filtering) of the data which can prevent the detection of brief intervals. Although a number of approaches have been used to correct for the undetected intervals (missed events) when identifying kinetic models and estimating parameters, none of them provide a general method which takes into account the true effects of noise and limited time resolution. This paper presents such a method. The approach is to use simulated single-channel currents to incorporate the true effects of filtering and noise on missed events and interval durations. The simulated currents are then analyzed in a manner identical to that used to analyze the experimental currents. An iterative search process using likelihood comparison of two-dimensional dwell-time distributions obtained from the simulated and experimental single-channel currents then allows the most likely rate constants to be determined. The large errors and false solutions that can result from the more typically applied assumptions of no noise and an absolute dead time (idealized filtering) are excluded by the iterative simulation method, and the correlation information contained in the two-dimensional distributions should increase the ability to distinguish among different gating mechanisms. The iterative simulation method is generally applicable to channels which typically open to a single conductance level. For these channels the method places no restrictions on the proposed gating mechanism or the form of the predicted dwell-time distributions. PMID:1703449

  8. Dynamic determination of kinetic parameters for the interaction between polypeptide hormones and cell-surface receptors in the perfused rat liver by the multiple-indicator dilution method

    SciTech Connect

    Sato, H.; Sugiyama, Y.; Sawada, Y.; Iga, T.; Sakamoto, S.; Fuwa, T.; Hanano, M. )

    1988-11-01

    Hepatic elimination of epidermal growth factor (EGF) via receptor-mediated endocytosis was studied by a multiple-indicator dilution method in the isolated perfused rat liver, in which cell polarity and spatial organization are maintained. In this method EGF was given with inulin, an extracellular reference, as a bolus into the portal vein, and dilution curves of both compounds in the hepatic vein effluent were analyzed. Analysis of the dilution curve for EGF, compared with that for somatostatin, which showed no specific binding to isolated liver plasma membranes, resulted as follows: (i) both extraction ratio and distribution volume of {sup 125}I-labeled EGF decreased as the injected amount of unlabeled EGF increased; (ii) the ratio plot of the dilution curve for EGF exhibited an upward straight line initially for a short period of time, whereas the ratio plot of somatostatin gradually decreased. The multiple-indicator dilution method was used for other peptides also. Insulin and glucagon, known to have hepatocyte receptors, behaved similarly to EGF in shape of their ratio plots. The kinetic parameters calculated by this analysis were comparable with reported values obtained by in vitro direct binding measurements at equilibrium using liver homogenates. They conclude that the multiple-indicator dilution method is a good tool for analyzing the dynamics of peptide hormones-cell-surface receptor interaction under a condition in which spatial architecture of the liver is maintained.

  9. Magnetic hyperthermia properties of nanoparticles inside lysosomes using kinetic Monte Carlo simulations: Influence of key parameters and dipolar interactions, and evidence for strong spatial variation of heating power

    NASA Astrophysics Data System (ADS)

    Tan, R. P.; Carrey, J.; Respaud, M.

    2014-12-01

    Understanding the influence of dipolar interactions in magnetic hyperthermia experiments is of crucial importance for fine optimization of nanoparticle (NP) heating power. In this study we use a kinetic Monte Carlo algorithm to calculate hysteresis loops that correctly account for both time and temperature. This algorithm is shown to correctly reproduce the high-frequency hysteresis loop of both superparamagnetic and ferromagnetic NPs without any ad hoc or artificial parameters. The algorithm is easily parallelizable with a good speed-up behavior, which considerably decreases the calculation time on several processors and enables the study of assemblies of several thousands of NPs. The specific absorption rate (SAR) of magnetic NPs dispersed inside spherical lysosomes is studied as a function of several key parameters: volume concentration, applied magnetic field, lysosome size, NP diameter, and anisotropy. The influence of these parameters is illustrated and comprehensively explained. In summary, magnetic interactions increase the coercive field, saturation field, and hysteresis area of major loops. However, for small amplitude magnetic fields such as those used in magnetic hyperthermia, the heating power as a function of concentration can increase, decrease, or display a bell shape, depending on the relationship between the applied magnetic field and the coercive/saturation fields of the NPs. The hysteresis area is found to be well correlated with the parallel or antiparallel nature of the dipolar field acting on each particle. The heating power of a given NP is strongly influenced by a local concentration involving approximately 20 neighbors. Because this local concentration strongly decreases upon approaching the surface, the heating power increases or decreases in the vicinity of the lysosome membrane. The amplitude of variation reaches more than one order of magnitude in certain conditions. This transition occurs on a thickness corresponding to approximately 1.3 times the mean distance between two neighbors. The amplitude and sign of this variation is explained. Finally, implications of these various findings are discussed in the framework of magnetic hyperthermia optimization. It is concluded that feedback on two specific points from biology experiments is required for further advancement of the optimization of magnetic NPs for magnetic hyperthermia. The present simulations will be an advantageous tool to optimize magnetic NPs heating power and interpret experimental results.

  10. 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. PMID:20083403

  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-Pea, 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 (? max?=?0.101h(-1), K s?=?2.56g/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 700mL 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 (1.7mmol/day), the highest cumulative H2 volume (310mL), and 25% chemical oxygen demand (COD) removal were obtained with an initial substrate (FVW) concentration of 37g COD/L. The lowest H2 production rates were obtained with relatively low initial substrate concentrations of 5 and 11g 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. PMID:23832860

  12. Reduction of chlorinated methanes with nano-scale Fe particles: effects of amphiphiles on the dechlorination reaction and two-parameter regression for kinetic prediction.

    PubMed

    Feng, Jing; Zhu, Bao-Wei; Lim, Teik-Thye

    2008-12-01

    The influences of amphiphiles, including humic acid (HA) and various types of surfactants, on dechlorination of carbon tetrachloride (CTC) and chloroform (CF) by the nano-scale Fe particles were investigated. Since the amphiphiles would modify the surface tension between the liquid-liquid and solid-liquid interface, in the presence of amphiphile matrix solution the Fe corrosion rate and the parent compound dechlorination rate would be different from those in the ultrapure water. Among the four amphiphile solutions, Fe corrosion rate was the highest in the anionic surfactant sodium dodecyl sulfate (SDS) solution, presumably due to the existence of chemisorption between the hydrophilic head of SDS and Fe particles. The dechlorination rates of CTC and CF could be described with the pseudo-first order kinetic model. The influences of amphiphiles on the dechlorination reaction rate were related to the species of parent compound and concentration of the matrix solution. The influences of HA on the dechlorination of CTC and CF were the most significant compared to other matrix solutions. At relatively low HA concentration (<0.1 g L(-1)), the HA molecules (serving as electron transfer mediator) would significantly accelerate the dechlorination rate of CF. The two-parameter regression with energy of the lowest unoccupied molecular orbital (E(LUMO)) and HA concentration as the descriptors was developed to predict the specific reduction rate constants of chlorinated methanes in HA solution. The analysis of variance (ANOVA) indicated the existence of significant relationship between the dechlorination rate constants and the two descriptors. PMID:18809199

  13. 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

  14. Biosorption of Cr(VI) by Ceratocystis paradoxa MSR2 using isotherm modelling, kinetic study and optimization of batch parameters using response surface methodology.

    PubMed

    Samuel, Melvin S; E A Abigail, M; 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 2 g 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

  15. Glucuronidation of paracetamol by human liver microsomes in vitro / enzyme kinetic parameters and interactions with short-chain aliphatic alcohols and opiates.

    PubMed

    Boldt, Petra; Rothschild, Markus A; Kaeferstein, Herbert

    2007-01-01

    In this study, glucuronidation of paracetamol (CAS 103-90-2) by human liver microsomes and the effects of aliphatic alcohols and opiates were investigated. Paracetamol glucuronidation was optimised for various incubation conditions. Ten different aliphatic alcohols and the opiates morphine, codeine and dihydrocodeine were analysed as inhibitors of paracetamol glucuronidation. Furthermore, the effects of paracetamol on morphine-3 and codeine glucuronidation were investigated. Enzyme kinetic analysis was carried out via determination of the parameters Km, Vmax, Ki and the type of inhibition. Except for methanol and ethanol, all Investigated alcohols inhibited glucuronidation of paracetamol. Ki values ranged between 4.59 mmol/l (n-pentanol) and 340.54 mmol/l (2-propanol). Extent of inhibition strongly depended on the structure and clearly increased with the length of the alkyl chain. All tested opiates inhibited paracetamol glucuronidation with Ki values between 4.02 mmol/l (dihydrocodeine) and 11.44 mmol/l (morphine). Paracetamol itself turned out to be an inhibitor of opiate glucuronidation. The apparent Ki values were 4.62 mmol/l (inhibition of morphine-3 glucuronidation) and 9.44 mmol/l (inhibition of codeine glucuronidation). A mixed inhibition type was determined for all substances. The in vitro studies show a great inhibition potential for the analysed substances. Transferring the results to the in vivo situation, a higher liver toxicity of paracetamol can be assumed, if concomitantly a lot of alcoholic beverages with congener alcohols--e.g. fruit schnapps or whisky--are drunk or if opiates--as analgesics or narcotics--are taken in higher doses. PMID:18380412

  16. 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.

  17. 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.

  18. 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.

  19. Neutron monitors and muon detectors for solar modulation studies: Interstellar flux, yield function, and assessment of critical parameters in count rate calculations

    NASA Astrophysics Data System (ADS)

    Maurin, D.; Cheminet, A.; Derome, L.; Ghelfi, A.; Hubert, G.

    2015-01-01

    Particles count rates at given Earth location and altitude result from the convolution of (i) the interstellar (IS) cosmic-ray fluxes outside the solar cavity, (ii) the time-dependent modulation of IS into Top-of-Atmosphere (TOA) fluxes, (iii) the rigidity cut-off (or geomagnetic transmission function) and grammage at the counter location, (iv) the atmosphere response to incoming TOA cosmic rays (shower development), and (v) the counter response to the various particles/energies in the shower. Count rates from neutron monitors or muon counters are therefore a proxy to solar activity. In this paper, we review all ingredients, discuss how their uncertainties impact count rate calculations, and how they translate into variation/uncertainties on the level of solar modulation ϕ (in the simple Force-Field approximation). The main uncertainty for neutron monitors is related to the yield function. However, many other effects have a significant impact, at the 5-10% level on ϕ values. We find no clear ranking of the dominant effects, as some depend on the station position and/or the weather and/or the season. An abacus to translate any variation of count rates (for neutron and μ detectors) to a variation of the solar modulation ϕ is provided.

  20. 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; Mrikofer-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

  1. Increasing Yield

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Maize yield improvement in the 20th century represents one of the great success stories of plant breeding and agronomy. Maize grain yield in the United States has increased on average by 0.122 metric tons per hectare per year since 1945 (Figure 1). This is in sharp contrast to essentially zero gain ...

  2. HCl yield and chemical kinetics study of the reaction of Cl atoms with CH3I at the 298 K temperature using the infra-red tunable diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Sharma, R. C.; Blitz, M.; Wada, R.; Seakins, P. W.

    2014-07-01

    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 1014 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 1014 molecule cm-3 of [CH3I] and 24% at the concentration 4.0 1015 molecule cm-3 of [CH3I], at constant concentration 4.85 1012 molecule cm-3 of [CH3], and at 7.3 1012 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.

  3. 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] 7.010(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 1.0010(14) molecule cm(-3) of [CH3I] and 24% at the concentration 4.010(15) molecule cm(-3) of [CH3I], at constant concentration 4.8510(12) molecule cm(-3) of [CH3], and at 7.310(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 = (2.750.35)10(-10) s(-1)) and CH3I+CH3ICl = product2 (k = 1.900.15)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. PMID:24667422

  4. 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 addition to the tertiary carbon-carbon double bond (HO{sub 2} addition at CD/C2 carbon atom of isobutene) has a lower activation energy than addition to the secondary carbon-carbon double bond CD/C/H, which is lower than addition to the primary carbon-carbon bond CD/H2; the values are 12.11(11.56), 11.08(10.34), and 7.63(7.03) kcal/mol, respectively, at CBS-q//MP2(full)/6-31G(d) level. Data in parentheses are calculations at the CBS-q//B3LYP/6-31G(d) level. The E{sub a} for addition to primary carbon-carbon double bonds of ethylene, propene, and isobutene also show a decreasing trend 13.49(12.89), 12.16(11.20), and 10.70(10.59) kcal/mol, respectively. The high-pressure limit rate constants are calculated.

  5. Kinetic and process studies on free and solid acid catalyzed hydrolysis of biomass substrates

    SciTech Connect

    Abasaeed, A.E.

    1987-01-01

    Trifluoroacetic acid (TFA) was tested as a catalyst for cellulose hydrolysis. Eighty percent conversion of cellulose into glucose was obtained with concentrated TFA. The kinetics of TFA catalyzed cellulose hydrolysis was investigated. The reaction was found to follow first order kinetics for both hydrolysis and decomposition. The kinetic parameters were determined from experimental data covering conditions of 160-180 C, 10-30% acid, and 1:2 solid to liquid ratio. The hydrolysis reaction was found to be more sensitive to temperature than the decomposition reaction. Use of TFA was further investigated as a pretreatment for enzymatic hydrolysis of cellulose. A two-fold increase in sugar yields was obtained for TFA pretreated samples in comparison to untreated ones. The kinetics of hydrolysis of prehydrolyzed wood by sulfuric acid was investigated. The substrate was first treated with 0.75% acid at 184 C for 4 minutes to remove hemicellulose. The kinetic parameters were determined in the range of 198-215 C and 1-3% acid. A heterogeneous kinetic model was developed to study the effect of particle size on acid hydrolysis of cellulose. It was found that as the chip size increases, maximum glucose yield decreases and reaction time at which maximum yield occurs increases. Acidic zeolites (LZ-M-8) were investigated as catalysts for hydrolysis reaction of inulin into fructose. The hydrolysis reaction was found to follow first order kinetics. Products containing 96 and 75% fructose were obtained upon hydrolysis respectively from inulin and extract.

  6. 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.

  7. 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.

  8. OH Yields from Gas-Phase Ozonolysis of Isoprene

    NASA Astrophysics Data System (ADS)

    Malkin, T. L.; Goddard, A.; Heard, D. E.; Seakins, P. W.

    2008-12-01

    Environmental chambers are an important part of an integrated and multifaceted approach to understanding chemical processes in the atmosphere, by bridging the gap between laboratory measurements of individual elementary reactions and the complexity of the real atmosphere. The University of Leeds HIRAC (Highly Instrumented Reactor of Atmospheric Chemistry) chamber is a 2 m3 stainless steel vessel capable of operating at a variety of temperatures and pressures, enabling wide ranging kinetics experiments [D.R. Glowacki et al., Atmos. Chem. Phys., 7,5371,(2007)]. Ozone-alkene reactions are a non-photolytic source of OH, HO2 and RO2 radicals and are a significant source of these radicals in urban and rural air. We have used four different methods to measure OH yields in the HIRAC chamber. These are (1) laser- induced fluorescence at low pressure (FAGE) (detection limit of ~106 molecule cm-3); which provides a direct, calibrated measurement of the OH radical concentration. (2) An indirect method to measure OH yields by use of an OH radical scavenger (cyclohexane) producing stable products (cyclohexanol and cyclohexanone), the concentrations of which allow OH yields to be determined after suitable calibration. (3) A second indirect method utilises 1,3,5-trimethylbenzene (TMB) as an OH tracer, which is consumed by reaction with OH radicals. Analysis of the diminution in concentration of TMB allows the estimation of OH radical production yields. (4) Also a kinetic study was utilised, in which the decay of isoprene follows pseudo-first order kinetics using a 10 fold excess of ozone over alkene. The decay rate of isoprene was monitored using gas chromatography (GC) and FTIR, and was found to be exponential in all cases. From the decrease of the effective rate constant upon the addition of cyclohexane, the OH yield was determined. These 4 different techniques were used to measure the OH yield of O3 + isoprene. The three indirect techniques have been used to determine OH yields for ozone + isoprene of 0.267 0.024, 0.265 0.020 and 0.253 0.026 for detection by OH scavenger, kinetic study and OH tracer, respectively. The reaction between O3 and isoprene has been studied by the direct detection the OH concentrations using FAGE, with excellent precision. A numerical model based on the Master Chemical Mechanism (MCM), with the OH yield as a variable parameter, was used to calculate the OH concentration, and a best fit to the OH FAGE concentration data, gave a yield of 0.255 0.022 was determined. These techniques were then utilised to determine a pressure dependence of the OH yield for ozonolysis of isoprene.

  9. 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 following heats of formation for the RS radicals in units of kcal/mol: Delta-H(sub f)(sub 0)(SH) = 34.07 +/- 0.72, Delta-H(sub f)(sub 298)(SH) = 34.18 +/- 0.68, Delta-H(sub f)(sub 0)(CH3S) = 31.44 +/- 0.54, Delta-H(sub f)(sub 298)(CH3S) = 29.78 +/- 0.44; errors are 2 sigma and represent estimates of absolute accuracy. The SH heat of formation determined from our data agrees well with literature values but has reduced error limits compared to other available values. The CH3S heat of formation determined from our date is near the low end of the range of previous estimates and is 3-4 kcal/mol lower than values derived from recent molecular beam photofragmentation studies.

  10. 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 to exert only limited effects on the REC traits. Instead, breeders may be able to exploit genetic variations in the %CY, particularly RECFAT and RECPROTEIN. This last component is not explained by the milk protein content, suggesting that its direct selection could be beneficial for cheese production aptitude. Collectively, our findings indicate that breeding strategies aimed at enhancing CY and REC could be easily and rapidly implemented for dairy cattle populations in which FTIR spectra are routinely acquired from individual milk samples. PMID:25958274

  11. EVALUATION OF CHEMICAL REACTION MECHANISMS FOR PHOTOCHEMICAL SMOG. PART 3. SENSITIVITY OF EKMA (EMPIRICAL KINETIC MODELING APPROACH) TO CHEMICAL MECHANISM AND INPUT PARAMETERS

    EPA Science Inventory

    Six chemical reaction mechanisms for photochemical smog were used to study the effect of input parameters on volatile organic compound (VOC) control requirements needed to reduce ozone. The parameters studied were initial VOC composition, dilution rate, post 8-A.M. emissions, bas...

  12. In-storage psychrophilic anaerobic digestion: acclimated microbial kinetics.

    PubMed

    King, Susan; Courvoisier, Pierre; Guiot, Serge; Barrington, Suzelle

    2012-01-01

    In-storage psychrophilic anaerobic digestion develops by microbial acclimation in covered swine-manure storage tanks, producing CH4 and stabilizing organic matter. To optimize the system's performance, the process kinetics must be understood. The objective of this study was to evaluate kinetic parameters describing the major stages in the digestion process, and to investigate the effect of temperature acclimation on these parameters. Specific activity tests were performed using manure inocula and five substrates at three incubation temperatures. Extant substrate activities were determined analytically for each case, and intrinsic kinetic parameters for glucose uptake were estimated by grid search fitting to the Monod model. The results demonstrate that this acclimated microbial community exhibits different kinetic parameters to those of the mesophilic communities currently modelled in the literature, with increased activity at low temperatures, varying with substrate and temperature. For glucose, the higher uptake is accompanied by lower microbial yield and half-saturation constant. Decomposing these values suggests that active psychrophilic and mesophilic microbial populations co-exist within the community. This work also confirms that a new method of assessing microbial substrate kinetics must be developed for manure microbial communities, separating microbial mass from other suspended organics. PMID:22988638

  13. 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. PMID:26432268

  14. Characterizing O2 uptake response kinetics during exercise.

    PubMed

    Whipp, B J; Casaburi, R

    1982-05-01

    It has recently been proposed that the half time for the kinetics of VO2 during exercise may be accurately determined from a linear fit to the exponential response on linear coordinates. We demonstrate that although this is the case for two periods of data utilization, it is not true for any others, and that small variations in this period markedly influence the estimate. Furthermore, it is necessary to know the parameters of the response to determine the appropriate period of data collection. We conclude that the proposed linear estimation procedure is likely to yield erroneous values for VO2 kinetics during exercise. PMID:7107106

  15. Combustion kinetics of coal dust

    SciTech Connect

    Sal`nikov, A.V.; Repic, B.S.; Radulovic, P.T.; Jovanovic, L.L.

    1995-10-01

    A method for determining parameters that are important for the combustion kinetics of coal dust is developed. Values of these parameters for six types of lignite are obtained from experimental results on combustion of coal dust in a laboratory furnace.

  16. Kinetics of changes in shelf life parameters during storage of pearl millet based kheer mix and development of a shelf life prediction model.

    PubMed

    Bunkar, Durga Shankar; Jha, Alok; Mahajan, Ankur; Unnikrishnan, V S

    2014-12-01

    Pearl millet, dairy whitener and sugar powder were blended for preparing pearl millet kheer mix. Pearl millet based kheer mix samples were stored at 8, 25, 37 and 45C under nitrogen flushing environment. Changes in HMF and TBA formation in the dry mix and sensory changes in reconstituted kheer were studied upto 180days. In fresh dry mix, the average value of HMF recorded was 4.87?mol/g which increased to 11.23, 13.67, 18.13, and 21.43?mol/g at 8, 25, 37 and 45C, respectively after 180days of storage. From an initial value of 0.067, the TBA value increased to 0.219, 0.311, 0.432 and 0.613 at 532nm at 8, 25, 37 and 45C, respectively after 180days of storage. Data generated from the chemical kinetics of HMF and TBA development that progressed during storage of pearl millet kheer mix were modeled using Arrhenius equations to predict the shelf life of the product. Changes in HMF and TBA followed first order reaction kinetics. It was found that the potential shelf life of the pearl millet based kheer mix was 396days at 8 and 288days at 25C, respectively. PMID:25477640

  17. 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.

  18. 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.; Hll, Sabina-Roxana; Khn, 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 EadieHofstee (EH) -transformations pointed at biphasic MichaelisMenten kinetics (2 MM, EH: Km1 1.21.8 mM, Km2 6.69.0 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 in sucrose uptake by sieve elements, (d) Affinity for sucrose uptake by sieve elements exceeds by far that by phloem parenchyma cells, (e) Patch-clamp studies provide a feasible basis for quantification of sucrose uptake by single cells. The consequences of the findings for whole-plant carbohydrate partitioning are discussed. PMID:23914194

  19. 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, Hillerd, 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 data set, but the coefficient of determination of validation values for the external validation sets were much lower for all traits (0.30 to 0.73), and particularly for fat recovery (0.05 to 0.18), for the training sets compared with the full data set. For each testing subset, the (co)variance components for the measured and FTIR-predicted phenotypes were estimated using bivariate Bayesian analyses and linear models. The intraherd heritabilities for the predicted traits obtained from our internal cross-validation using the whole data set ranged from 0.085 for daily yield of curd solids to 0.576 for protein recovery, and were similar to those obtained from the measured traits (0.079 to 0.586, respectively). The heritabilities estimated from the testing data set used for external validation were more variable but similar (on average) to the corresponding values obtained from the whole data set. Moreover, the genetic correlations between the predicted and measured traits were high in general (0.791 to 0.996), and they were always higher than the corresponding phenotypic correlations (0.383 to 0.995), especially for the external validation subset. In conclusion, we herein report that application of the cross-validation technique to the whole data set tended to overestimate the predictive ability of FTIR spectra, give more precise phenotypic predictions than the calibrations obtained using smaller data sets, and yield genetic correlations similar to those obtained from the measured traits. Collectively, our findings indicate that FTIR predictions have the potential to be used as indicator traits for the rapid and inexpensive selection of dairy populations for improvement of cheese yield, milk nutrient recovery in curd, and daily cheese production per cow. PMID:25108864

  20. Kinetic Rate Law Parameter Measurements on a Borosilicate Waste Glass: Effect of Temperature, pH, and Solution Composition on Alkali Ion Exchange

    SciTech Connect

    Pierce, Eric M.; McGrail, B. Peter; Icenhower, Jonathan P.; Cordova, Elsa A.; Steele, Jackie L.; Baum, Steven R.

    2004-08-01

    The reaction kinetics of glass is controlled by matrix dissolution and ion exchange (IEX). Dissolution of an alkali-rich simulated borosilicate waste glass was investigated using single-pass flow-through (SPFT) experiments. Experiments were conducted as a function of temperature, pH, and solution composition by varying the SiO2 (aq) activity in the influent solution. Results showed that under dilute conditions matrix dissolution increased with increasing pH and temperature, and decreased with increasing SiO2 (aq) activity. IEX rates decreased with increasing pH and temperature, and increased with increasing SiO2 (aq) activity. Over the solution composition range interrogated in this study the dominant dissolution mechanism changed from matrix dissolution to IEX. These results suggest that secondary reactions may become dominant under certain environmental conditions and emphasize the need to incorporate these reactions into dissolution rate models.

  1. Kinetics of the processes, plasma parameters, and output characteristics of a UV emitter operating on XeI molecules and iodine molecules and atoms

    SciTech Connect

    Shuaibov, A. K.; Grabovaya, I. A.; Minya, A. I.; Homoki, Z. T.; Kalyuzhnaya, A. G.; Shchedrin, A. I.

    2011-03-15

    A kinetic model of the processes occurring in the plasma of a high-power low-pressure gas-discharge lamp is presented, and the output characteristics of the lamp are described. The lamp is excited by a longitudinal glow discharge and emits the I{sub 2}(D Prime -A Prime ) 342-nm and XeI(B-X) 253-nm bands and the 206.2-nm spectral line of atomic iodine. When the emitter operates in a sealed-off mode on the p(He): p(Xe): p(I{sub 2}) = 400: 120: (100-200) Pa mixture, the fractions of the UV radiation power of iodine atoms, exciplex molecules of xenon iodide, and iodine molecules comprise 55, 10, and 35%, respectively. At the optimal partial pressure, the maximum total radiation power of the lamp reaches 37 W, the energy efficiency being about 15%.

  2. [Features of the effects of disaccharide structure of saccharose on kinetic parameters of hepatic lipid synthesis from glucose (mechanism of disaccharide effect)].

    PubMed

    Virovets, O A; Shpitonkov, M I; Sokolov, A I; Gapparov, M M

    1990-01-01

    Effects of saccharose or invert sugar on kinetics of lipid synthesis in the rat liver were investigated using 1-14C-glucose as a precursor. The diet containing 30% of saccharose (of the total energy value) for 40 days was found to be sufficient to increase the radioactive carbon flux through total liver lipids more than twice, and through rapidly metabolized neutral lipids and phospholipids more than 4 and 3 times, consequently. On the contrary, when the invert sugar diet was used the radioactive carbon flux through total lipids in the liver was reduced up to 54% of the control level, the lowest radioactive carbon flux was observed through the rapidly metabolized fraction of phospholipids--6% of the control level, only. These changes were caused by the corresponding alterations in lipid synthesis constants. PMID:2275123

  3. Kinetic Demonstration.

    ERIC Educational Resources Information Center

    Burgardt, Erik D.; Ryan, Hank

    1996-01-01

    Presents a unit on chemical reaction kinetics that consists of a predemonstration activity, the demonstration, and a set of postdemonstration activities that help students transfer the concepts to actual chemical reactions. Simulates various aspects of chemical reaction kinetics. (JRH)

  4. 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)

  5. Advanced oxidation of the commercial nonionic surfactant octylphenol polyethoxylate TritonTM X-45 by the persulfate/UV-C process: effect of operating parameters and kinetic evaluation

    NASA Astrophysics Data System (ADS)

    Arslan-Alaton, Idil; Olmez-Hanci, Tugba; Genc, Bora; Dursun, Duygu

    2013-03-01

    This study explored the potential use of a sulfate radical (SO4?-)-based photochemical oxidation process to treat the commercial nonionic surfactant octylphenol polyethoxylate (OPPE) TritonTMX-45. For this purpose, the effect of initial S2O82- (0-5.0 mM) and OPPE (10-100 mg/L) concentrations on OPPE and its organic carbon content (TOC) removal were investigated at an initial reaction pH of 6.5. Results indicated that very fast OPPE degradation (100%) accompanied with high TOC abatement rates (90%) could be achieved for 10 and 20 mg/L aqueous OPPE at elevated S2O82- concentrations (>2.5 mM). S2O82-/UV-C treatment was still capable of complete OPPE removal up to an initial concentration of 40 mg/L in the presence of 2.5 mM S2O82-. On the other hand, TOC removal efficiencies dropped down to only 40% under the same reaction conditions. S2O82-/UV-C oxidation of OPPE was also compared with the relatively well-known and established H2O2/UV-C oxidation process. Treatment results showed that the performance of S2O82-/UV-C was comparable to that of H2O2/UV-C oxidation for the degradation and mineralization of OPPE. In order to elucidate the relative reactivity and selectivity of SO4?- and HO?, bimolecular reaction rate coefficients of OPPE with SO4?- and HO? were determined by employing competition kinetics with aqueous phenol (47 ?M) selected as the reference compound. The first-order abatement rate coefficient obtained for OPPE during S2O82-/UV-C oxidation (0.044 min-1) was found to be significantly lower than that calculated for phenol (0.397 min-1). In the case of H2O2/UV-C oxidation however, similar first-order abatement rate coefficients were obtained for both OPPE (0.087 min-1) and phenol (0.140 min-1). Second-order reaction rate coefficients for OPPE with SO4?- and HO? were determined as 9.8?108 M-1s-1 and 4.1?109 M-1s-1, respectively. The kinetic study also revealed that the selectivity of SO4?- was found to be significantly higher than that of HO?.

  6. 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)

  7. Evaluation and modeling of thermal kinetic degradation for PVA doped PbS quantum dot

    SciTech Connect

    Mahmoud, Waleed E.; Al-Heniti, S.H.

    2011-09-15

    Highlights: {yields} Synthesis of PVA doped PbS quantum dots. {yields} Data fitting using integral and differential thermal kinetic models for calculating activation energy. {yields} Prediction of thermal degradation using iso-conversion model. -- Abstract: The kinetic analysis of the thermogravimetric curves for the thermal decomposition processes of PVA/PbS was performed. The samples were heated in nitrogen, with three different heating rates: 10, 20 and 30 {sup o}C min{sup -1}. Various forms of non-isothermal methods of analysis for determining the kinetic parameters were used. The differential and integral models were used to calculate the activation energies. Comparing with pure PVA, the results showed that the maximum activation energy of thermal degradation is achieved for PVA/PbS nanocomposite. Isoconversion model is used for predicting the thermal degradation acceleration. The results showed that the acceleration of thermal degradation for pure PVA was faster than PVA/PbS nanocomposite.

  8. Characterization of the atrazine sorption process on Andisol and Ultisol volcanic ash-derived soils: kinetic parameters and the contribution of humic fractions.

    PubMed

    Bez, Mara E; Fuentes, Edwar; Espinoza, Jeannette

    2013-07-01

    Atrazine sorption was studied in six Andisol and Ultisol soils. Humic and fulvic acids and humin contributions were established. Sorption on soils was well described by the Freundlich model. Kf values ranged from 2.2-15.6 ?g(1-1/n)mL(1/n)g?. The relevance of humic acid and humin was deduced from isotherm and kinetics experiments. KOC values varied between 221 and 679 mLg? for these fractions. Fulvic acid presented low binding capacity. Sorption was controlled by instantaneous equilibrium followed by a time-dependent phase. The Elovich equation, intraparticle diffusion model, and a two-site nonequilibrium model allowed us to conclude that (i) there are two rate-limited phases in Andisols related to intrasorbent diffusion in organic matter and retarded intraparticle diffusion in the organo-mineral complex and that (ii) there is one rate-limited phase in Ultisols attributed to the mineral composition. The lower organic matter content of Ultisols and the slower sorption rate and mechanisms involved must be considered to assess the leaching behavior of atrazine. PMID:23711282

  9. Measurement of blood protease kinetic parameters with self-assembled monolayer ligand binding assays and label-free MALDI-TOF MS.

    PubMed

    Patrie, Steven M; Roth, Michael J; Plymire, Daniel A; Maresh, Erica; Zhang, Junmei

    2013-11-01

    We report novel ligand binding assay (LBA) surface modalities that permit plasma protease catalytic efficiency (kcat/km) determination by MALDI-TOF MS without the use of liquid chromatography or internal standards such as chemical or metalized labels. Two model LBAs were constructed on planar self-assembled monolayers (SAMs) and used to evaluate the clinically relevant metalloprotease ADAMTS-13 kinetics in plasma. The SAM chemistries were designed to improve biosampling efficiency by minimization of nonspecific adsorption of abundant proteins present at ~100,000 the concentration of the endogenous enzyme. In the first protocol, in-solution digestion of the ADAMTS-13 substrate (vWFh) was performed with immunoaffinity enrichment of the reaction substrate and product to SAM arrays. The second configuration examined protease kcat/km via a surface digestion modality where different substrates were covalently immobilized to the SAM at controlled surface density for optimized protease screens. The results show the MALDI-TOF MS LBA platforms provide limits of quantitation to ~1% protease activity (~60 pM enzyme concentration) in <1 h analysis time, a ~16 improvement over other MS-based LBA formats. Implementation of a vacuum-sublimed MALDI matrix provided good MALDI-TOF MS intra- and interday repeatability, ~1.2 and ~6.6% RSD, respectively. Platform reliability permitted kcat/km determination without internal standards with observed values ~10 improved versus conventional fluorophoric assays. Application of the assays to 12 clinical plasma samples demonstrated proof-of-concept for clinical applications. Overall, this work demonstrates that rationally designed surface chemistries for MALDI-TOF MS may serve as an alternative, label-free methodology with potential for a wide range of biotechnology applications related to targeted enzyme molecular diagnostics. PMID:24107006

  10. 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

    2016-04-01

    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. PMID:26305411

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

    NASA Astrophysics Data System (ADS)

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

    2007-10-01

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

  12. A calculator program for least-squares parameter estimation according to the one-compartment kinetic model with zero-order input.

    PubMed

    Messori, A; Donati-Cori, G; Tendi, E

    1984-01-01

    A calculator program that performs a nonlinear least-squares fit to data conforming to the one-compartment model with zero-order input is described. The program, which is designed for the Hewlett-Packard HP-41 CV calculator, is based on the Gauss-Newton iterative algorithm as modified by Hartley. A subroutine for calculation of initial parameter estimates is incorporated into the program. Plasma concentration data relative to a single oral dose of a sustained-release theophylline formulation are used to demonstrate the practical application of the program. PMID:6547651

  13. Causal network inference using biochemical kinetics

    PubMed Central

    Oates, Chris J.; Dondelinger, Frank; Bayani, Nora; Korkola, James; Gray, Joe W.; Mukherjee, Sach

    2014-01-01

    Motivation: Networks are widely used as structural summaries of biochemical systems. Statistical estimation of networks is usually based on linear or discrete models. However, the dynamics of biochemical systems are generally non-linear, suggesting that suitable non-linear formulations may offer gains with respect to causal network inference and aid in associated prediction problems. Results: We present a general framework for network inference and dynamical prediction using time course data that is rooted in non-linear biochemical kinetics. This is achieved by considering a dynamical system based on a chemical reaction graph with associated kinetic parameters. Both the graph and kinetic parameters are treated as unknown; inference is carried out within a Bayesian framework. This allows prediction of dynamical behavior even when the underlying reaction graph itself is unknown or uncertain. Results, based on (i) data simulated from a mechanistic model of mitogen-activated protein kinase signaling and (ii) phosphoproteomic data from cancer cell lines, demonstrate that non-linear formulations can yield gains in causal network inference and permit dynamical prediction and uncertainty quantification in the challenging setting where the reaction graph is unknown. Availability and implementation: MATLAB R2014a software is available to download from warwick.ac.uk/chrisoates. Contact: c.oates@warwick.ac.uk or sach@mrc-bsu.cam.ac.uk Supplementary information: Supplementary data are available at Bioinformatics online. PMID:25161235

  14. Ethene-Norbornene Copolymerization with Homogeneous Metallocene and Half-Sandwich Catalysts: Kinetics and Relationships between Catalyst Structure and Polymer Structure. 3. Copolymerization Parameters and Copolymerization Diagrams.

    PubMed

    Ruchatz; Fink

    1998-07-28

    The copolymerization parameters of the ethene-norbornene copolymerization using various metallocene and half-sandwich catalysts were determined on the basis of composition data with linear graphical methods: Aside from r1 and r2, values for r11 and r21 could be determined in the case of alternating copolymerizations. In this connection, r21 differs significantly from catalyst to catalyst and reflects the different tendency of each catalyst to produce copolymers with an alternating monomer sequence. The maximum norbornene contents in the copolymer could be achieved by use of sterically less hindered metallocene catalysts. As an exception to this, the half-sandwich catalysts produced copolymers with surprisingly low norbornene contents. PMID:9680398

  15. 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.

  16. Kinetic Turbulence

    NASA Astrophysics Data System (ADS)

    Howes, Gregory G.

    The weak collisionality typical of turbulence in many diffuse astrophysical plasmas invalidates an MHD description of the turbulent dynamics, motivating the development of a more comprehensive theory of kinetic turbulence. In particular, a kinetic approach is essential for the investigation of the physical mechanisms responsible for the dissipation of astrophysical turbulence and the resulting heating of the plasma. This chapter reviews the limitations of MHD turbulence theory and explains how kinetic considerations may be incorporated to obtain a kinetic theory for astrophysical plasma turbulence. Key questions about the nature of kinetic turbulence that drive current research efforts are identified. A comprehensive model of the kinetic turbulent cascade is presented, with a detailed discussion of each component of the model and a review of supporting and conflicting theoretical, numerical, and observational evidence.

  17. 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. PMID:24654385

  18. Kinetics and mechanism of X + ClNO yields XCl + NO (X = Cl, F, Br, OH, O, N) from 220 to 450 K. Correlation of reactivity and activation energy with electron affinity of X

    SciTech Connect

    Abbatt, J.P.D.; Toohey, D.W.; Fenter, F.F.; Stevens, P.S.; Brune, W.H.; Anderson, J.G. )

    1989-02-09

    The rate constants for a series of radical reactions with ClNO, X + ClNO {yields} products where X = Cl, F, Br, OH, O, N, have been measured as a function of temperature in discharge flow systems at pressures between 1 and 2 Torr of helium buffer gas. Radicals were detected by resonance fluorescence (X = Cl, Br, OH, O), laser magnetic resonance (X = OH), and chemical conversion/resonance fluorescence (X = F, N). The rate constants, with units of cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} and to 95% confidence level, are for Cl + ClNO {yields} Cl{sub 2} + NO, ((6.6 {plus minus} 1.2) {times} 10{sup {minus}11}) e{sup (128{plus minus}46)/T}; for F + ClNO {yields} FCl + NO, ((1.4 {plus minus} 0.4) {times} 10{sup {minus}10}) e{sup ({minus}28{plus minus}84)/T}; for Br + ClNO {yields} BrCl + NO, ((1.5 {plus minus} 0.2) {times} 10{sup {minus}11}) e{sup ({minus}52{plus minus}43)/T}; for OH + ClNO {yields} ClOH + NO, ((9.0 {plus minus} 4.5) {times} 10{sup {minus}12}) e{sup ({minus}1130{plus minus}170)/T}; for OH + ClNO {yields} HONO + Cl, ((9.2 {plus minus} 6.5) {times} 10{sup {minus}14}) e{sup (240{plus minus}130)/T}; for O + ClNO {yields} ClO + NO, ((8.3 {plus minus} 0.9) {times} 10{sup {minus}12}) e{sup ({minus}1520{plus minus}35)/T}; and for N + ClNO {yields} NCl + NO, ((9.2 {plus minus} 2.2) {times} 10{sup {minus}12}) e{sup ({minus}2250{plus minus}90)/T}. Both the reaction activation energies and the logarithms of the room temperature rate constants are found to correlate strongly with the electron affinity of the radical in such a way that high electron affinity leads to enhanced reactivity. The reactivity trend is rationalized by a frontier orbital interaction dominated by the ease with which electron transfer from the ClNO molecule to the X radical can occur to stabilize a polar transition state, a mechanism shown to be widely prevalent in radical-molecule systems.

  19. Pyrolysis kinetics of waste PVC pipe.

    PubMed

    Kim, S

    2001-01-01

    The pyrolysis kinetics of waste PVC pipe was investigated with a thermal gravimetric analysis system at heating rates of 5, 10, and 30 degrees C/min in a nitrogen atmosphere. Freeman-Carroll method was employed to evaluate kinetic parameters. Two dominant peaks were observed on derivative gravimetric curves, hypothetically suggesting a two-stage apparent reaction model. The first-stage reaction was likely to be represented by stoichiometric reaction to yield volatiles (mainly HCl) and intermediates. The second-stage reaction might be described by thermal degradation of intermediates competitively into gas, liquid, and solid by-products. Quasi-isothermal operations were introduced to verify the reaction types of the first and second reaction. The generation reaction of intermediates achieved at lower temperatures was carried out independently with their decomposition reaction at higher temperatures. The effects of additives on the pyrolysis kinetics of waste PVC pipe seem to be significant, especially on the first-stage reaction. The first-stage reaction was retarded. A merged peak at low temperatures was observed on the derivative thermogravimetry (DTG) curve instead of two peaks usually observed for that of pure PVC resin. The first peak on the DTG curve of pure PVC resin may shift more, resulting in the complete overlap of two peaks. The quantity of evolved HCl was likely to decrease because of interaction of metal components of stabilizers with either HCl or active chlorine atom or both. The final residual fraction increased as a result of pyrolysis of organic forms of additives to yield extra char. On the other hand, the second-stage reaction kinetics demonstrates a similar pattern to that of pure PVC resin, implying that the effects of additives may be less significant in comparison with that at the first-stage reaction. PMID:11530916

  20. 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. PMID:18025584

  1. The influence of CaCl{sub 2} on the kinetics of the reaction 1 tremolite + 3 calcite + 2 quartz {yields} 5 diopside + 3 CO{sub 2} + 1 H{sub 2}O. An experimental investigation

    SciTech Connect

    Winkler, U.; Luettge, A.

    1999-05-01

    The effects of temperature and CaCl{sub 2} concentration on the kinetics of this mineral reaction were studied experimentally in cold sealed pressure vessels. Results were obtained in 130 runs under conditions equivalent to medium pressure amphibolite facies. Experiments were performed with and without CaCl{sub 2} dissolved in a supercritical CO{sub 2} - H{sub 2}O mixture (CaCl{sub 2} = 0 to 0.5 mol/l water; X{sub CO{sub 2}} = 0.75 and 0.25). The pressure was 5 {+-} 0.05 kb, and the temperatures ranged from 630 to 720 C ({+-}3 C), with six different temperature oversteps of 13 up to 103 C above the equilibrium temperature at 617 C. Percent conversion, measured by CO{sub 2} production as a function of time for a period of up to 34 days (816 hrs), is presented, and the appropriate reaction rate constants (up to k = 5 x 10{sup {minus}8} mol/m{sup 2} sec) as well as the apparent activation energies (E{sub app} = 255--470 kJ/mol) are extracted from the measured data. The observed asymmetric sigmoidal shape of all conversion versus time curves indicates changes in the rate-limiting process during the reaction. The development of the overall kinetics as a result of the combination of the different sub-processes (dissolution, nucleation, and growth of reactants and product) are discussed. Analysis of the experimental results shows that the reaction rates obtained from a chloride-bearing fluid are an order of magnitude larger than those obtained from chloride-free experiments. The implications for natural systems are quite important, because their results suggest that reaction rates may indeed be much faster than originally expected. Additionally, there seems to be evidence that nucleation starts earlier and is increased in the presence of a fluid that has even a low chloride content.

  2. 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.

  3. Effect of driver impedance on dense plasma focus Z-pinch neutron yield

    NASA Astrophysics Data System (ADS)

    Sears, Jason; Link, Anthony; Schmidt, Andrea; Welch, Dale

    2014-12-01

    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.

  4. Inverse Kinetics

    Energy Science and Technology Software Center (ESTSC)

    2000-03-20

    Given the space-independent, one energy group reactor kinetics equations and the initial conditions, this prgram determines the time variation of reactivity required to produce the given input of flux-time data.

  5. Calculation of Kinetics Parameters for the NBSR

    SciTech Connect

    Hanson A. L.; Diamond D.

    2012-03-06

    The delayed neutron fraction and prompt neutron lifetime have been calculated at different times in the fuel cycle for the NBSR when fueled with both high-enriched uranium (HEU) and low-enriched uranium (LEU) fuel. The best-estimate values for both the delayed neutron fraction and the prompt neutron lifetime are the result of calculations using MCNP5-1.60 with the most recent ENDFB-VII evaluations. The best-estimate values for the total delayed neutron fraction from fission products are 0.00665 and 0.00661 for the HEU fueled core at startup and end-of-cycle, respectively. For the LEU fuel the best estimate values are 0.00650 and 0.00648 at startup and end-of-cycle, respectively. The present recommendations for the delayed neutron fractions from fission products are smaller than the value reported previously of 0.00726 for the HEU fuel. The best-estimate values for the contribution from photoneutrons will remain as 0.000316, independent of the fuel or time in the cycle.The values of the prompt neutron lifetime as calculated with MCNP5-1.60 are compared to values calculated with two other independent methods and the results are in reasonable agreement with each other. The recommended, conservative values of the neutron lifetime for the HEU fuel are 650 {micro}s and 750 {micro}s for the startup and end-of-cycle conditions, respectively. For LEU fuel the recommended, conservative values are 600 {micro}s and 700 {micro}s for the startup and end-of-cycle conditions, respectively. In all three calculations, the prompt neutron lifetime was determined to be longer for the end-of-cycle equilibrium condition when compared to the startup condition. The results of the three analyses were in agreement that the LEU fuel will exhibit a shorter prompt neutron lifetime when compared to the HEU fuel.

  6. Kinetic analysis for macrocyclizations involving anionic template at the transition state.

    PubMed

    Mart-Centelles, Vicente; Burguete, M Isabel; Luis, Santiago V

    2012-01-01

    Several kinetic models for the macrocyclization of a C? 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. PMID:22666148

  7. Computed tomography assessment of cerebral perfusion using a distributed parameter tracer kinetics model: validation with H(2)((15))O positron emission tomography measurements and initial clinical experience in patients with acute stroke.

    PubMed

    Bisdas, Sotirios; Donnerstag, Frank; Berding, Georg; Vogl, Thomas J; Thng, Choon Hua; Koh, Tong San

    2008-02-01

    We describe a distributed parameter (DP) model for tracer kinetic analysis in brain and validate the derived perfusion values with positron emission tomography (PET) scans. The proposed model is applied on actual clinical cases of hemispheric stroke. Nine patients with experienced transient ischaemic attack or minor stroke and a stenosis of the internal carotid artery were referred for computed tomography (CT) and PET imaging. The applicability of the DP model in clinical practice was tested in seven patients with acute stroke who received a baseline perfusion CT study and a noncontrast follow-up CT study after 2.4+/-1.8 days. The mean blood flow (F) value for all patients with carotid stenosis in the pooled data (54 regions of interest (ROIs)) was 37.9+/-11.2 mL/min per 100 g in perfusion CT and 35.6+/-9.8 mL/min per 100 g in perfusion PET imaging [r=0.77 (P=0.00)]. Regression analysis of the pooled ROIs for every patient revealed significant correlation between F values in seven patients [r=0.50 to 0.79 (r(2)-values ranged from 0.45 to 0.79), (0.01 < or = P < or = 0.05)]. Parametric maps that corresponded to all physiologic parameters were generated for every perfusion CT in the patients with acute stroke using the DP model. The ischaemic area was better delineated in F, intravascular blood volume and lag time (t(lag)) maps. The correlation coefficient comparing the visually outlined regions of abnormality between the t(lag) parametric map and the follow-up CT scans was 0.81 (P=0.003). In conclusion, DP physiological model using more realistic pharmacokinetics is feasible in dynamic contrast-enhanced CT of the brain in patients with acute and chronic cerebrovascular disease. PMID:17593946

  8. 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.

  9. Kinetic and stoichiometric characterization of a fixed biofilm reactor by pulse respirometry.

    PubMed

    Ordaz, Alberto; Oliveira, Catarina S; Quijano, Guillermo; Ferreira, Eugenio C; Alves, Madalena; Thalasso, Frdric

    2012-01-01

    An in situ respirometric technique was applied to a sequential biofilm batch reactor treating a synthetic wastewater containing acetate. In this reactor, inoculated with mixed liquor from a wastewater plant, unglazed ceramic tiles were used as support media while maintaining complete mixing regime. A total of 8 kinetic and stoichiometric parameters were determined by in situ pulse respirometry; namely substrate oxidation yield, biomass growth yield, storage yield, storage growth yield, substrate affinity constant, storage affinity constant, storage kinetic constant and maximum oxygen uptake rate. Additionally, biofilm growth was determined from support media sampling showing that the colonization process occurred during the first 40 days, reaching an apparent steady-state afterward. Similarly, most of the stoichiometric and kinetic parameters were changing over time but reached steady values after day 40. During the experiment, the respirometric method allowed to quantify the amount of substrate directed to storage, which was significant, especially at substrate concentration superior to 30mg CODL(-1). The Activated Sludge Model 3 (ASM3), which is a model that takes into account substrate storage mechanisms, fitted well experimental data and allowed confirming that feast and famine cycles in SBR favor storage. These results also show that in situ pulse respirometry can be used for fixed-bed reactors characterization. PMID:22100265

  10. Kinetic study of Acid hydrolysis of rice straw.

    PubMed

    Sarkar, Nibedita; Aikat, Kaustav

    2013-01-01

    Rice straw is a renewable, cheap, and abundant waste in tropical countries. The pentose content of rice straw can be used as a substrate for many types of value-added products such as xylitol and biofuel. Dilute acid hydrolysis mainly releases pentose from rice straw. The objective of the study was to determine the effect of H2SO4 concentration and reaction time on the xylose production. The variation of the main product xylose with the reaction time was described by a kinetic model and kinetic parameters were calculated to describe the variation of the xylose production with time. The optimum yield (19.35?g/L) was obtained at 0.24?mol/L H2SO4 and 30 minutes. PMID:25969789

  11. Kinetic Study of Acid Hydrolysis of Rice Straw

    PubMed Central

    Sarkar, Nibedita; Aikat, Kaustav

    2013-01-01

    Rice straw is a renewable, cheap, and abundant waste in tropical countries. The pentose content of rice straw can be used as a substrate for many types of value-added products such as xylitol and biofuel. Dilute acid hydrolysis mainly releases pentose from rice straw. The objective of the study was to determine the effect of H2SO4 concentration and reaction time on the xylose production. The variation of the main product xylose with the reaction time was described by a kinetic model and kinetic parameters were calculated to describe the variation of the xylose production with time. The optimum yield (19.35?g/L) was obtained at 0.24?mol/L H2SO4 and 30 minutes. PMID:25969789

  12. Kinetics of batch fermentations for ethanol production with Zymomonas mobilis growing on Jerusalem Artichoke juice.

    PubMed

    Favela-Torres, E; Allais, J J; Baratti, J

    1986-06-01

    A flocculent strain of Zymomonas mobilis was used for ethanol production from Jerusalem Artichoke juice containing 113-245 g/L sugar in batch fermentation. The kinetic and yields parameters are calculated using a new method based on polynomial equations for the variation of biomass, ethanol, and sugar concentrations with time. The results show that. Z. mobilis can convert rapidly and efficiently Jerusalem Artichoke juice to ethanol. When a sugar concentration of 248 gL was used, 100 g/L ethanol was formed with an ethanol yield based on sugar utilized of 0.47 g/g (92% of theoretical LP). PMID:18555403

  13. Kinetics of batch fermentations for ethanol production with Zymomonas mobilis growing on Jerusalem artichoke juice

    SciTech Connect

    Favela-Torres, E.; Allais, J.J.; Baratti, J.

    1986-06-01

    A flocculent strain of Zymomonas mobilis was used for ethanol production from Jerusalem artichoke juice containing 113-245 g/l sugar in batch fermentation. The kinetic and yields parameters are calculated using a new method based on polynomial equations for the variation of biomass, ethanol, and sugar concentrations with time. The results show that Z. mobilis can convert rapidly and efficiently Jerusalem artichoke juice to ethanol. When a sugar concentraton of 248 g/l was used, 100g/l ethanol was formed with an ethanol yield based on sugar utilized of 0.47 g/g (92% of theoretical). 27 references.

  14. 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...

  15. 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.

  16. 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 R(adj) was shown to be more suitable in describing the kinetics of vanillin extraction. By fitting the parameters C(eq), k?, k?, and f, a kinetics model was constructed to describe vanillin extraction in terms of irradiation power, ethanol concentration, and extraction time. PMID:24295676

  17. A descriptive model for the kinetics of a homogeneous fluorometric immunoassay.

    PubMed

    Zuber, E; Rosso, L; Darbouret, B; Socquet, F; Mathis, G; Flandrois, J P

    1997-02-01

    A descriptive mathematical model was chosen to fit the antigen-antibody association kinetics of a new homogeneous immunometric assay for prolactin, involving time-resolved fluorescence detection (TRACE technology, Time Resolved Amplified Cryptate Emission). We paid special attention to the methodology and criteria applied, to yield a convenient and statistically valid model, designed to allow potential exploitation of kinetic information in the data processing of the assay. We compared specific parameterizations of an hyperbolic model, the Gompertz, and the monomolecular models on the basis of morphological considerations, a statistical analysis of fit, and an assessment of the parameters estimation quality, over a wide range of antigen concentrations. The monomolecular model gave the best fit, and the most precise and stable estimation of its parameters. The study of parameter properties confirmed this choice. PMID:9139047

  18. MAIZE YIELD POTENTIAL: CRITICAL PROCESSES AND SIMULATION MODELING IN A HIGH-YIELDING ENVIRONMENT

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Accurate parameters describing processes of maize (Zea mays L.) growth and grain yield production in high-yielding, irrigated conditions provide a system for studying grain yield potential in different environments. In this study we measured maize leaf area index (LAI), the light extinction coeffic...

  19. Kinetic modeling of kraft delignification of Eucalyptus globulus

    SciTech Connect

    Santos, A.; Rodriguez, F.; Gilarranz, M.A.; Moreno, D.; Garcia-Ochoa, F.

    1997-10-01

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

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

    PubMed

    No, 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. PMID:26574285

  1. Development of a kinetic model for alcohol synthesis over a cesium-promoted Cu/ZnO catalyst

    SciTech Connect

    Herman, R.G.; Klier, K. ); Smith, K.J. ); Young, C.W. )

    1991-01-01

    This paper reports on a kinetic reaction network developed for the synthesis of oxygenates from synthesis gave over Cs-promoted Cu/ZnO catalysts in a differential reaction regime. The most important carbon- carbon bond forming reactions of the model are linear growth by addition of an oxygenated C{sub 1} intermediate to an alcohol chain that yields linear alcohols and a {beta}-addition aldol condensation type mechanism between an oxygenated C{sub 1} intermediate and an aldehydic C{sub n} intermediate that yields 2-methyl-branched primary alcohols. The most important carbon-oxygen bond forming reaction is a methoxide addition, {eta}{sub 0}, that yields methyl esters. Estimates of the kinetic parameters show that the {beta} addition is faster than linear growth, which results in high selectivities to branched alcohols, i.e., 2-methyl-1- propanol.

  2. Chemical kinetics of geminal recombination

    SciTech Connect

    Levin, P.P.; Khudyakov, I.V.; Brin, E.F.; Kuz'min, V.A.

    1988-09-01

    The kinetics of geminal recombination of triplet radical pairs formed in photoreduction of benzophenone by p-cresol in glycerin solution was studied by pulsed laser photolysis. The experiments were conducted at several temperatures and in a constant magnetic field of H = 0.34 T. The parameters in six kinetic equations describing geminal recombination were determined with a computer. The values of the sums of the squares of the residual deviations of the approximation were obtained. It was found that the kinetics are best described by the functions proposed by Noyes and Shushin. It was shown that it is necessary to use the mutual diffusion coefficient of the radicals, which is significantly smaller than the sum of the estimations of the experimental values of the radical diffusion coefficients, for describing the kinetics due to the correlations of the molecular motions of the radicals in the cage.

  3. Precision measurement of the direct CP violation parameter. var epsilon. prime /. var epsilon. via the four K yields 2. pi. decay modes and a high sensitivity search for CP violating rare K sub L decays, Task J

    SciTech Connect

    Wah, Yau W.

    1992-04-01

    This report discusses the progress on the measurement of the direct CP violation parameter {var epsilon}{prime}/{var epsilon} and the rare KL decay. The progress has been as follows: (A) results from the complete E731 data set which was collected in the 1987/88 fixed target run; preparations for and the taking of the data for (B) E773 (CPT symmetry test) and (C) E799 (rare decay study); and finally (D) R D for a new detector to further study {var epsilon}{prime}/{var epsilon} and rate decays.

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

    PubMed

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

    1991-09-01

    The in vivo kinetic behavior of [11C]flumazenil ([11C]FMZ), a non-subtype-specific central benzodiazepine antagonist, is characterized using compartmental analysis with the aim of producing an optimized data acquisition protocol and tracer kinetic model configuration for the assessment of [11C]FMZ binding to benzodiazepine receptors (BZRs) in human brain. The approach presented is simple, requiring only a single radioligand injection. Dynamic positron emission tomography data were acquired on 18 normal volunteers using a 60- to 90-min sequence of scans and were analyzed with model configurations that included a three-compartment, four-parameter model, a three-compartment, three-parameter model, with a fixed value for free plus nonspecific binding; and a two-compartment, two-parameter model. Statistical analysis indicated that a four-parameter model did not yield significantly better fits than a three-parameter model. Goodness of fit was improved for three- versus two-parameter configurations in regions with low receptor density, but not in regions with moderate to high receptor density. Thus, a two-compartment, two-parameter configuration was found to adequately describe the kinetic behavior of [11C]FMZ in human brain, with stable estimates of the model parameters obtainable from as little as 20-30 min of data. Pixel-by-pixel analysis yields functional images of transport rate (K1) and ligand distribution volume (DV"), and thus provides independent estimates of ligand delivery and BZR binding. PMID:1651944

  5. 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.

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

    PubMed Central

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

    1978-01-01

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

  7. Kinetics of amino acid production from bean dregs by hydrolysis in sub-critical water.

    PubMed

    Zhu, Guangyong; Zhu, Xian; Fan, Qi; Wan, Xueliang

    2011-04-01

    Amino acids play an important physiological role in all life-forms and can be recovered from bean dregs waste using sub-critical water hydrolysis. This work deals with the hydrolysis kinetics of bean dregs. Kinetics was conducted in a temperature range of 200-240C using a 300-ml stainless steel batch reactor. Since the reaction kinetics in sub-critical water is very complicated, a simplified kinetic model to describe the hydrolysis of bean dregs is proposed: a single consecutive reaction. The differential equations resulting from the model were fit to experimental data to obtain kinetic rate constants. By means of the Arrhenius plot, the activation energy as well as the pre-exponential factor was determined. A good agreement between the simplified model and the experimental data was obtained. The kinetic parameters provided useful information for understanding the hydrolysis reaction of bean dregs. The experimental results show that the best hydrolysis technology is: reaction temperature 200C, reaction time 20 min. Under this condition, the total amino acid yield reaches 52.9%. Based on the results, this method could become an efficient method for bean dregs liquefaction, producing valuable amino acid. PMID:20830496

  8. 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 (45-55C), pH (4-5), initial sucrose concentration (ISC: 300-500g/L) and enzyme concentration (4-32 U/mL) were varied. A maximum FOS yield of 60% was observed at ISC 500g/L, pH 4.5 with enzyme activity 32 U/mL and at 55C. 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. PMID:26437965

  9. 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) 1011 exp(?10.62(0.66)/RT), k2 = 1.20(0.38) 1011 exp(?7.12(1.059)/RT) in the temperature range 293623 K (A/cm3 molecule1 s1, Ea/kJ mol1). 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 ?fH298(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 ?fH298(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 (?fH298(C2H5) = 119 2 kJ/mol) despite using two very different experimental techniques. PMID:24134055

  10. [Kinetic analysis of the chemotaxis of bacteria].

    PubMed

    Zaval'skiĭ, L Iu

    1988-01-01

    On the basis of a kinetic model of bacterial chemotactic movement the system of differential equations was reduced to describe the phenomenon of bacterial bonds migration. It follows that Keller-Segel equation is a private case of a more general "diffusion approximation" of the kinetic model. The functional parameters of the reduced equation for E. coli K-12 are estimated. PMID:3390483

  11. 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

  12. 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…

  13. Determining Enzyme Kinetics for Systems Biology with Nuclear Magnetic Resonance Spectroscopy

    PubMed Central

    Eicher, Johann J.; Snoep, Jacky L.; Rohwer, Johann M.

    2012-01-01

    Enzyme kinetics for systems biology should ideally yield information about the enzymes activity under in vivo conditions, including such reaction features as substrate cooperativity, reversibility and allostery, and be applicable to enzymatic reactions with multiple substrates. A large body of enzyme-kinetic data in the literature is based on the uni-substrate Michaelis-Menten equation, which makes unnatural assumptions about enzymatic reactions (e.g., irreversibility), and its application in systems biology models is therefore limited. To overcome this limitation, we have utilised NMR time-course data in a combined theoretical and experimental approach to parameterize the generic reversible Hill equation, which is capable of describing enzymatic reactions in terms of all the properties mentioned above and has fewer parameters than detailed mechanistic kinetic equations; these parameters are moreover defined operationally. Traditionally, enzyme kinetic data have been obtained from initial-rate studies, often using assays coupled to NAD(P)H-producing or NAD(P)H-consuming reactions. However, these assays are very labour-intensive, especially for detailed characterisation of multi-substrate reactions. We here present a cost-effective and relatively rapid method for obtaining enzyme-kinetic parameters from metabolite time-course data generated using NMR spectroscopy. The method requires fewer runs than traditional initial-rate studies and yields more information per experiment, as whole time-courses are analyzed and used for parameter fitting. Additionally, this approach allows real-time simultaneous quantification of all metabolites present in the assay system (including products and allosteric modifiers), which demonstrates the superiority of NMR over traditional spectrophotometric coupled enzyme assays. The methodology presented is applied to the elucidation of kinetic parameters for two coupled glycolytic enzymes from Escherichia coli (phosphoglucose isomerase and phosphofructokinase). 31P-NMR time-course data were collected by incubating cell extracts with substrates, products and modifiers at different initial concentrations. NMR kinetic data were subsequently processed using a custom software module written in the Python programming language, and globally fitted to appropriately modified Hill equations. PMID:24957764

  14. 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 distance of a non-pressurized riser, and can increase casting yield by decreasing the required number of risers. All case studies for this projects were completed and compiled into an SFSA Technical Report that is submitted part of this Final Report

  15. Arbitrary amplitude kinetic Alfven solitary waves and double layers in a non-Maxwellian plasma

    SciTech Connect

    Gogoi, Runmoni; Khan, Manoranjan

    2010-11-15

    To investigate the existence of kinetic Alfven wave solitons, warm adiabatic ions and kappa distributed electrons are considered in a magnetized plasma. The kappa distribution (having the spectral index {kappa}) is a velocity distribution that has a high energy tail but approaches the Maxwellian when {kappa}{yields}{infinity}. In this work, by using the Sagdeev pseudopotential method, an exact analytical expression for arbitrary amplitude solitary kinetic Alfven wave is derived. For different sets of plasma parameter values, the Sagdeev potential {Psi} ({phi}) has been calculated numerically. It is found that the spectral index {kappa} plays a significant role in determining the shape and size of the solitary waves and double layers. Also, it is observed that both compressive solitary waves and double layers exist depending on the values of different plasma parameters.

  16. 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.

  17. Direct reconstruction of cardiac PET kinetic parametric images using a preconditioned conjugate gradient approach

    PubMed Central

    Rakvongthai, Yothin; Ouyang, Jinsong; Guerin, Bastien; Li, Quanzheng; Alpert, Nathaniel M.; El Fakhri, Georges

    2013-01-01

    Purpose: Our research goal is to develop an algorithm to reconstruct cardiac positron emission tomography (PET) kinetic parametric images directly from sinograms and compare its performance with the conventional indirect approach. Methods: Time activity curves of a NCAT phantom were computed according to a one-tissue compartmental kinetic model with realistic kinetic parameters. The sinograms at each time frame were simulated using the activity distribution for the time frame. The authors reconstructed the parametric images directly from the sinograms by optimizing a cost function, which included the Poisson log-likelihood and a spatial regularization terms, using the preconditioned conjugate gradient (PCG) algorithm with the proposed preconditioner. The proposed preconditioner is a diagonal matrix whose diagonal entries are the ratio of the parameter and the sensitivity of the radioactivity associated with parameter. The authors compared the reconstructed parametric images using the direct approach with those reconstructed using the conventional indirect approach. Results: At the same bias, the direct approach yielded significant relative reduction in standard deviation by 12%29% and 32%70% for 50 106 and 10 106 detected coincidences counts, respectively. Also, the PCG method effectively reached a constant value after only 10 iterations (with numerical convergence achieved after 4050 iterations), while more than 500 iterations were needed for CG. Conclusions: The authors have developed a novel approach based on the PCG algorithm to directly reconstruct cardiac PET parametric images from sinograms, and yield better estimation of kinetic parameters than the conventional indirect approach, i.e., curve fitting of reconstructed images. The PCG method increases the convergence rate of reconstruction significantly as compared to the conventional CG method. PMID:24089922

  18. Kinetically Trapped Tetrahedral Cages via Alkyne Metathesis.

    PubMed

    Lee, Semin; Yang, Anna; Moneypenny, Timothy P; Moore, Jeffrey S

    2016-02-24

    In dynamic covalent synthesis, kinetic traps are perceived as disadvantageous, hindering the system from reaching its thermodynamic equilibrium. Here we present the near-quantitative preparation of tetrahedral cages from simple tritopic precursors using alkyne metathesis. While the cages are the presumed thermodynamic sink, we experimentally demonstrate that the products no longer exchange their vertices once they have formed. The example reported here illustrates that kinetically trapped products may facilitate high yields of complex products from dynamic covalent synthesis. PMID:26854552

  19. Soybean Yield and Genetics

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Seed yield is both the most important soybean breeding objective and the most challenging. The increase in the number of breeders and the increasing application of technology has done little to increase the rate of yield improvement over the past 20 years, but current rapid changes in technology and...

  20. 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. PMID:25381606

  1. 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.

  2. 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. PMID:18401758

  3. Reaction Kinetics of the Hydrothermal Treatment of Lignin

    NASA Astrophysics Data System (ADS)

    Zhang, Bo; Huang, Hua-Jiang; Ramaswamy, Shri

    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.

  4. 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. PMID:26364230

  5. 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. PMID:12861621

  6. Kinetics of reactive wetting

    SciTech Connect

    Yost, F.G.

    2000-04-14

    The importance of interfacial processes in materials joining has a long history. A significant amount of work has suggested that processes collateral to wetting can affect the extent of wetting and moderate or retard wetting rate. Even very small additions of a constituent, known to react with the substrate, cause pronounced improvement in wetting and are exploited in braze alloys, especially those used for joining to ceramics. In the following a model will be constructed for the wetting kinetics of a small droplet of metal containing a constituent that diffuses to the wetting line and chemically reacts with a flat, smooth substrate. The model is similar to that of Voitovitch et al. and Mortensen et al. but incorporates chemical reaction kinetics such that the result contains both diffusion and reaction kinetics. The model is constructed in the circular cylinder coordinate system, satisfies the diffusion equation under conditions of slow flow, and considers diffusion and reaction at the wetting line to be processes in series. This is done by solving the diffusion equation with proper initial and boundary conditions, computing the diffusive flux at the wetting line, and equating this to both the convective flux and reaction flux. This procedure is similar to equating the current flowing in components of a series circuit. The wetting rate will be computed versus time for a variety of diffusion and reaction conditions. A transition is observed from nonlinear (diffusive) to linear (reactive) behavior as the control parameters (such as the diffusion coefficient) are modified. This is in agreement with experimental observations. The adequacy of the slow flow condition, used in this type of analysis, is discussed and an amended procedure is suggested.

  7. 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 quantitative agreement with experiment.

  8. Dose dependent oxidation kinetics of lipids in fish during irradiation processing

    NASA Astrophysics Data System (ADS)

    Tükenmez, İbrahi˙m.; Ersen, M. Sitki; Bak.¨oǦlu, A. Tayfur; Bi˙çer, Ahmet; Pamuk, Veci˙h.İ

    1997-10-01

    Kinetic aspects of the development of lipid oxidation in complex foods as fish in the course of irradiation were analyzed with respect to the associated formation of malonaldehyde (MA) through the reactions modified so as to be consistent with those in complex foods as fish. Air-packed anchovy ( Engraulis encrasicholus) samples in polyethylene pouches were irradiated at the doses of 1, 2, 5, 10, 15, 20 and 25 kGy at 20°C in a Cs-137 gamma irradiator of 1.806 kGy/h dose rate. Immediately after each irradiation, MA contents of irradiated and unirridiated samples were determined by thiobarbituric acid test. Based on the MA formation, a kinetic model to simulate the apparent oxidation of lipid in fish as a function of irradiation dose was derived from the rate equations consistent with modified reactions. Kinetic parameters and simulation were related to conditions of lipid oxidation, and associated rancidity state of fish with respect to the doses applied in different irradiation-preservation processes. Numerical values of kinetic parameters based on the MA formation were found as a threshold dose of 0.375 kGy, an apparent yield of 1.871 μmol/kg kGy, and a maximum attainable concentration of 15.853 μmol/kg which may be used for process control and dosimetry.

  9. Argentina wheat yield model

    NASA Technical Reports Server (NTRS)

    Callis, S. L.; Sakamoto, C.

    1984-01-01

    Five models based on multiple regression were developed to estimate wheat yields for the five wheat growing provinces of Argentina. Meteorological data sets were obtained for each province by averaging data for stations within each province. Predictor variables for the models were derived from monthly total precipitation, average monthly mean temperature, and average monthly maximum temperature. Buenos Aires was the only province for which a trend variable was included because of increasing trend in yield due to technology from 1950 to 1963.

  10. Argentina soybean yield model

    NASA Technical Reports Server (NTRS)

    Callis, S. L.; Sakamoto, C.

    1984-01-01

    A model based on multiple regression was developed to estimate soybean yields for the country of Argentina. A meteorological data set was obtained for the country by averaging data for stations within the soybean growing area. Predictor variables for the model were derived from monthly total precipitation and monthly average temperature. A trend variable was included for the years 1969 to 1978 since an increasing trend in yields due to technology was observed between these years.

  11. Argentina corn yield model

    NASA Technical Reports Server (NTRS)

    Callis, S. L.; Sakamoto, C.

    1984-01-01

    A model based on multiple regression was developed to estimate corn yields for the country of Argentina. A meteorological data set was obtained for the country by averaging data for stations within the corn-growing area. Predictor variables for the model were derived from monthly total precipitation, average monthly mean temperature, and average monthly maximum temperature. A trend variable was included for the years 1965 to 1980 since an increasing trend in yields due to technology was observed between these years.

  12. Relativistic nonextensive kinetic theory

    NASA Astrophysics Data System (ADS)

    Hamity, Victor H.; Barraco, Daniel E.

    2000-07-01

    We present, in a coherent rigorous way, a generalization of the relativistic kinetic theory of particles that includes the monoparametric (parameter q) family of thermal equilibrium distributions of Tsallis thermostatistics. The q-depending entropy function leads to a local distribution function with a well-defined generalized temperature (not depending on q) but with other quantities such as the energy density, pressure, particle number density, etc., depending on q. In general, this extension forms the basis for relativistic thermodynamics of equilibrium and nonequilibrium transport processes that includes nonextensivity. Astrophysics and cosmology are two of the areas where Tsallis theory may find important applications. This is due to the nonextensive thermodynamical behaviour associated with the long range of gravitational interaction. Thus, a relativistic nonextensive kinetic theory may be appropriate for the treatment of a number of real systems, like the system of galaxies, hot gases of particles and plasmas. Also, it may be used to study a number of interesting problems in cosmology, like, for instance, the distribution of bubbles sizes, and consequently the level of inhomogeneity generated, in a scalar-tensor theory of gravity, as well as to apply it to another constituents, if we could extend the known history of the universe back to quark/hadron transition and electroweak phase transition.

  13. Saffman-Taylor fingers with kinetic undercooling.

    PubMed

    Gardiner, Bennett P J; McCue, Scott W; Dallaston, Michael C; Moroney, Timothy J

    2015-02-01

    The mathematical model of a steadily propagating Saffman-Taylor finger in a Hele-Shaw channel has applications to two-dimensional interacting streamer discharges which are aligned in a periodic array. In the streamer context, the relevant regularization on the interface is not provided by surface tension but instead has been postulated to involve a mechanism equivalent to kinetic undercooling, which acts to penalize high velocities and prevent blow-up of the unregularized solution. Previous asymptotic results for the Hele-Shaw finger problem with kinetic undercooling suggest that for a given value of the kinetic undercooling parameter, there is a discrete set of possible finger shapes, each analytic at the nose and occupying a different fraction of the channel width. In the limit in which the kinetic undercooling parameter vanishes, the fraction for each family approaches 1/2, suggesting that this "selection" of 1/2 by kinetic undercooling is qualitatively similar to the well-known analog with surface tension. We treat the numerical problem of computing these Saffman-Taylor fingers with kinetic undercooling, which turns out to be more subtle than the analog with surface tension, since kinetic undercooling permits finger shapes which are corner-free but not analytic. We provide numerical evidence for the selection mechanism by setting up a problem with both kinetic undercooling and surface tension and numerically taking the limit that the surface tension vanishes. PMID:25768606

  14. 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.

  15. Modeling recovery and recrystallization kinetics in cold-rolled Ti-Nb stabilized interstitial-free steel

    NASA Astrophysics Data System (ADS)

    Mukunthan, K.; Hawbolt, E. B.

    1996-11-01

    The recovery and recrystallization kinetics in an 80 pct cold-rolled Ti-Nb stabilized interstitial-free (IF) steel have been characterized for isothermal (500 to 760 °C) and continuous heating (0.025 °C s-1 to 20.2 °C s-1 annealing. Isothermal recovery kinetics, as monitored by {220} X-ray peak resolution measurements, were described using a semiempirical logarithmic equation. The IF steel recovered relatively easily, with approximately 45 to 60 pct of the total peak resolution occurring prior to the onset of recrystallization. An iterative procedure was adopted to separate the diffraction effects associated with the concurrent recovery and recrystallization processes. Microstructural observations indicated that the recrystallization event was heterogeneous, with preferential nucleation and early site saturation at grain boundaries in the cold-rolled material. Isothermal recrystallization kinetics, determined by quantitative metallography, were described using the Johnson-Mehl-Avrami-Kol-mogorov (JMAK) and Speich-Fisher (SF) relationships. An alternative description of the isothermal recrystallization kinetics was provided by the experimentally determined microstructural path function, independent of the thermal path, and an empirical kinetic function describing the interface averaged growth rate. The kinetic analysis yielded an apparent recrystallization activation energy of 501.7 kJ/mole, indicating severe retardation of recrystallization in IF steels. Recovery and recrystallization kinetics during continuous heating have been modeled using the isothermal kinetic parameters, assuming the validity of the principle of additivity. The results were validated by experimental measurements obtained at heating rates simulating both batch and continuous annealing. Although the Scheil additivity equation overestimated the recrystallization start time for continuous heating conditions, the associated higher temperature and more rapid initial recrystallization resulted in similar overall kinetics.

  16. Effect of annealing on the kinetic properties and band parameters of Hg{sub 1?x?y}Cd{sub x}Eu{sub y}Se semiconductor crystals

    SciTech Connect

    Kovalyuk, T. T. Maistruk, E. V.; Maryanchuk, P. D.

    2014-12-15

    The results of studies of the kinetic properties of Hg{sub 1?x?y}Cd{sub x}Eu{sub y}Se semiconductor crystals in the ranges of temperatures T = 77300 K and magnetic fields H = 0.55 kOe before and after heat treatment of the samples in Se vapors are reported. It is established that annealing of the samples in Se vapors induces a decrease in the electron concentration. From the concentration dependence of the electron effective mass at the Fermi level, the band gap, the matrix element of interband interaction, and the electron effective mass at the bottom of the conduction band are determined.

  17. Kinetics of thermal decomposition of surrogate solid wastes

    SciTech Connect

    Missoum, A.; Gupta, A.K.; Chen, J.; Keating, E.L.

    1996-12-31

    Decomposition behavior of different materials in a controlled environment at different heating rates are presented. The surrogate materials used are cellulose, polyethylene, polystyrene, polypropylene, nylon and bisphenol-A-polycarbonate. A series of tests were performed using a Perkin-Elmer 7 series thermal analysis system. Two heating rates of 10 C/minute and 100 C/minute were used. The temperature dependence and mass load characteristics of materials was obtained and used to obtain Arrhenius kinetic parameters and therefore the decomposition rates under defined conditions of pressure, temperature, environment, heating rate and waste composition. This information is helpful in characterizing and understanding the thermal decomposition properties of these materials during their thermal destruction. The decomposition rates are affected by the heating rate. The higher the heating rate the faster the decomposition. The results show that an increase in heating rate shifted thermal decomposition to higher temperatures and that the temperature at which maximum devolatilization began and ended was affected by heating rate. The kinetic parameters were calculated and the char yield from the different samples was less than 2% by weight except for polycarbonate which was around 5%. The remaining char in nylon and polycarbonate is attributed to the inert impurities in these materials. The thermal decomposition of the materials studied here could be related to their composition. It was found that polyethylene, polypropylene and polycarbonate have comparable decomposition rates over the same temperature range. Cellulose has the lowest decomposition rate and polystyrene has the highest.

  18. Pharmacokinetics of progesterone in lactating dairy cows: gaining some insights into the metabolism from kinetic modeling.

    PubMed

    Turino, L N; Mariano, R N; Cabrera, M I; Scndolo, D E; Maciel, M G; Grau, R J A

    2010-03-01

    Progesterone pharmacokinetics were analyzed for plasma hormone concentrations ranging from linear to saturated metabolism in lactating Holstein cows with differing daily milk yields. The adequacy of 2-coupled first-order (bi-exponential equation), hyperbolic (Michaelis-Menten equation), and sigmoidal (Hill equation) kinetic models to describe the experimental progesterone pharmacokinetic profiles was examined on a statistical basis. After nonlinear regression and statistical analysis of the data-fitting capability, a simple one-compartment model based on Hill equation proved to be most adequate. This model indicates an enzyme-catalyzed metabolism of progesterone involving cooperative substrate-binding sites, resulting from allosteric effects that yield a sigmoidal saturation rate curve. Kinetic parameters were estimated for 2 groups of lactating Holstein cows with different daily milk yields. We found, for the first time, a remarkable quantitative agreement of the Hill coefficient value with that reported in pharmacokinetic studies involving cytochrome P450, family 3, subfamily A (CYP3A)-mediated reactions in other mammals, humans included. It seems that positive cooperativity makes enzymes much more sensitive to plasma progesterone concentration, and their activities can undergo significant changes in a narrow range of concentration as characteristic of sigmoidal behavior. Therefore, the values of classical pharmacokinetic parameters, such as the elimination constant, half-life, and clearance rate, were found to be highly dependent on the plasma progesterone concentration. PMID:20172219

  19. Nonphotochemical quenching of excitation energy in photosystem II. A picosecond time-resolved study of the low yield of chlorophyll a fluorescence induced by single-turnover flash in isolated spinach thylakoids.

    PubMed

    Vasil'ev, S; Bruce, D

    1998-08-01

    Chlorophyll a fluorescence emission is widely used as a noninvasive measure of a number of parameters related to photosynthetic efficiency in oxygenic photosynthetic organisms. The most important component for the estimation of photochemistry is the relative increase in fluorescence yield between dark-adapted samples which have a maximal capacity for photochemistry and a minimal fluorescence yield (F0) and light-saturated samples where photochemistry is saturated and fluorescence yield is maximal (Fm). However, when photosynthesis is saturated with a short (less than 50 micro(s)) flash of light, which induces only one photochemical turnover of photosystem II, the maximal fluorescence yield is significantly lower (Fsat) than when saturation is achieved with a millisecond duration multiturnover flash (Fm). To investigate the origins of the difference in fluorescence yield between these two conditions, our time-resolved fluorescence apparatus was modified to allow collection of picosecond time-resolved decay kinetics over a short time window immediately following a saturating single-turnover flash (Fsat) as well as after a multiturnover saturating pulse (Fm). Our data were analyzed with a global kinetic model based on an exciton radical pair equilibrium model for photosystem II. The difference between Fm and Fsat was modeled well by changing only the rate constant for quenching of excitation energy in the antenna of photosystem II. An antenna-based origin for the quenching was verified experimentally by the observation that addition of the antenna quencher 5-hydroxy-1,4-naphthoquinone to thylakoids under Fm conditions resulted in decay kinetics and modeled kinetic parameters very similar to those observed under Fsat conditions in the absence of added quinone. Our data strongly support the origin of low fluorescence yield at Fsat to be an antenna-based nonphotochemical quenching of excitation energy in photosystem II which has not usually been considered explicitly in calculations of photochemical and nonphotochemical quenching parameters. The implications of our data with respect to kinetic models for the excited-state dynamics of photosystem II and the practical applications of the fluorescence yield parameters Fm and Fsat to calculations of photochemical yield are discussed. PMID:9693000

  20. Science Yield Modeling with EXOSIMS

    NASA Astrophysics Data System (ADS)

    Garrett, Daniel; Savransky, Dmitry

    2016-01-01

    Accurately modeling science yield of an exoplanet direct imaging mission to build confidence in the achievement of science goals can be almost as complicated as designing the mission itself. It is challenging to compare science simulation results and systematically test the effects of changing instrument or mission designs. EXOSIMS (Exoplanet Open-Source Imaging Mission Simulator) addresses this by generating ensembles of mission simulations for exoplanet direct imaging missions to estimate distributions of science yield. EXOSIMS consists of stand-alone modules written in Python which may be individually modified without requiring modifications to the code elsewhere. This structure allows for user driven systemic exploration of the effects of changing designs on the estimated science yield.The modules of EXOSIMS are classified as either input or simulation modules. Input modules contain specific mission design parameters and functions. These include Planet Population, Star Catalog, Optical System, Zodiacal Light, Planet Physical Model, Observatory, Time Keeping, and Post-Processing. Simulation modules perform tasks requiring input from one or more input modules as well as calling functions from other simulation modules. These include Completeness, Target List, Simulated Universe, Survey Simulation, and Survey Ensemble. The required parameters and functionality of each of these modules is defined in the documentation for EXOSIMS.EXOSIMS is available to the public at https://github.com/dsavransky/EXOSIMS. Included in the documentation is an interface control document which defines the required inputs and outputs to each input and simulation module. Future development of EXOSIMS is intended to be community-driven. Mission planners and instrument designers may quickly write their own modules, following the guidelines in the interface control document, and drop them directly into the code without making additional modifications elsewhere. It is expected that EXOSIMS will be highly useful for designing and planning future exoplanet direct imaging missions.

  1. Waste lubricating oil removal in a batch reactor by mixed bacterial consortium: a kinetic study.

    PubMed

    Bhattacharya, Munna; Guchhait, Sugata; Biswas, Dipa; Datta, Sriparna

    2015-11-01

    The growth kinetics and biodegradation of two waste lubricating oil samples including waste engine oil (WEO) and waste transformer oil (WTO) were studied using pure isolates and mixed culture of Ochrobactrum sp. C1 and Bacillus sp. K1. The mixed culture significantly influenced degradation efficiency of the pure isolates through bioaugmentation process. In particular, the mixed culture was capable of growing on various n-alkanes and polycyclic aromatic hydrocarbons and was able to tolerate unusually high concentrations of waste lubricants (WEO-86.0 g/L and WTO-81.5 g/L). The initial concentration of waste lubricating oils has been varied in the range of 1-10 % (v/v). Under this experimental range, the bacterial growth has been observed to follow Haldane-type kinetics characterizing the presence of substrate inhibition. Haldane model was used to fit the exponential growth data and the following kinetic parameters were obtained: μ max = 0.078 h(-1), K S = 23.101 g/L, K i = 43.844 g/L for WEO; and μ max = 0.044 h(-1), K S = 10.662 g/L, K i = 58.310 g/L for WTO. The values of intrinsic kinetic parameters, like specific growth rate μ max, half saturation constant, K S, inhibition constant, K i and the maximum substrate concentration, S max and growth yield coefficient Y x/s , have been determined using each model hydrocarbon and their mixture as limiting substrate. Relative changes in the values of the kinetic parameters have been correlated to the number of carbon atoms present in n-alkanes. The metabolites from degradation of model hydrocarbon compounds have been identified by GC-MS to elucidate the possible pathway of waste lubricating oil degradation process. PMID:26271337

  2. Arbitrary amplitude kinetic Alfven solitons in a plasma with a q-nonextensive electron velocity distribution

    SciTech Connect

    Liu, Y.; Liu, S. Q.; Dai, B.

    2011-09-15

    Arbitrary amplitude solitary kinetic Alfven waves (KAWs) in a plasma with q-nonextensive electrons are investigated by the conventional Sagdeev pseudopotential method, through which the existence of solitary KAWs is analyzed theoretically and numerically. It is shown only solitons with density hump can exist, the amplitude of which depends sensitively on the parameter q and the plasma {beta}. There is an upper limit for the amplitude of solitary wave which decreases with the increase of q and {beta}. The results obtained in the framework of Maxwellian distribution are reproduced when q {yields} 1.

  3. Chemical and Biological Kinetics

    NASA Astrophysics Data System (ADS)

    Emanuel', N. M.

    1981-10-01

    Examples of the application of the methods and ideas of chemical kinetics in various branches of chemistry and biology are considered and the results of studies on the kinetics and mechanisms of autoxidation and inhibited and catalysed oxidation of organic substances in the liquid phase are surveyed. Problems of the kinetics of the ageing of polymers and the principles of their stabilisation are discussed and certain trends in biological kinetics (kinetics of tumour growth, kinetic criteria of the effectiveness of chemotherapy, problems of gerontology, etc.) are considered. The bibliography includes 281 references.

  4. Dimensional analysis for establishing the testing criteria of kinetic study with respirometry.

    PubMed

    Wu, Y S; Chiang, C F; Lu, C J

    2003-01-01

    The kinetic study of a microbial system requires the determination of kinetic parameters under a set of operating variables. Previous researchers indicated that initial conditions, such as S0/X0 and S0/KS may influence the reliability of the parameter estimation. However, little study has been done to identify the sensitivity of system variables to the parameter estimation. This study proposes a novel dimensional analysis and identifies six dimensionless groups: mu(m)/fw, kd/fw, Yg, S0/KS, KS/S0, and 1/(fw theta(c) - 1). By incorporating the SP-moving algorithm proposed by Wu and coworkers in 2001, an algorithm was proposed in this study to perform a sensitivity analysis on the six dimensionless groups. Results of this analysis reveal that S0/X0 is more sensitive than S0/KS, as also evidenced by the fact that gross growth yield (Yg) is sensitive and affecting S0/X0. The analysis also suggests that the theta(c)-based wasting frequency (fw theta(c)) is more sensitive than the daily wasting frequency (fw). A critical minimum value of 1.3 for S0/X0 and a maximum value of 0.1 for S0/KS were suggested to establish the testing criteria for the kinetic study under the respirometric conditions. PMID:12906300

  5. Yield gaps and yield relationships in US soybean production systems

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The magnitude of yield gaps (YG) (potential yield farmer yield) provides some indication of the prospects for increasing crop yield to meet the food demands of future populations. Quantile regression analysis was applied to county soybean [Glycine max (L.) Merrill] yields (1971 2011) from Kentuc...

  6. Cesium removal and kinetics equilibrium: Precipitation kinetics

    SciTech Connect

    Barnes, M.J.

    1999-12-17

    This task consisted of both non-radioactive and radioactive (tracer) tests examining the influence of potentially significant variables on cesium tetraphenylborate precipitation kinetics. The work investigated the time required to reach cesium decontamination and the conditions that affect the cesium precipitation kinetics.

  7. Optimization and kinetic modeling of cell-associated camptothecin production from an endophytic Fusarium oxysporum NFX06.

    PubMed

    Musavi, Sogra Fathima; Dhavale, Abhinandan; Balakrishnan, Raj Mohan

    2015-01-01

    The production of cell-associated camptothecin (CPT) from an endophytic fungus Fusarium oxysporum NFX06 isolated from Nothapodytes foetida and its kinetics studies were proposed. Response surface methodology (RSM) based on central composite design (CCD) was used to construct a model to describe the effects of substrate concentration. Three independent variables (dextrose, peptone, and MgSO4) were successfully employed to study the yield of CPT under submerged fermentation. The maximum yield of CPT obtained from CCD was about 598.0 ng/g biomass. The model-validated optimum predicted CPT yield and experimental CPT yield from the biomass were found to be 628.08 ng/g and 610.09 ng/g at the concentrations of dextrose 42.64 (g/L), peptone 9.23 (g/L), and MgSO4 0.26 (g/L) respectively. The predicted yield of CPT was 4.90% higher than the value obtained from CCD and 2.85% higher than the value obtained from experiment conducted at optimum conditions. The kinetic parameters, maximum specific growth rate μmax=1.212 day(-1), growth-associated CPT production coefficient (α=29.35 ng/g biomass), and non-growth-associated CPT production coefficient (β=0.03 ng CPT/g biomass-day) were obtained. The logistic model was found suitable to predict mycelial growth with a high determination coefficient (R2). Luedeking-Piret and modified Luedeking-Piret models were employed to represent the product kinetics and substrate consumption kinetics. A good concurrence was found between the experimental and predicted values, representing that the unstructured models were able to illustrate the fermentation profile effectively. PMID:24840354

  8. Estimates of explosive yield

    NASA Technical Reports Server (NTRS)

    1977-01-01

    Explosive yield as a function of propellant type and accident conditions was discussed along with the characteristics of propellant explosions. Three types of fuel-hypergolic, liquid oxygen-hydrocarbon, and liquid oxygen-liquid-hydrogen were considered. Data are also given on three modes (failure modes) of mixing: confinement by missile, confinement by ground surface, and high velocity impact.

  9. Kinetic efficiencies of stellar wind bubbles

    NASA Astrophysics Data System (ADS)

    van Buren, D.

    1986-07-01

    The theoretical fraction of a stellar wind's energy converted into the kinetic energy of an expanding swept-up shell is 20 percent in the classical theory of stellar wind bubbles. Observational estimates of this conversion factor based on the amount of ionized material in wind-swept shells about Wolf-Rayet stars generally yield results of 1 percent. If there is a substantial amount of neutral material in the shell, it will not be counted and the kinetic efficiency will be underestimated. Presented here is a dynamical estimate which accounts for this neutral material in deducing the kinetic efficiencies of stellar wind bubbles. Bubbles classified as wind-blown shells have kinetic efficiencies in line with theoretical expectations for energy-conserving evolution in a homogeneous medium. Ringlike nebulae have significantly lower efficiencies, probably because they have been 'poisoned' by the photoevaporation of clouds engulfed during evolution into a cloudy substrate.

  10. A liquefaction kinetic research needs assessment

    SciTech Connect

    Ferrance, J.; Warzinski, R.P.

    1996-12-31

    In February 1989, the Department of Energy released its assessment of the research needs for coal liquefaction. Under direct liquefaction, 4 of the 12 recommendations focused on developing models and determining kinetics. Reasons accompanying these recommendations stressed the need to understand the retrograde reactions, the reactions taking place as the coal is heated to the reaction temperature, and the effects Of coal types and solvent on liquefaction reactions. By understanding the liquefaction process better, suggestions for improving the process may be made. A good kinetic model would provide a basis for testing suggestions which would attempt to control reactions or effects in the development of improved liquefaction technologies. Brandes et al. suggests that a kinetic model could also possibly have a large impact on the economics of coal liquefaction! Cost factors which could be studied using a kinetic model include: coal preparations, reactor throughput, hydrogen usage, catalyst usage, yields and selectivity, and process control.

  11. Ozone mass transfer and kinetics experiments

    SciTech Connect

    Bollyky, L.J.; Beary, M.M.

    1981-12-01

    Experiments were conducted at the Hanford Site to determine the most efficient pH and temperature levels for the destruction of complexants in Hanford high-level defense waste. These complexants enhance migration of radionuclides in the soil and inhibit the growth of crystals in the evaporator-crystallizer. Ozone mass transfer and kinetics tests have been outlined for the determination of critical mass transfer and kinetics parameters of the ozone-complexant reaction.

  12. Effects of Experimental Conditions on Extraction Yield of Extracellular Polymeric Substances by Cation Exchange Resin

    PubMed Central

    Cho, Jinwoo; Hermanowicz, Slawomir W.; Hur, Jin

    2012-01-01

    Effects of experimental conditions on the yield of extracellular polymeric substances (EPSs) extraction by cation exchange resin (CER) were investigated using activated sludge flocs. The experimental variables included resin dose, extraction time, sample dilution, and storage time. An empirical model was proposed to describe the kinetics of extraction process. The extraction yield increases with the extraction time and CER dose until it reached the maximum amount of EPS extraction. The maximum yield of EPS was affected as well by the sample dilution, exhibiting a decreasing trend with increasing dilution factor. It was also found that the amount of EPS extracted from a raw sample depends on the storage time. Once EPS was extracted from the sample, however, the EPS keeps its original quantity under storage at 4C. Based on the model, the maximum amount of EPS extraction and yield rate could be estimated for different conditions. Comparing the model parameters allows one to quantitatively compare the extraction efficiencies under various extracting conditions. Based on the results, we recommend the original sample should be diluted with the volume ratio of above 1?:?2 and a raw sample should be treated quickly to prevent the reduction of sample homogeneity and original integrity. PMID:22919352

  13. Reaction {pi}N {yields} {pi}{pi}N near threshold

    SciTech Connect

    Frlez, E.

    1993-11-01

    The LAMPF E1179 experiment used the {pi}{sup 0} spectrometer and an array of charged particle range counters to detect and record {pi}{sup +}{pi}{sup 0}, {pi}{sup 0}p, and {pi}{sup +}{pi}{sup 0}p coincidences following the reaction {pi}{sup +}p {yields} {pi}{sup 0}{pi}{sup +}p near threshold. The total cross sections for single pion production were measured at the incident pion kinetic energies 190, 200, 220, 240, and 260 MeV. Absolute normalizations were fixed by measuring {pi}{sup +}p elastic scattering at 260 MeV. A detailed analysis of the {pi}{sup 0} detection efficiency was performed using cosmic ray calibrations and pion single charge exchange measurements with a 30 MeV {pi}{sup {minus}} beam. All published data on {pi}N {yields} {pi}{pi}N, including our results, are simultaneously fitted to yield a common chiral symmetry breaking parameter {xi} ={minus}0.25{plus_minus}0.10. The threshold matrix element {vert_bar}{alpha}{sub 0}({pi}{sup 0}{pi}{sup +}p){vert_bar} determined by linear extrapolation yields the value of the s-wave isospin-2 {pi}{pi} scattering length {alpha}{sub 0}{sup 2}({pi}{pi}) = {minus}0.041{plus_minus}0.003 m{sub {pi}}{sup {minus}1}, within the framework of soft-pion theory.

  14. Investigation of kinetic and thermodynamic characteristics of removal of tetracycline with sponge like, tannin based cryogels.

    PubMed

    Er?an, Mehtap; Ba?da, Esra; Ba?da, Efkan

    2013-04-01

    The removal of tetracycline (TC) from aqueous environment by new type of sorbents, tannin based cryogels (TAB CRGs) and control cryogels (CRGs) was studied in a batch system. The experimental parameters that affect the sorption of TC were optimized to achieve maximum removal yield. Prepared cryogels were characterized by SEM imaging, IR spectroscopy (ATR). Produced TAB cryogels have thin polymeric walls and interconnected large pores. The TAB cryogels are elastic and sponge like; its water content can easily be removed by only compressed with hand. The TAB cryogels restore their original shape and size within seconds after soaked in water. On the other, elasticity of blank CRG is lower. The Freundlich and Langmuir adsorption isotherms were conducted to deduce the mechanism of the process. The kinetics of TC adsorption was moderately fast and almost reached equilibrium in 150 min and the results followed pseudo-second-order kinetic model. PMID:23298591

  15. Kinetics and modeling of gas formation in the thermal decomposition of powdery cellulose and pine sawdust

    SciTech Connect

    Bilbao, R.; Arauzo, J.; Salvador, M.L.

    1995-03-01

    The formation of different gases in the thermal decomposition of cellulose and pine sawdust has been studied. The kinetic constants of CO{sub 2} and H{sub 2} formation in cellulose decomposition have been determined from results obtained in isothermal experiments. These kinetic constants have been taken as representative of pine sawdust decomposition at T > 292 C, and values for lower temperatures have bene obtained from isothermal experiments performed with pine sawdust. For both materials, a simple model without adjustable parameters has been applied that allows one to calculate the local temperature, solid conversion, and yield of each gas. The results obtained in dynamic experiments with heating rates ranging between 2 and 53 C/min have been compared with the theoretical results, and an acceptable agreement has been achieved.

  16. Improved Experimental and Computational Methodology for Determining the Kinetic Equation and the Extant Kinetic Constants of Fe(II) Oxidation by Acidithiobacillus ferrooxidans?

    PubMed Central

    Molchanov, Sharon; Gendel, Yuri; Ioslvich, Ilya; Lahav, Ori

    2007-01-01

    The variety of kinetics expressions encountered in the literature and the unreasonably broad range of values reported for the kinetics constants of Acidithiobacillus ferrooxidans underscore the need for a unifying experimental procedure and for the development of a reliable kinetics equation. Following an extensive and critical review of reported experimental techniques, a method based on batch pH-controlled kinetics experiments lasting less than one doubling time was developed for the determination of extant kinetics constants. The Fe(II) concentration in the experiments was measured by a method insensitive to Fe(III) interference. Kinetics parameters were determined by nonlinear fitting of the integrated form of the Monod equation to yield a KS of 31 4 mg Fe2+ liter?1 (mean standard deviation), a KP of 139 20 mg Fe3+ liter?1, and a ?max of 0.082 0.002 h?1. The corresponding kinetics equation was as follows: \\documentclass[10pt]{article} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{pmc} \\pagestyle{empty} \\oddsidemargin -1.0in \\begin{document} \\begin{equation*}\\frac{dS}{dt}= \\left \\left(-\\frac{0.082}{2.3{\\cdot}10^{7}}\\right) \\right \\frac{S{\\cdot}X}{31(1+\\displaystyle\\frac{P_{0}+S_{0}-S}{139})+S}\\end{equation*}\\end{document} where S represents the Fe(II) concentration in mg liter?1, P0 represents the initial Fe(III) concentration in mg liter?1, X represents the suspended bacterial cell concentration in cells ml?1, and t represents time in hours. The measured data fit this equation exceptionally well, with an R2 of >0.99. Fe(III) inhibition was found to be of a competitive nature. Contrary to previous reports, the results show that the concentration of Acidithiobacillus ferrooxidans cells has no affect on the kinetics constants. The kinetics equation can be considered applicable only to A. ferrooxidans cells grown under environmental conditions similar to those of the inoculum tested in the study. In contrast, the experimental and computational procedure is completely general and can be applied to A. ferrooxidans irrespective of the culture history. PMID:17261516

  17. Oxygen reduction at the platinum/Nafion{reg_sign} interface: Electrode kinetics and mass transport

    SciTech Connect

    Parthasarathy, A.

    1992-12-31

    Research in solid polymer electrolyte fuel cells is gaining momentum because of the prospects of attaining high energy efficiencies and power densities, essential for transportation and space applications. The most advanced solid polymer electrolytes for these fuel cells are the perfluorosulfonate ionomers (PFSIs) such as duPont`s Naflon and the Dow PFSIs. The high oxygen solubility, chemical stability, proton conductivity and permselectivity exhibited by Naflon and the Dow PFSI`s make them ideal candidates as electrolytes for fuel cells. Furthermore, the minimal anion adsorption on electrodes from fluorinated acids enhances oxygen reduction kinetics. The primary objectives of this work were to determine the concentration and diffusion coefficient of oxygen in Naflon, and the electrode kinetic parameters for the reduction of oxygen at the Pt/Nafion interface under totally solid-state conditions. Cyclic voltammetric and potentiostatic transient measurements were made at the Pt/Nafion interface. Slow sweep voltammograms yielded Tafel parameters for oxygen reduction. From the two-section Tafel, plot, the calculated exchange current densities were found to be higher than those obtained at any other Pt/acid interface. From an analysis of the transients, the values of oxygen solubility and diffusion coefficient in Naflon were determined. Electrochemical impedance spectroscopic (EIS) investigations were then used to study oxygen reduction under lower humidfication conditions. EIS clearly permits the discrimination of electrode kinetics, mass transport of O{sub 2} and the electrical characteristics of the membrane. A temperature-dependence study in the range of 30{degrees}C to 80{degrees}C yielded the activation energy for oxygen reduction at the Pt/Naflon interface. The diffusion coefficient of oxygen in Nafion increases with temperature while its solubility decreases. the pressure-dependence of oxygen reduction kinetics shows that the reaction order of oxygen is unity.

  18. Atmospheric Fluorescence Yield

    NASA Technical Reports Server (NTRS)

    Adams, James H., Jr.; Christl, M. J.; Fountain, W. F.; Gregory, J. C.; Martens, K.; Sokolsky, P.; 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 fluorescence from these showers. Accurate knowledge of the conversion from atmospheric fluorescence to energy loss by ionizing particles in the atmosphere is key to this technique. In this paper we discuss a small balloon-borne instrument to make the first in situ measurements versus altitude of the atmospheric fluorescence yield. The instrument can also be used in the lab to investigate the dependence of the fluorescence yield in air on temperature, pressure and the concentrations of other gases that present in the atmosphere. The results can be used to explore environmental effects on and improve the accuracy of cosmic ray energy measurements for existing ground-based experiments and future space-based experiments.

  19. Kinetic modeling of perchloroethylene coal desulfurization process

    SciTech Connect

    Lee, T.; Tartamella, T.L.; Lee, S.; Kulik, C.J.

    1994-12-31

    Batch extraction data was used to model the hybrid mechanism of chemical reaction and physical solvation involved in the perchloroethylene coal desulfurization process. Two models, pseudo-first order and second order, are presented to represent the extraction mechanism. Multiple parameter estimates have been found which minimize the model-data discrepancies. Novel methods have been devised to illustrate multiple estimates of the kinetic parameters. Ill-posedness of the kinetic modeling problem has been analyzed using the expression for extractability and the Hessian matrix of the model-data discrepancy function. In an effort to present the sensitivity of parameters to the kinetic models, a novel method called eigenvalue analysis has been developed. A comparison is also made between the second order model and the pseudo-first order model.

  20. Biohydrogen Production and Kinetic Modeling Using Sediment Microorganisms of Pichavaram Mangroves, India

    PubMed Central

    Mullai, P.; Sridevi, K.

    2013-01-01

    Mangrove sediments host rich assemblages of microorganisms, predominantly mixed bacterial cultures, which can be efficiently used for biohydrogen production through anaerobic dark fermentation. The influence of process parameters such as effect of initial glucose concentration, initial medium pH, and trace metal (Fe2+) concentration was investigated in this study. A maximum hydrogen yield of 2.34, 2.3, and 2.6?mol H2 mol?1 glucose, respectively, was obtained under the following set of optimal conditions: initial substrate concentration10,000?mg?L?1, initial pH6.0, and ferrous sulphate concentration100?mg?L?1, respectively. The addition of trace metal to the medium (100?mg?L?1 FeSO47H2O) enhanced the biohydrogen yield from 2.3?mol H2?mol?1 glucose to 2.6?mol H2 mol?1 glucose. Furthermore, the experimental data was subjected to kinetic analysis and the kinetic constants were estimated with the help of well-known kinetic models available in the literature, namely, Monod model, logistic model and Luedeking-Piret model. The model fitting was found to be in good agreement with the experimental observations, for all the models, with regression coefficient values >0.92. PMID:24319679

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

    PubMed

    Liu, Kuan-Miao; Liu, Kuan-Ju

    2016-01-01

    Enzymatic syntheses of fatty acid anilides are important owing to their wide range of industrial applications in detergents, shampoo, cosmetics, and surfactant formulations. The amidation reaction of Mucor miehei lipase Lipozyme IM20 was investigated for direct amidation of triacylglycerol in organic solvents. The process parameters (reaction temperature, substrate molar ratio, enzyme amount) were optimized to achieve the highest yield of anilide. The maximum yield of palmitanilide (88.9%) was achieved after 24h of reaction at 40°C at an enzyme concentration of 1.4% (70mg). Kinetics of lipase-catalyzed amidation of aniline with tripalmitin has been investigated. The reaction rate could be described in terms of the Michaelis-Menten equation with a Ping-Pong Bi-Bi mechanism and competitive inhibition by both the substrates. The kinetic constants were estimated by using non-linear regression method using enzyme kinetic modules. The enzyme operational stability study showed that Lipozyme IM20 retained 38.1% of the initial activity for the synthesis of palmitanilide (even after repeated use for 48h). Palmitanilide, a fatty acid amide, exhibited potent antimicrobial activity toward Bacillus cereus. PMID:26672452

  2. Kinetic Modeling of Esterification of Ethylene Glycol with Acetic Acid

    SciTech Connect

    Yadav, Vishnu P.; Maity, Sunil K.; Mukherjee, Rudra Palash; Bantraj, Kandi

    2010-10-26

    The reaction kinetics of the esterification of ethylene glycol with acetic acid in the presence of cation exchange resin has been studied and kinetic models based on empirical and Langmuir approach has been developed. The Langmuir based model involving eight kinetic parameters fits experimental data much better compared to empirical model involving four kinetic parameters. The effect of temperature and catalyst loading on the reaction system has been analyzed. Further, the activation energy and frequency factor of the rate constants for Langmuir based model has been estimated.

  3. Kinetic Modeling of Esterification of Ethylene Glycol with Acetic Acid

    NASA Astrophysics Data System (ADS)

    Yadav, Vishnu P.; Mukherjee, Rudra Palash; Bantraj, Kandi; Maity, Sunil K.

    2010-10-01

    The reaction kinetics of the esterification of ethylene glycol with acetic acid in the presence of cation exchange resin has been studied and kinetic models based on empirical and Langmuir approach has been developed. The Langmuir based model involving eight kinetic parameters fits experimental data much better compared to empirical model involving four kinetic parameters. The effect of temperature and catalyst loading on the reaction system has been analyzed. Further, the activation energy and frequency factor of the rate constants for Langmuir based model has been estimated.

  4. Fission Yield Predictions with TALYS

    SciTech Connect

    Duijvestijn, M.C.; Koning, A.J.

    2005-05-24

    The nuclear model code TALYS has been extended to enable the prediction of fission yields. The mass yield curves are extracted from temperature-dependent multi-modal random-neck rupture calculations. Charge yields of the fission fragment are determined using the scission-point model and subsequently folded with the mass yields. We present a comparison of several fission-fragment mass yields and isotopic yields with experimental data.

  5. Predicting yields for autotrophic and cometabolic processes

    SciTech Connect

    Andrews, G.

    1995-12-31

    The goal of bioprocess engineering is to state how the optimum design and control strategy for a bioprocess follow from the metabolism of the particular microorganism. A necessary step toward this goal is to show how the parameters used in quantitative descriptions of a process (e.g., yield and maintenance coefficients) are related to those describing the metabolism [e.g., Y{sub ATP}, (P/O)]. The {open_quotes}yield equation{close_quotes} approach to this problem involves dividing metabolism into the separate pathways for catabolism, anabolism, respiration, and product formation and balancing the production and consumption of reducing equivalents and ATP. The general approach, demonstrated previously for heterotrophic cell growth and products of fermentation, is illustrated by three new examples: the cell yield for chemoautotrophic iron-oxidizing bacteria, the cometabolic degradation of chloroform by methanotrophic bacteria, and the theoretical yield of succinic acid from glucose.

  6. The kinetic chemical equilibrium regime

    NASA Astrophysics Data System (ADS)

    Ern, Alexandre; Giovangigli, Vincent

    We investigate reactive gas mixtures in the kinetic chemical equilibrium regime. Our starting point is a generalized Boltzmann equation with a chemical source term valid for arbitrary reaction mechanisms and yielding a positive entropy production. We first study the Enskog expansion in the kinetic chemical equilibrium regime. We derive a new set of macroscopic equations in the zeroth- and first-order regimes, expressing conservation of element densities, momentum and energy. The transport fluxes arising in the Navier-Stokes equilibrium regime are the element diffusion velocities, the heat flux vector and the pressure tensor and are written in terms of transport coefficients. Upon introducing species diffusion velocities, the kinetic equilibrium regime appears to be formally equivalent to the one obtained for gas mixtures in chemical nonequilibrium and then letting the chemical reactions approach equilibrium. The actual values of the transport coefficients are, however, different. Finally, we derive the entropy conservation equation in the Navier-Stokes equilibrium regime and show that the source term is positive and that it is compatible with Onsagers reciprocal relations.

  7. Regression Models For Saffron Yields in Iran

    NASA Astrophysics Data System (ADS)

    S. H, Sanaeinejad; S. N, Hosseini

    Saffron is an important crop in social and economical aspects in Khorassan Province (Northeast of Iran). In this research wetried to evaluate trends of saffron yield in recent years and to study the relationship between saffron yield and the climate change. A regression analysis was used to predict saffron yield based on 20 years of yield data in Birjand, Ghaen and Ferdows cities.Climatologically data for the same periods was provided by database of Khorassan Climatology Center. Climatologically data includedtemperature, rainfall, relative humidity and sunshine hours for ModelI, and temperature and rainfall for Model II. The results showed the coefficients of determination for Birjand, Ferdows and Ghaen for Model I were 0.69, 0.50 and 0.81 respectively. Also coefficients of determination for the same cities for model II were 0.53, 0.50 and 0.72 respectively. Multiple regression analysisindicated that among weather variables, temperature was the key parameter for variation ofsaffron yield. It was concluded that increasing temperature at spring was the main cause of declined saffron yield during recent years across the province. Finally, yield trend was predicted for the last 5 years using time series analysis.

  8. Combustion kinetics and reaction pathways

    SciTech Connect

    Klemm, R.B.; Sutherland, J.W.

    1993-12-01

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

  9. Kinetics of Uranium(VI) Desorption from Contaminated Sediments: Effect of Geochemical Conditions and Model Evaluation

    SciTech Connect

    Liu, Chongxuan; Shi, Zhenqing; Zachara, John M.

    2009-09-01

    Stirred-flow cell experiments were performed to investigate the kinetics of uranyl [U(VI)] desorption from a contaminated sediment collected from the Hanford 300 Area at the US Department of Energy (DOE) Hanford Site, Washington. Three influent solutions of variable pH, Ca and carbonate concentrations that affected U(VI) aqueous and surface speciation were used under dynamic flow conditions to evaluate the effect of geochemical conditions on the rate of U(VI) desorption. The measured rate of U(VI) desorption varied with solution chemical composition that evolved as a result of thermodynamic and kinetic interactions between the influent solutions and sediment. The solution chemical composition that led to a lower equilibrium U(VI) sorption to the solid phase yielded a faster desorption rate. The experimental results were used to evaluate a multi-rate, surface complexation model (SCM) that has been proposed to describe U(VI) desorption kinetics in the Hanford sediment that contained complex sorbed U(VI) species in mass transfer limited domains. The model was modified and supplemented by including multi-rate, ion exchange reactions to describe the geochemical interactions between the solutions and sediment. With the same set of model parameters, the modified model reasonably well described the evolution of major ions and the rates of U(VI) desorption under variable geochemical and flow conditions, implying that the multi-rate SCM is an effective way to describe U(VI) desorption kinetics in subsurface sediments.

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

    PubMed

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

    2010-10-01

    Human metabolic diseases are typically network diseases. This holds not only for multifactorial diseases, such as metabolic syndrome or Type 2 diabetes, but even when a single gene defect is the primary cause, where the adaptive response of the entire network determines the severity of disease. The latter may differ between individuals carrying the same mutation. Understanding the adaptive responses of human metabolism naturally requires a systems biology approach. Modelling of metabolic pathways in micro-organisms and some mammalian tissues has yielded many insights, qualitative as well as quantitative, into their control and regulation. Yet, even for a well-known pathway such as glycolysis, precise predictions of metabolite dynamics from experimentally determined enzyme kinetics have been only moderately successful. In the present review, we compare kinetic models of glycolysis in three cell types (African trypanosomes, yeast and skeletal muscle), evaluate their predictive power and identify limitations in our understanding. Although each of these models has its own merits and shortcomings, they also share common features. For example, in each case independently measured enzyme kinetic parameters were used as input. Based on these 'lessons from glycolysis', we will discuss how to make best use of kinetic computer models to advance our understanding of human metabolic diseases. PMID:20863302

  11. SYSTEMS BIOLOGY FROM MICROORGANISMS TO HUMAN METABOLIC DISEASES THE ROLE OF DETAILED KINETIC MODELS

    PubMed Central

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

    2012-01-01

    Human metabolic diseases are typically network diseases. This holds not only for multifactorial diseases, such as metabolic syndrome or type II diabetes: even when a single gene defect is the primary cause, the adaptive response of the entire network determines the severity of disease. The latter may differ between individuals carrying the same mutation. Understanding the adaptive responses of human metabolism naturally requires a systems biology approach. Modelling of metabolic pathways in micro-organisms and some mammalian tissues has yielded many insights - qualitative as well as quantitative - into their control and regulation. Yet, even for a well-known pathway like glycolysis precise predictions of metabolite dynamics from experimentally determined enzyme-kinetics have been only moderately successful. Here, we compare kinetic models of glycolysis in three cell types (African trypanosomes, yeast and skeletal muscle), evaluate their predictive power and identify limitations in our understanding. While each of these models has its own merits and shortcomings, they also share common features. For example, in each case independently measured enzyme kinetic parameters were used as input. Based on these lessons from glycolysis, we will discuss how to make best use of kinetic computer models to advance our understanding of human metabolic diseases. PMID:20863302

  12. Kinetic modeling of the adsorption and desorption of CO2 on ?-Fe2O3.

    PubMed

    Breyer, Christine; Reichert, Dirk; Seidel, Juergen; Httl, Regina; Mertens, Florian; Kureti, Sven

    2015-10-28

    The present paper addresses the interaction of CO2 with polycrystalline ?-Fe2O3 revealing considerable catalytic activity in CO oxidation to yield CO2. The mechanism of adsorption and desorption of CO2 was investigated by diffuse reflectance infrared fourier transform spectroscopy (DRIFTS), while the kinetics was examined by temperature-programmed desorption (CO2-TPD). For numeric modeling as well as simulation of the surface coverage, an elementary kinetic mean field model was constructed using Arrhenius-based rate expressions. The kinetic parameters of desorption were taken from fitting calculations (A2 = 3.01 10(5) mol (m(2) s)(-1), E2(0) = 112.8 kJ mol(-1), ?2 = 70.2 kJ mol(-1)), whereas the adsorption was considered to be non-activated and the pre-exponential factor was estimated from kinetic gas theory (A1 = 0.0192 m s(-1), E1 = 0 kJ mol(-1)). For model validation, predicted and experimental CO2-TPD profiles were compared and thermodynamic consistency was evaluated by using differential scanning calorimetry (?adsH(250 C) = -129 kJ mol(-1)) as well as literature data. PMID:26411579

  13. Optimization and kinetic analysis on the sulfuric acid - Catalyzed depolymerization of wheat straw.

    PubMed

    Wu, Qian-Qian; Ma, Yu-Long; Chang, Xuan; Sun, Yong-Gang

    2015-09-20

    The objectives of this work were to optimize the experimental condition and to study the kinetic behavior of wheat straw depolymerization with sulfuric acid (2 wt%, 3 wt%, and 4 wt%) at different temperatures (120°C, 130°C, and 140°C). The two-fraction kinetic model was obtained for the prediction of the generations of product and by-product during depolymerization. The kinetic parameters of the two-fraction model were analyzed using an Arrhenius-type equation. Applying the kinetic two-fraction model, the optimum condition for wheat straw depolymerization was 3 wt% H2SO4 at 130°C for 75 min, which yielded a high concentration of fermentable sugars (xylose 8.934 g/L, glucose 1.363 g/L, and arabinose 1.203 g/L) and low concentrations of microbial inhibitors (furfural 0.526 g/L and acetic acid 1.192 g/L). These results suggest that the model obtained in this study can satisfactorily describe the formation of degradation products and the depolymerization mechanism of wheat straw. PMID:26050891

  14. Kinetic Modeling of Martian Atmosphere Aerobraking Plasma

    NASA Astrophysics Data System (ADS)

    Drake, Dereth; Smithwick, Evan

    2014-10-01

    During Martian atmospheric aerobraking the plasma that forms around a spacecraft can be considered a high-volume plasma reactor that is sustained by the dissipation of the spacecraft's kinetic energy. At altitudes below 100 km, it has been shown that the plasma parameters vary considerably depending on the spacecraft's trajectory. However, in the range which is applicable to aerobraking, 100 km < h < 200 km, little of this work has been completed. We have evaluated a simple kinetic model to determine a probable range of plasma parameters for altitudes between 100 and 200 km using existing Martian atmospheric data and available probe trajectories.

  15. Yielding elastic tethers stabilize robust cell adhesion.

    PubMed

    Whitfield, Matt J; Luo, Jonathon P; Thomas, Wendy E

    2014-12-01

    Many bacteria and eukaryotic cells express adhesive proteins at the end of tethers that elongate reversibly at constant or near constant force, which we refer to as yielding elasticity. Here we address the function of yielding elastic adhesive tethers with Escherichia coli bacteria as a model for cell adhesion, using a combination of experiments and simulations. The adhesive bond kinetics and tether elasticity was modeled in the simulations with realistic biophysical models that were fit to new and previously published single molecule force spectroscopy data. The simulations were validated by comparison to experiments measuring the adhesive behavior of E. coli in flowing fluid. Analysis of the simulations demonstrated that yielding elasticity is required for the bacteria to remain bound in high and variable flow conditions, because it allows the force to be distributed evenly between multiple bonds. In contrast, strain-hardening and linear elastic tethers concentrate force on the most vulnerable bonds, which leads to failure of the entire adhesive contact. Load distribution is especially important to noncovalent receptor-ligand bonds, because they become exponentially shorter lived at higher force above a critical force, even if they form catch bonds. The advantage of yielding is likely to extend to any blood cells or pathogens adhering in flow, or to any situation where bonds are stretched unequally due to surface roughness, unequal native bond lengths, or conditions that act to unzip the bonds. PMID:25473833

  16. Compartment modeling of dynamic brain PET—The impact of scatter corrections on parameter errors

    SciTech Connect

    Häggström, Ida Karlsson, Mikael; Larsson, Anne; Schmidtlein, C. Ross

    2014-11-01

    Purpose: The aim of this study was to investigate the effect of scatter and its correction on kinetic parameters in dynamic brain positron emission tomography (PET) tumor imaging. The 2-tissue compartment model was used, and two different reconstruction methods and two scatter correction (SC) schemes were investigated. Methods: The GATE Monte Carlo (MC) software was used to perform 2 × 15 full PET scan simulations of a voxelized head phantom with inserted tumor regions. The two sets of kinetic parameters of all tissues were chosen to represent the 2-tissue compartment model for the tracer 3′-deoxy-3′-({sup 18}F)fluorothymidine (FLT), and were denoted FLT{sub 1} and FLT{sub 2}. PET data were reconstructed with both 3D filtered back-projection with reprojection (3DRP) and 3D ordered-subset expectation maximization (OSEM). Images including true coincidences with attenuation correction (AC) and true+scattered coincidences with AC and with and without one of two applied SC schemes were reconstructed. Kinetic parameters were estimated by weighted nonlinear least squares fitting of image derived time–activity curves. Calculated parameters were compared to the true input to the MC simulations. Results: The relative parameter biases for scatter-eliminated data were 15%, 16%, 4%, 30%, 9%, and 7% (FLT{sub 1}) and 13%, 6%, 1%, 46%, 12%, and 8% (FLT{sub 2}) for K{sub 1}, k{sub 2}, k{sub 3}, k{sub 4}, V{sub a}, and K{sub i}, respectively. As expected, SC was essential for most parameters since omitting it increased biases by 10 percentage points on average. SC was not found necessary for the estimation of K{sub i} and k{sub 3}, however. There was no significant difference in parameter biases between the two investigated SC schemes or from parameter biases from scatter-eliminated PET data. Furthermore, neither 3DRP nor OSEM yielded the smallest parameter biases consistently although there was a slight favor for 3DRP which produced less biased k{sub 3} and K{sub i} estimates while OSEM resulted in a less biased V{sub a}. The uncertainty in OSEM parameters was about 26% (FLT{sub 1}) and 12% (FLT{sub 2}) larger than for 3DRP although identical postfilters were applied. Conclusions: SC was important for good parameter estimations. Both investigated SC schemes performed equally well on average and properly corrected for the scattered radiation, without introducing further bias. Furthermore, 3DRP was slightly favorable over OSEM in terms of kinetic parameter biases and SDs.

  17. Continuous growth kinetics of Candida utilis in pineapple cannery effluent

    SciTech Connect

    Prior, B.A.

    1984-01-01

    Candida utilis was grown on a pineapple cannery effluent as the sole carbon and energy source in a chemostat at dilution rates between 0.10 and 0.62 h/sup -1/ to determine the growth kinetics. The principal sugars in the effluent were sucrose, glucose, and fructose. The cell yield coefficient on carbohydrate varied with dilution rate and a maximum value of 0.63 was observed at a dilution rate of 0.33 h/sup -1/. The steady-state concentrations of carbohydrate, reducing sugar, and chemical oxygen demand (COD) appeared to follow Monod saturation kinetics with increasing dilution rate, although none of the measured parameters represented a pure substrate. The maximum specific growth rate and reducing sugar saturation constant were 0.64 h/sup -1/ and 0.060 g/L, respectively. A maximum cell mass productivity of 2.3 g/L h was observed at a dilution rate of 0.51 h/sup -1/. At this dilution rate, only 68% of the COD was removed. A 95% COD removal was attained at a dilution rate of 0.10 h/sup -1/. Optimal yeast productivity and COD reduction occurred at a dilution rate of 0.33 h/sup -1/.

  18. Temperature dependence of protein folding kinetics in living cells.

    PubMed

    Guo, Minghao; Xu, Yangfan; Gruebele, Martin

    2012-10-30

    We measure the stability and folding rate of a mutant of the enzyme phosphoglycerate kinase (PGK) inside bone tissue cells as a function of temperature from 38 to 48 C. To facilitate measurement in individual living cells, we developed a rapid laser temperature stepping method capable of measuring complete thermal melts and kinetic traces in about two min. We find that this method yields improved thermal melts compared to heating a sample chamber or microscope stage. By comparing results for six cells with in vitro data, we show that the protein is stabilized by about 6 kJ/mole in the cytoplasm, but the temperature dependence of folding kinetics is similar to in vitro. The main difference is a slightly steeper temperature dependence of the folding rate in some cells that can be rationalized in terms of temperature-dependent crowding, local viscosity, or hydrophobicity. The observed rate coefficients can be fitted within measurement uncertainty by an effective two-state model, even though PGK folds by a multistate mechanism. We validate the effective two-state model with a three-state free energy landscape of PGK to illustrate that the effective fitting parameters can represent a more complex underlying free energy landscape. PMID:22665776

  19. Continuous growth kinetics of Candida utilis in pineapple cannery effluent.

    PubMed

    Prior, B A

    1984-07-01

    Candida utilis was grown on a pineapple cannery effluent as the sole carbon and energy source in a chemostat at dilution rates between 0.10 and 0.62 h(-1) to determine the growth kinetics. The principal sugars in the effluent were sucrose, glucose, and fructose. The cell yield coefficient on carbohydrate varied with dilution rate and a maximum value of 0.63 was observed at a dilution rate of 0.33 h(-1). The steady-state concentrations of carbohydrate, reducing sugar, and chemical oxygen demand (COD) appeared to follow Monod saturation kinetics with increasing dilution rate, although none of the measured parameters represented a pure substrate. The maximum specific growth rate and reducing sugar saturation constant were 0.64 h(-1) and 0.060 g/L, respectively. A maximum cell mass productivity of 2.3 g/L h was observed at a dilution rate of 0.51 h(-1). At this dilution rate, only 68% of the COD was removed. A 95% COD removal was attained at a dilution rate of 0.10 h(-1). Optimal yeast productivity and COD reduction occurred at a dilution rate of 0.33 h(-1). PMID:18553441

  20. Mechanisms and kinetics of coal hydrogenation

    SciTech Connect

    Baldwin, R M; Furlong, M W

    1981-05-01

    Colorado School of Mines is engaged in an experimental program to develop comprehensive models for the effects of coal composition upon the kinetics and mechanisms of coal hydrogenation, for the effects of mineral matter additives (disposable catalysts) upon kinetics and mechanisms of coal hydrogenation, and for the kinetics and mechanisms of the hydrogenation of coal derived products such as preasphaltenes, and asphaltenes. Experimental work was completed on a suite of bituminous coals, thus completing the initial phase of the coal reactivity study. Eleven of the 14 coals of the suite were successfully run in duplicate. Conversion to THF solubles was correlated well by pseudo-second order kinetics. The resulting kinetic rate constants correlated with H/C ratio, mean-max vitrinite reflectance, and a specially-defined fraction of reactive macerals. The data did not correlate well with O/C ratios of the parent coals. Computer-derived statistical fits of various kinetic models were limited in their effectiveness at fitting the experimental data. Experimental work on the first phase of the disposal catalyst studies was completed. Statistical significance testing of the experimental data showed: fractional conversion and yield of light hydrocarbon products increased with time; and mineral properties of the additives were more significant in increasing overall conversion than the additive surface areas. The relative effects of the additives are given.

  1. b{yields}s penguin amplitude in charmless B{yields}PP decays

    SciTech Connect

    Gronau, Michael; Rosner, Jonathan L.

    2005-04-01

    The b{yields}s penguin amplitude affects a number of B meson decays to two pseudoscalar (P) mesons in which potential anomalies are being watched carefully, though none has yet reached a statistically compelling level. These include (a) a sum of rates for B{sup 0}{yields}K{sup 0}{pi}{sup 0} and B{sup +}{yields}K{sup +}{pi}{sup 0} enhanced relative to half the sum for B{sup 0}{yields}K{sup +}{pi}{sup -} and B{sup +}{yields}K{sup 0}{pi}{sup +} (b) a time-dependent CP asymmetry parameter S for B{sup 0}{yields}K{sup 0}{pi}{sup 0} which is low in comparison with the expected value of sin2{beta}{approx_equal}0.73, and (c) a similar deviation in the parameter S for B{sup 0}{yields}{eta}{sup '}K{sub S}. These and related phenomena involving vector mesons in the final state are discussed in a unified way in and beyond the standard model. Future experiments which would conclusively indicate the presence of new physics are identified. Several of these involve decays of the strange B meson B{sub s}. In the standard model we prove an approximate sum rule for CP rate differences in B{sup 0}{yields}K{sup +}{pi}{sup -}, B{sup +}{yields}K{sup +}{pi}{sup 0} and B{sup 0}{yields}K{sup 0}{pi}{sup 0}, predicting a negative sign for the latter asymmetry.

  2. Drilling ban yields verdict

    SciTech Connect

    Nation, L.M.

    1992-01-01

    This paper briefly reviews a lawsuit which is under appeal by the State of Michigan regarding a takings claim filed over a petroleum exploration site. The dispute arose as a result of a 1987 decision by the Michigan Department of Natural Resources forbidding the property owners from developing the mineral rights leased to Miller Brothers in the Huron/Manistee National Forest. This area is bisected by a trend of Silurian Niagaran reef complexes which has a known production history throughout the State. The dunes area of the national forest has been deemed a wilderness area. As a result of the State's decision, the courts have awarded a sum of 71 million dollars to the developer to cover damages and lost resources. The reserve estimates were taken from adjacent areas which showed that the Niagaran reefs are relatively consistent in their yield.

  3. Kinetic studies and model development for the formation of galacto-oligosaccharides from lactose using synthesized thermo-responsive bioconjugate.

    PubMed

    Palai, Tapas; Kumar, Ashok; Bhattacharya, Prashant K

    2015-03-01

    In an earlier study by us [47], thermo-responsive bioconjugate (poly-N-isopropylacrylamide-?-galactosidase) was synthesized and characterized. This study utilizes the prowess of such smart bioconjugate for the enzymatic synthesis of galacto-oligosaccharides (GOS) from lactose at various initial lactose concentrations (ILC), enzyme concentrations, and temperatures, while maintaining a constant pH of 6. A maximum GOS yield of 35% (on dry basis) was observed at 100g/L ILC and 0.275mg/mL (0.055U/mL) conjugated protein. The GOS yield remained approximately the same for 50 and 100g/L ILC, beyond which, it decreased. As the enzyme concentration increased, the equilibrium formation of GOS increased and eventually attained a plateau when the concentration of conjugated protein exceeded 0.275mg/mL (0.055U/mL). GOS yield increased on raising the temperature from 30 to 40C, and declined thereafter. The apparent kinetic parameters were estimated from a five-step, nine-parameter kinetic model, which was then simulated using the COPASI package. The simulated results demonstrated an excellent match with the experimental data. PMID:25659631

  4. Determining the bistability parameter ranges of artificially induced lac operon using the root locus method.

    PubMed

    Avcu, N; Alyrk, H; Demir, G K; Pekergin, F; Cavas, L; Gzeli?, C

    2015-06-01

    This paper employs the root locus method to conduct a detailed investigation of the parameter regions that ensure bistability in a well-studied gene regulatory network namely, lac operon of Escherichia coli (E. coli). In contrast to previous works, the parametric bistability conditions observed in this study constitute a complete set of necessary and sufficient conditions. These conditions were derived by applying the root locus method to the polynomial equilibrium equation of the lac operon model to determine the parameter values yielding the multiple real roots necessary for bistability. The lac operon model used was defined as an ordinary differential equation system in a state equation form with a rational right hand side, and it was compatible with the Hill and Michaelis-Menten approaches of enzyme kinetics used to describe biochemical reactions that govern lactose metabolism. The developed root locus method can be used to study the steady-state behavior of any type of convergent biological system model based on mass action kinetics. This method provides a solution to the problem of analyzing gene regulatory networks under parameter uncertainties because the root locus method considers the model parameters as variable, rather than fixed. The obtained bistability ranges for the lac operon model parameters have the potential to elucidate the appearance of bistability for E. coli cells in in vivo experiments, and they could also be used to design robust hysteretic switches in synthetic biology. PMID:25864166

  5. Effect of Driver Impedance on Dense Plasma Focus Z-Pinch Neutron Yield and Beam Acceleration

    NASA Astrophysics Data System (ADS)

    Sears, J.; Link, A.; Ellsworth, J.; Falabella, S.; Rusnak, B.; Tang, V.; Schmidt, A.; Welch, D.

    2014-10-01

    We explore the effect of driver characteristics on dense plasma focus (DPF) neutron yield and beam acceleration using particle-in-cell (PIC) simulations of a kJ-scale DPF. Our PIC simulations are fluid for the run-down phase and transition to fully kinetic for the pinch phase. 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. Simulations are benchmarked to measurements of a table top kJ DPF experiment with neutron yield measured with He3-based detectors. Simulated neutron yield scales approximately with the fourth power of peak current, I4. We also probe the accelerating fields by measuring the acceleration of a 4 MeV deuteron beam and by measuring the DPF self-generated beam energy distribution, finding gradients higher than 50 MV/m. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 and supported by the Laboratory Directed Research and Development Program (11-ERD-063) at LLNL.

  6. The effect of particle inlet conditions on FCC riser hydrodynamics and product yields.

    SciTech Connect

    Chang, S. L.; Golchert, B.; Lottes, S. A.; Zhou, C. Q.; Huntsinger, A.; Petrick, M.

    1999-10-11

    Essential to today's modern refineries and the gasoline production process are fluidized catalytic cracking units. By using a computational fluid dynamics (CFD) code developed at Argonne National Laboratory to simulate the riser, parametric and sensitivity studies were performed to determine the effect of catalyst inlet conditions on the riser hydrodynamics and on the product yields. Simulations were created on the basis of a general riser configuration and operating conditions. The results of this work are indications of riser operating conditions that will maximize specific product yields. The CFD code is a three-dimensional, multiphase, turbulent, reacting flow code with phenomenological models for particle-solid interactions, droplet evaporation, and chemical kinetics. The code has been validated against pressure, particle loading, and product yield measurements. After validation of the code, parametric studies were performed on various parameters such as the injection velocity of the catalyst, the angle of injection, and the particle size distribution. The results indicate that good mixing of the catalyst particles with the oil droplets produces a high degree of cracking in the riser.

  7. Kinetic proofreading models for cell signaling predict ways to escape kinetic proofreading

    PubMed Central

    Hlavacek, William S.; Redondo, Antonio; Metzger, Henry; Wofsy, Carla; Goldstein, Byron

    2001-01-01

    In the context of cell signaling, kinetic proofreading was introduced to explain how cells can discriminate among ligands based on a kinetic parameter, the ligand-receptor dissociation rate constant. In the kinetic proofreading model of cell signaling, responses occur only when a bound receptor undergoes a complete series of modifications. If the ligand dissociates prematurely, the receptor returns to its basal state and signaling is frustrated. We extend the model to deal with systems where aggregation of receptors is essential to signal transduction, and present a version of the model for systems where signaling depends on an extrinsic kinase. We also investigate the kinetics of signaling molecules, messengers, that are generated by aggregated receptors but do not remain associated with the receptor complex. We show that the extended model predicts modes of signaling that exhibit kinetic discrimination for some range of parameters but for other parameter values show little or no discrimination and thus escape kinetic proofreading. We compare model predictions with experimental data. PMID:11390967

  8. Kinetic-energy-momentum tensor in electrodynamics