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Sample records for accurate kinetic parameters

  1. A two-parameter kinetic model based on a time-dependent activity coefficient accurately describes enzymatic cellulose digestion

    PubMed Central

    Kostylev, Maxim; Wilson, David

    2014-01-01

    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 ML. (1913) Biochem Z 49:333–369), but 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 a 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 and can thus 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

  2. Kinetic parameters from thermogravimetric analysis

    NASA Technical Reports Server (NTRS)

    Kiefer, Richard L.

    1993-01-01

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

  3. Determination of kinetic parameters for biomass combustion.

    PubMed

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

    2016-09-01

    The aim of this work is to provide a wide database of kinetic data for the most common biomass by thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). Due to the characteristic parameters of DTG curves, a two-stage reaction model is proposed and the kinetic parameters obtained from model-based methods with energy activation values for first and second stages in the range 1.75·10(4)-1.55·10(5)J/mol and 1.62·10(4)-2.37·10(5)J/mol, respectively. However, it has been found that Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose model-free methods are not suitable to determine the kinetic parameters of biomass combustion since the assumptions of these two methods were not accomplished in the full range of the combustion process. PMID:27233095

  4. Accurate parameter estimation for unbalanced three-phase system.

    PubMed

    Chen, Yuan; So, Hing Cheung

    2014-01-01

    Smart grid is an intelligent power generation and control console in modern electricity networks, where the unbalanced three-phase power system is the commonly used model. Here, parameter estimation for this system is addressed. After converting the three-phase waveforms into a pair of orthogonal signals via the α β-transformation, the nonlinear least squares (NLS) estimator is developed for accurately finding the frequency, phase, and voltage parameters. The estimator is realized by the Newton-Raphson scheme, whose global convergence is studied in this paper. Computer simulations show that the mean square error performance of NLS method can attain the Cramér-Rao lower bound. Moreover, our proposal provides more accurate frequency estimation when compared with the complex least mean square (CLMS) and augmented CLMS. PMID:25162056

  5. A simple and accurate resist parameter extraction method for sub-80-nm DRAM patterns

    NASA Astrophysics Data System (ADS)

    Lee, Sook; Hwang, Chan; Park, Dong-Woon; Kim, In-Sung; Kim, Ho-Chul; Woo, Sang-Gyun; Cho, Han-Ku; Moon, Joo-Tae

    2004-05-01

    Due to the polarization effect of high NA lithography, the consideration of resist effect in lithography simulation becomes increasingly important. In spite of the importance of resist simulation, many process engineers are reluctant to consider resist effect in lithography simulation due to time-consuming procedure to extract required resist parameters and the uncertainty of measurement of some parameters. Weiss suggested simplified development model, and this model does not require the complex kinetic parameters. For the device fabrication engineers, there is a simple and accurate parameter extraction and optimizing method using Weiss model. This method needs refractive index, Dill"s parameters and development rate monitoring (DRM) data in parameter extraction. The parameters extracted using referred sequence is not accurate, so that we have to optimize the parameters to fit the critical dimension scanning electron microscopy (CD SEM) data of line and space patterns. Hence, the FiRM of Sigma-C is utilized as a resist parameter-optimizing program. According to our study, the illumination shape, the aberration and the pupil mesh point have a large effect on the accuracy of resist parameter in optimization. To obtain the optimum parameters, we need to find the saturated mesh points in terms of normalized intensity log slope (NILS) prior to an optimization. The simulation results using the optimized parameters by this method shows good agreement with experiments for iso-dense bias, Focus-Exposure Matrix data and sub 80nm device pattern simulation.

  6. Accurate quantification of diffusion and binding kinetics of non-integral membrane proteins by FRAP.

    PubMed

    Berkovich, Ronen; Wolfenson, Haguy; Eisenberg, Sharon; Ehrlich, Marcelo; Weiss, Matthias; Klafter, Joseph; Henis, Yoav I; Urbakh, Michael

    2011-11-01

    Non-integral membrane proteins frequently act as transduction hubs in vital signaling pathways initiated at the plasma membrane (PM). Their biological activity depends on dynamic interactions with the PM, which are governed by their lateral and cytoplasmic diffusion and membrane binding/unbinding kinetics. Accurate quantification of the multiple kinetic parameters characterizing their membrane interaction dynamics has been challenging. Despite a fair number of approximate fitting functions for analyzing fluorescence recovery after photobleaching (FRAP) data, no approach was able to cope with the full diffusion-exchange problem. Here, we present an exact solution and matlab fitting programs for FRAP with a stationary Gaussian laser beam, allowing simultaneous determination of the membrane (un)binding rates and the diffusion coefficients. To reduce the number of fitting parameters, the cytoplasmic diffusion coefficient is determined separately. Notably, our equations include the dependence of the exchange kinetics on the distribution of the measured protein between the PM and the cytoplasm, enabling the derivation of both k(on) and k(off) without prior assumptions. After validating the fitting function by computer simulations, we confirm the applicability of our approach to live-cell data by monitoring the dynamics of GFP-N-Ras mutants under conditions with different contributions of lateral diffusion and exchange to the FRAP kinetics. PMID:21810156

  7. Accurate and robust estimation of camera parameters using RANSAC

    NASA Astrophysics Data System (ADS)

    Zhou, Fuqiang; Cui, Yi; Wang, Yexin; Liu, Liu; Gao, He

    2013-03-01

    Camera calibration plays an important role in the field of machine vision applications. The popularly used calibration approach based on 2D planar target sometimes fails to give reliable and accurate results due to the inaccurate or incorrect localization of feature points. To solve this problem, an accurate and robust estimation method for camera parameters based on RANSAC algorithm is proposed to detect the unreliability and provide the corresponding solutions. Through this method, most of the outliers are removed and the calibration errors that are the main factors influencing measurement accuracy are reduced. Both simulative and real experiments have been carried out to evaluate the performance of the proposed method and the results show that the proposed method is robust under large noise condition and quite efficient to improve the calibration accuracy compared with the original state.

  8. Machine learning of parameters for accurate semiempirical quantum chemical calculations

    DOE PAGESBeta

    Dral, Pavlo O.; von Lilienfeld, O. Anatole; Thiel, Walter

    2015-04-14

    We investigate possible improvements in the accuracy of semiempirical quantum chemistry (SQC) methods through the use of machine learning (ML) models for the parameters. For a given class of compounds, ML techniques require sufficiently large training sets to develop ML models that can be used for adapting SQC parameters to reflect changes in molecular composition and geometry. The ML-SQC approach allows the automatic tuning of SQC parameters for individual molecules, thereby improving the accuracy without deteriorating transferability to molecules with molecular descriptors very different from those in the training set. The performance of this approach is demonstrated for the semiempiricalmore » OM2 method using a set of 6095 constitutional isomers C7H10O2, for which accurate ab initio atomization enthalpies are available. The ML-OM2 results show improved average accuracy and a much reduced error range compared with those of standard OM2 results, with mean absolute errors in atomization enthalpies dropping from 6.3 to 1.7 kcal/mol. They are also found to be superior to the results from specific OM2 reparameterizations (rOM2) for the same set of isomers. The ML-SQC approach thus holds promise for fast and reasonably accurate high-throughput screening of materials and molecules.« less

  9. Machine learning of parameters for accurate semiempirical quantum chemical calculations

    SciTech Connect

    Dral, Pavlo O.; von Lilienfeld, O. Anatole; Thiel, Walter

    2015-04-14

    We investigate possible improvements in the accuracy of semiempirical quantum chemistry (SQC) methods through the use of machine learning (ML) models for the parameters. For a given class of compounds, ML techniques require sufficiently large training sets to develop ML models that can be used for adapting SQC parameters to reflect changes in molecular composition and geometry. The ML-SQC approach allows the automatic tuning of SQC parameters for individual molecules, thereby improving the accuracy without deteriorating transferability to molecules with molecular descriptors very different from those in the training set. The performance of this approach is demonstrated for the semiempirical OM2 method using a set of 6095 constitutional isomers C7H10O2, for which accurate ab initio atomization enthalpies are available. The ML-OM2 results show improved average accuracy and a much reduced error range compared with those of standard OM2 results, with mean absolute errors in atomization enthalpies dropping from 6.3 to 1.7 kcal/mol. They are also found to be superior to the results from specific OM2 reparameterizations (rOM2) for the same set of isomers. The ML-SQC approach thus holds promise for fast and reasonably accurate high-throughput screening of materials and molecules.

  10. Construction of feasible and accurate kinetic models of metabolism: A Bayesian approach

    PubMed Central

    Saa, Pedro A.; Nielsen, Lars K.

    2016-01-01

    Kinetic models are essential to quantitatively understand and predict the behaviour of metabolic networks. Detailed and thermodynamically feasible kinetic models of metabolism are inherently difficult to formulate and fit. They have a large number of heterogeneous parameters, are non-linear and have complex interactions. Many powerful fitting strategies are ruled out by the intractability of the likelihood function. Here, we have developed a computational framework capable of fitting feasible and accurate kinetic models using Approximate Bayesian Computation. This framework readily supports advanced modelling features such as model selection and model-based experimental design. We illustrate this approach on the tightly-regulated mammalian methionine cycle. Sampling from the posterior distribution, the proposed framework generated thermodynamically feasible parameter samples that converged on the true values, and displayed remarkable prediction accuracy in several validation tests. Furthermore, a posteriori analysis of the parameter distributions enabled appraisal of the systems properties of the network (e.g., control structure) and key metabolic regulations. Finally, the framework was used to predict missing allosteric interactions. PMID:27417285

  11. Direct computation of parameters for accurate polarizable force fields

    SciTech Connect

    Verstraelen, Toon Vandenbrande, Steven; Ayers, Paul W.

    2014-11-21

    We present an improved electronic linear response model to incorporate polarization and charge-transfer effects in polarizable force fields. This model is a generalization of the Atom-Condensed Kohn-Sham Density Functional Theory (DFT), approximated to second order (ACKS2): it can now be defined with any underlying variational theory (next to KS-DFT) and it can include atomic multipoles and off-center basis functions. Parameters in this model are computed efficiently as expectation values of an electronic wavefunction, obviating the need for their calibration, regularization, and manual tuning. In the limit of a complete density and potential basis set in the ACKS2 model, the linear response properties of the underlying theory for a given molecular geometry are reproduced exactly. A numerical validation with a test set of 110 molecules shows that very accurate models can already be obtained with fluctuating charges and dipoles. These features greatly facilitate the development of polarizable force fields.

  12. Accurate 3D quantification of the bronchial parameters in MDCT

    NASA Astrophysics Data System (ADS)

    Saragaglia, A.; Fetita, C.; Preteux, F.; Brillet, P. Y.; Grenier, P. A.

    2005-08-01

    The assessment of bronchial reactivity and wall remodeling in asthma plays a crucial role in better understanding such a disease and evaluating therapeutic responses. Today, multi-detector computed tomography (MDCT) makes it possible to perform an accurate estimation of bronchial parameters (lumen and wall areas) by allowing a quantitative analysis in a cross-section plane orthogonal to the bronchus axis. This paper provides the tools for such an analysis by developing a 3D investigation method which relies on 3D reconstruction of bronchial lumen and central axis computation. Cross-section images at bronchial locations interactively selected along the central axis are generated at appropriate spatial resolution. An automated approach is then developed for accurately segmenting the inner and outer bronchi contours on the cross-section images. It combines mathematical morphology operators, such as "connection cost", and energy-controlled propagation in order to overcome the difficulties raised by vessel adjacencies and wall irregularities. The segmentation accuracy was validated with respect to a 3D mathematically-modeled phantom of a pair bronchus-vessel which mimics the characteristics of real data in terms of gray-level distribution, caliber and orientation. When applying the developed quantification approach to such a model with calibers ranging from 3 to 10 mm diameter, the lumen area relative errors varied from 3.7% to 0.15%, while the bronchus area was estimated with a relative error less than 5.1%.

  13. Accurate label-free reaction kinetics determination using initial rate heat measurements

    PubMed Central

    Ebrahimi, Kourosh Honarmand; Hagedoorn, Peter-Leon; Jacobs, Denise; Hagen, Wilfred R.

    2015-01-01

    Accurate label-free methods or assays to obtain the initial reaction rates have significant importance in fundamental studies of enzymes and in application-oriented high throughput screening of enzyme activity. Here we introduce a label-free approach for obtaining initial rates of enzyme activity from heat measurements, which we name initial rate calorimetry (IrCal). This approach is based on our new finding that the data recorded by isothermal titration calorimetry for the early stages of a reaction, which have been widely ignored, are correlated to the initial rates. Application of the IrCal approach to various enzymes led to accurate enzyme kinetics parameters as compared to spectroscopic methods and enabled enzyme kinetic studies with natural substrate, e.g. proteases with protein substrates. Because heat is a label-free property of almost all reactions, the IrCal approach holds promise in fundamental studies of various enzymes and in use of calorimetry for high throughput screening of enzyme activity. PMID:26574737

  14. Towards accurate kinetic modeling of prompt NO formation in hydrocarbon flames via the NCN pathway

    SciTech Connect

    Sutton, Jeffrey A.; Fleming, James W.

    2008-08-15

    A basic kinetic mechanism that can predict the appropriate prompt-NO precursor NCN, as shown by experiment, with relative accuracy while still producing postflame NO results that can be calculated as accurately as or more accurately than through the former HCN pathway is presented for the first time. The basic NCN submechanism should be a starting point for future NCN kinetic and prompt NO formation refinement.

  15. qPIPSA: Relating enzymatic kinetic parameters and interaction fields

    PubMed Central

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

    2007-01-01

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

  16. Obtaining and estimating kinetic parameters from the literature.

    PubMed

    Neves, Susana R

    2011-09-20

    This Teaching Resource provides lecture notes, slides, and a student assignment for a lecture on strategies for the development of mathematical models. Many biological processes can be represented mathematically as systems of ordinary differential equations (ODEs). Simulations with these mathematical models can provide mechanistic insight into the underlying biology of the system. A prerequisite for running simulations, however, is the identification of kinetic parameters that correspond closely with the biological reality. This lecture presents an overview of the steps required for the development of kinetic ODE models and describes experimental methods that can yield kinetic parameters and concentrations of reactants, which are essential for the development of kinetic models. Strategies are provided to extract necessary parameters from published data. The homework assignment requires students to find parameters appropriate for a well-studied biological regulatory system, convert these parameters into appropriate units, and interpret how different values of these parameters may lead to different biological behaviors. PMID:21934111

  17. Obtaining and Estimating Kinetic Parameters from the Literature

    PubMed Central

    Neves, Susana R.

    2014-01-01

    This Teaching Resource provides lecture notes, slides, and a student assignment for a lecture on strategies for the development of mathematical models. Many biological processes can be represented mathematically as systems of ordinary differential equations (ODEs). Simulations with these mathematical models can provide mechanistic insight into the underlying biology of the system. A prerequisite for running simulations, however, is the identification of kinetic parameters that correspond closely with the biological reality. This lecture presents an overview of the steps required for the development of kinetic ODE models and describes experimental methods that can yield kinetic parameters and concentrations of reactants, which are essential for the development of kinetic models. Strategies are provided to extract necessary parameters from published data. The homework assignment requires students to find parameters appropriate for a well-studied biological regulatory system, convert these parameters into appropriate units, and interpret how different values of these parameters may lead to different biological behaviors. PMID:21934111

  18. Accurate lattice parameter measurements of stoichiometric uranium dioxide

    NASA Astrophysics Data System (ADS)

    Leinders, Gregory; Cardinaels, Thomas; Binnemans, Koen; Verwerft, Marc

    2015-04-01

    The paper presents and discusses lattice parameter analyses of pure, stoichiometric UO2. Attention was paid to prepare stoichiometric samples and to maintain stoichiometry throughout the analyses. The lattice parameter of UO2.000±0.001 was evaluated as being 547.127 ± 0.008 pm at 20 °C, which is substantially higher than many published values for the UO2 lattice constant and has an improved precision by about one order of magnitude. The higher value of the lattice constant is mainly attributed to the avoidance of hyperstoichiometry in the present study and to a minor extent to the use of the currently accepted Cu Kα1 X-ray wavelength value. Many of the early studies used Cu Kα1 wavelength values that differ from the currently accepted value, which also contributed to an underestimation of the true lattice parameter.

  19. Clinically accurate fetal ECG parameters acquired from maternal abdominal sensors

    PubMed Central

    CLIFFORD, Gari; SAMENI, Reza; WARD, Mr. Jay; ROBINSON, Julian; WOLFBERG, Adam J.

    2011-01-01

    OBJECTIVE To evaluate the accuracy of a novel system for measuring fetal heart rate and ST-segment changes using non-invasive electrodes on the maternal abdomen. STUDY DESIGN Fetal ECGs were recorded using abdominal sensors from 32 term laboring women who had a fetal scalp electrode (FSE) placed for a clinical indication. RESULTS Good quality data for FHR estimation was available in 91.2% of the FSE segments, and 89.9% of the abdominal electrode segments. The root mean square (RMS) error between the FHR data calculated by both methods over all processed segments was 0.36 beats per minute. ST deviation from the isoelectric point ranged from 0 to 14.2% of R-wave amplitude. The RMS error between the ST change calculated by both methods averaged over all processed segments was 3.2%. CONCLUSION FHR and ST change acquired from the maternal abdomen is highly accurate and on average is clinically indistinguishable from FHR and ST change calculated using FSE data. PMID:21514560

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

    PubMed

    Kumar, B Shiva; Venkateswarlu, Ch

    2014-08-01

    The complex nature of biological reactions in biofilm reactors often poses difficulties in analyzing such reactors experimentally. Mathematical models could be very useful for their design and analysis. However, application of biofilm reactor models to practical problems proves somewhat ineffective due to the lack of knowledge of accurate kinetic models and uncertainty in model parameters. In this work, we propose an inverse modeling approach based on tabu search (TS) to estimate the parameters of kinetic and film thickness models. TS is used to estimate these parameters as a consequence of the validation of the mathematical models of the process with the aid of measured data obtained from an experimental fixed-bed anaerobic biofilm reactor involving the treatment of pharmaceutical industry wastewater. The results evaluated for different modeling configurations of varying degrees of complexity illustrate the effectiveness of TS for accurate estimation of kinetic and film thickness model parameters of the biofilm process. The results show that the two-dimensional mathematical model with Edward kinetics (with its optimum parameters as mu(max)rho(s)/Y = 24.57, Ks = 1.352 and Ki = 102.36) and three-parameter film thickness expression (with its estimated parameters as a = 0.289 x 10(-5), b = 1.55 x 10(-4) and c = 15.2 x 10(-6)) better describes the biofilm reactor treating the industry wastewater. PMID:25306783

  1. Predicting accurate line shape parameters for CO2 transitions

    NASA Astrophysics Data System (ADS)

    Gamache, Robert R.; Lamouroux, Julien

    2013-11-01

    The vibrational dependence of CO2 half-widths and line shifts are given by a modification of the model proposed by Gamache and Hartmann [Gamache R, Hartmann J-M. J Quant Spectrosc Radiat Transfer 2004;83:119]. This model allows the half-widths and line shifts for a ro-vibrational transition to be expressed in terms of the number of vibrational quanta exchanged in the transition raised to a power and a reference ro-vibrational transition. Calculations were made for 24 bands for lower rotational quantum numbers from 0 to 160 for N2-, O2-, air-, and self-collisions with CO2. These data were extrapolated to J″=200 to accommodate several databases. Comparison of the CRB calculations with measurement gives very high confidence in the data. In the model a Quantum Coordinate is defined by (c1 |Δν1|+c2 |Δν2|+c3|Δν3|)p. The power p is adjusted and a linear least-squares fit to the data by the model expression is made. The procedure is iterated on the correlation coefficient, R, until [|R|-1] is less than a threshold. The results demonstrate the appropriateness of the model. The model allows the determination of the slope and intercept as a function of rotational transition, broadening gas, and temperature. From the data of the fits, the half-width, line shift, and the temperature dependence of the half-width can be estimated for any ro-vibrational transition, allowing spectroscopic CO2 databases to have complete information for the line shape parameters.

  2. 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.

  3. 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

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

    PubMed

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

    2014-06-01

    Multiscale methods built purely on the kinetic theory of gases provide information about the molecular velocity distribution function. It is therefore both important and feasible to establish new breakdown parameters for assessing the appropriateness of a fluid description at the continuum level by utilizing kinetic information rather than macroscopic flow quantities alone. We propose a new kinetic criterion to indirectly assess the errors introduced by a continuum-level description of the gas flow. The analysis, which includes numerical demonstrations, focuses on the validity of the Navier-Stokes-Fourier equations and corresponding kinetic models and reveals that the new criterion can consistently indicate the validity of continuum-level modeling in both low-speed and high-speed flows at different Knudsen numbers. PMID:25019910

  5. Second-order accurate kinetic schemes for the ultra-relativistic Euler equations

    NASA Astrophysics Data System (ADS)

    Kunik, Matthias; Qamar, Shamsul; Warnecke, Gerald

    2003-12-01

    A second-order accurate kinetic scheme for the numerical solution of the relativistic Euler equations is presented. These equations describe the flow of a perfect fluid in terms of the particle density n, the spatial part of the four-velocity u and the pressure p. The kinetic scheme, is based on the well-known fact that the relativistic Euler equations are the moments of the relativistic Boltzmann equation of the kinetic theory of gases when the distribution function is a relativistic Maxwellian. The kinetic scheme consists of two phases, the convection phase (free-flight) and collision phase. The velocity distribution function at the end of the free-flight is the solution of the collisionless transport equation. The collision phase instantaneously relaxes the distribution to the local Maxwellian distribution. The fluid dynamic variables of density, velocity, and internal energy are obtained as moments of the velocity distribution function at the end of the free-flight phase. The scheme presented here is an explicit method and unconditionally stable. The conservation laws of mass, momentum and energy as well as the entropy inequality are everywhere exactly satisfied by the solution of the kinetic scheme. The scheme also satisfies positivity and L1-stability. The scheme can be easily made into a total variation diminishing method for the distribution function through a suitable choice of the interpolation strategy. In the numerical case studies the results obtained from the first- and second-order kinetic schemes are compared with the first- and second-order upwind and central schemes. We also calculate the experimental order of convergence and numerical L1-stability of the scheme for smooth initial data.

  6. Determining crystal growth kinetic parameters using optical fibre sensors

    NASA Astrophysics Data System (ADS)

    Boerkamp, M.; Lamb, D. W.; Lye, P. G.

    2012-12-01

    The capability of an 'intrinsic exposed core optical fibre sensor' (IECOFS) as a monitoring device of scale formation has been evaluated. The IECOFS has been used to measure kinetics parameters of calcium carbonate heterogeneous crystal growth such as the activation energy, the crystal growth rate and the induction time. The IECOFS was able to evaluate crystal growth inhibition through the use of chemical inhibitors.

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

    PubMed

    Liu, Fei; Heiner, Monika; Yang, Ming

    2016-01-01

    Stochastic Petri nets (SPNs) have been widely used to model randomness which is an inherent feature of biological systems. However, for many biological systems, some kinetic parameters may be uncertain due to incomplete, vague or missing kinetic data (often called fuzzy uncertainty), or naturally vary, e.g., between different individuals, experimental conditions, etc. (often called variability), which has prevented a wider application of SPNs that require accurate parameters. Considering the strength of fuzzy sets to deal with uncertain information, we apply a specific type of stochastic Petri nets, fuzzy stochastic Petri nets (FSPNs), to model and analyze biological systems with uncertain kinetic parameters. FSPNs combine SPNs and fuzzy sets, thereby taking into account both randomness and fuzziness of biological systems. For a biological system, SPNs model the randomness, while fuzzy sets model kinetic parameters with fuzzy uncertainty or variability by associating each parameter with a fuzzy number instead of a crisp real value. We introduce a simulation-based analysis method for FSPNs to explore the uncertainties of outputs resulting from the uncertainties associated with input parameters, which works equally well for bounded and unbounded models. We illustrate our approach using a yeast polarization model having an infinite state space, which shows the appropriateness of FSPNs in combination with simulation-based analysis for modeling and analyzing biological systems with uncertain information. PMID:26910830

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

    PubMed Central

    Liu, Fei; Heiner, Monika; Yang, Ming

    2016-01-01

    Stochastic Petri nets (SPNs) have been widely used to model randomness which is an inherent feature of biological systems. However, for many biological systems, some kinetic parameters may be uncertain due to incomplete, vague or missing kinetic data (often called fuzzy uncertainty), or naturally vary, e.g., between different individuals, experimental conditions, etc. (often called variability), which has prevented a wider application of SPNs that require accurate parameters. Considering the strength of fuzzy sets to deal with uncertain information, we apply a specific type of stochastic Petri nets, fuzzy stochastic Petri nets (FSPNs), to model and analyze biological systems with uncertain kinetic parameters. FSPNs combine SPNs and fuzzy sets, thereby taking into account both randomness and fuzziness of biological systems. For a biological system, SPNs model the randomness, while fuzzy sets model kinetic parameters with fuzzy uncertainty or variability by associating each parameter with a fuzzy number instead of a crisp real value. We introduce a simulation-based analysis method for FSPNs to explore the uncertainties of outputs resulting from the uncertainties associated with input parameters, which works equally well for bounded and unbounded models. We illustrate our approach using a yeast polarization model having an infinite state space, which shows the appropriateness of FSPNs in combination with simulation-based analysis for modeling and analyzing biological systems with uncertain information. PMID:26910830

  9. Least-squares estimation of batch culture kinetic parameters.

    PubMed

    Ong, S L

    1983-10-01

    This article concerns the development of a simple and effective least-squares procedure for estimating the kinetic parameters in Monod expressions from batch culture data. The basic approach employed in this work was to translate the problem of parameter estimation to a mathematical model containing a single decision variable. The resulting model was then solved by an efficient one-dimensional search algorithm which can be adapted to any microcomputer or advanced programmable calculator. The procedure was tested on synthetic data (substrate concentrations) with different types and levels of error. The effect of endogeneous respiration on the estimated values of the kinetic parameters was also assessed. From the results of these analyses the least-squares procedure developed was concluded to be very effective. PMID:18548565

  10. Are Patient-Specific Joint and Inertial Parameters Necessary for Accurate Inverse Dynamics Analyses of Gait?

    PubMed Central

    Reinbolt, Jeffrey A.; Haftka, Raphael T.; Chmielewski, Terese L.; Fregly, Benjamin J.

    2013-01-01

    Variations in joint parameter values (axis positions and orientations in body segments) and inertial parameter values (segment masses, mass centers, and moments of inertia) as well as kinematic noise alter the results of inverse dynamics analyses of gait. Three-dimensional linkage models with joint constraints have been proposed as one way to minimize the effects of noisy kinematic data. Such models can also be used to perform gait optimizations to predict post-treatment function given pre-treatment gait data. This study evaluates whether accurate patient-specific joint and inertial parameter values are needed in three-dimensional linkage models to produce accurate inverse dynamics results for gait. The study was performed in two stages. First, we used optimization analyses to evaluate whether patient-specific joint and inertial parameter values can be calibrated accurately from noisy kinematic data, and second, we used Monte Carlo analyses to evaluate how errors in joint and inertial parameter values affect inverse dynamics calculations. Both stages were performed using a dynamic, 27 degree-of-freedom, full-body linkage model and synthetic (i.e., computer generated) gait data corresponding to a nominal experimental gait motion. In general, joint but not inertial parameter values could be found accurately from noisy kinematic data. Root-mean-square (RMS) errors were 3° and 4 mm for joint parameter values and 1 kg, 22 mm, and 74,500 kg*mm2 for inertial parameter values. Furthermore, errors in joint but not inertial parameter values had a significant effect on calculated lower-extremity inverse dynamics joint torques. The worst RMS torque error averaged 4% bodyweight*height (BW*H) due to joint parameter variations but less than 0.25% BW*H due to inertial parameter variations. These results suggest that inverse dynamics analyses of gait utilizing linkage models with joint constraints should calibrate the model’s joint parameter values to obtain accurate joint

  11. 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

  12. 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

  13. 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.

  14. Measuring accurate body parameters of dressed humans with large-scale motion using a Kinect sensor.

    PubMed

    Xu, Huanghao; Yu, Yao; Zhou, Yu; Li, Yang; Du, Sidan

    2013-01-01

    Non-contact human body measurement plays an important role in surveillance, physical healthcare, on-line business and virtual fitting. Current methods for measuring the human body without physical contact usually cannot handle humans wearing clothes, which limits their applicability in public environments. In this paper, we propose an effective solution that can measure accurate parameters of the human body with large-scale motion from a Kinect sensor, assuming that the people are wearing clothes. Because motion can drive clothes attached to the human body loosely or tightly, we adopt a space-time analysis to mine the information across the posture variations. Using this information, we recover the human body, regardless of the effect of clothes, and measure the human body parameters accurately. Experimental results show that our system can perform more accurate parameter estimation on the human body than state-of-the-art methods. PMID:24064597

  15. Parallel kinetic Monte Carlo simulation framework incorporating accurate models of adsorbate lateral interactions

    SciTech Connect

    Nielsen, Jens; D’Avezac, Mayeul; Hetherington, James; Stamatakis, Michail

    2013-12-14

    Ab initio kinetic Monte Carlo (KMC) simulations have been successfully applied for over two decades to elucidate the underlying physico-chemical phenomena on the surfaces of heterogeneous catalysts. These simulations necessitate detailed knowledge of the kinetics of elementary reactions constituting the reaction mechanism, and the energetics of the species participating in the chemistry. The information about the energetics is encoded in the formation energies of gas and surface-bound species, and the lateral interactions between adsorbates on the catalytic surface, which can be modeled at different levels of detail. The majority of previous works accounted for only pairwise-additive first nearest-neighbor interactions. More recently, cluster-expansion Hamiltonians incorporating long-range interactions and many-body terms have been used for detailed estimations of catalytic rate [C. Wu, D. J. Schmidt, C. Wolverton, and W. F. Schneider, J. Catal. 286, 88 (2012)]. In view of the increasing interest in accurate predictions of catalytic performance, there is a need for general-purpose KMC approaches incorporating detailed cluster expansion models for the adlayer energetics. We have addressed this need by building on the previously introduced graph-theoretical KMC framework, and we have developed Zacros, a FORTRAN2003 KMC package for simulating catalytic chemistries. To tackle the high computational cost in the presence of long-range interactions we introduce parallelization with OpenMP. We further benchmark our framework by simulating a KMC analogue of the NO oxidation system established by Schneider and co-workers [J. Catal. 286, 88 (2012)]. We show that taking into account only first nearest-neighbor interactions may lead to large errors in the prediction of the catalytic rate, whereas for accurate estimates thereof, one needs to include long-range terms in the cluster expansion.

  16. Nonlinear estimation of Monod growth kinetic parameters from a single substrate depletion curve.

    PubMed Central

    Robinson, J A; Tiedje, J M

    1983-01-01

    Monod growth kinetic parameters were estimated by fitting sigmoidal substrate depletion data to the integrated Monod equation, using nonlinear least-squares analysis. When the initial substrate concentration was in the mixed-order region, nonlinear estimation of simulated data sets containing known measurement errors provided accurate estimates of the mu max, Ks, and Y values used to create these data. Nonlinear regression analysis of sigmoidal substrate depletion data was also evaluated for H2-limited batch growth of Desulfovibrio sp. strain G11. The integrated Monod equation can be more convenient for the estimation of growth kinetic parameters, particularly for gaseous substrates, but it must be recognized that the estimates of mu max, Ks, and Y obtained may be influenced by the growth rate history of the inoculum. PMID:6870238

  17. Study of kinetic parameters in a mechanistic model for bioethanol production through a screening technique and optimization.

    PubMed

    de Andrade, Rafael Ramos; Rivera, Elmer Ccopa; Atala, Daniel I P; Filho, Rubens Maciel; Filho, Francisco Maugeri; Costa, Aline C

    2009-08-01

    The accurate description of the kinetics and robust modeling of biotechnological processes can only be achieved by incorporating reliable methodologies to easily update the model when there are changes in operational conditions. The purpose of this work is to provide a systematic approach with which to perform model parameters screening and updating in biotechnological processes. Batch experiments are performed to develop a mechanistic model, considering the effect of temperature on the kinetics, and further experiments (batch fermentations using sugar cane molasses from a different harvest) are used to validate the effectiveness of screening before parameters updating. The reduction in the number of kinetic parameters to be re-estimated enabled by the screening procedure reduces significantly the complexity of the optimization, which makes the updating procedure to be significantly quicker, while resulting in accurate performance of the updated model. PMID:19125302

  18. A review of the kinetic detail required for accurate predictions of normal shock waves

    NASA Technical Reports Server (NTRS)

    Muntz, E. P.; Erwin, Daniel A.; Pham-Van-diep, Gerald C.

    1991-01-01

    Several aspects of the kinetic models used in the collision phase of Monte Carlo direct simulations have been studied. Accurate molecular velocity distribution function predictions require a significantly increased number of computational cells in one maximum slope shock thickness, compared to predictions of macroscopic properties. The shape of the highly repulsive portion of the interatomic potential for argon is not well modeled by conventional interatomic potentials; this portion of the potential controls high Mach number shock thickness predictions, indicating that the specification of the energetic repulsive portion of interatomic or intermolecular potentials must be chosen with care for correct modeling of nonequilibrium flows at high temperatures. It has been shown for inverse power potentials that the assumption of variable hard sphere scattering provides accurate predictions of the macroscopic properties in shock waves, by comparison with simulations in which differential scattering is employed in the collision phase. On the other hand, velocity distribution functions are not well predicted by the variable hard sphere scattering model for softer potentials at higher Mach numbers.

  19. Accurate and transferable extended Hückel-type tight-binding parameters

    NASA Astrophysics Data System (ADS)

    Cerdá, J.; Soria, F.

    2000-03-01

    We show how the simple extended Hückel theory can be easily parametrized in order to yield accurate band structures for bulk materials, while the resulting optimized atomic orbital basis sets present good transferability properties. The number of parameters involved is exceedingly small, typically ten or eleven per structural phase. We apply the method to almost fifty elemental and compound bulk phases.

  20. Kinetic parameters of composite propellants from thermogravimetric data

    SciTech Connect

    Rao, V.K.; Bardon, M.F.; Stowe, R.A.

    1995-07-01

    This paper presents a method of estimating all three global kinetic parameters, A (preexponential factor), E (energy of activation), and n (reaction order), from the results of a single dynamic (nonisothermal) thermogravimetry (TG) run on a propellant sample. The procedure will also show how satisfactorily pyrolysis of the propellant can be represented by the simple relation of Eq. 4 (d{alpha}/dT = (1{minus}{alpha}){sup n}(A/{phi})e{sup {minus}E/RT}) with constant values of A, E, and n where {alpha} = fractional reaction, T = temperature, {phi} = programmed increase in T, and R = universal gas constant.

  1. 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).

  2. 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.

  3. Evaluation of thermoluminescent kinetics parameters of inorganic dust from the camomile

    NASA Astrophysics Data System (ADS)

    Furetta, C.; Favalli, A.; Zaragoza, E. Cruz; Gomez-Ros, J. M.; Kitis, G.

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

  4. Identification of accurate nonlinear rainfall-runoff models with unique parameters

    NASA Astrophysics Data System (ADS)

    Schoups, G.; Vrugt, J. A.; Fenicia, F.; van de Giesen, N.

    2009-04-01

    We propose a strategy to identify models with unique parameters that yield accurate streamflow predictions, given a time-series of rainfall inputs. The procedure consists of five general steps. First, an a priori range of model structures is specified based on prior general and site-specific hydrologic knowledge. To this end, we rely on a flexible model code that allows a specification of a wide range of model structures, from simple to complex. Second, using global optimization each model structure is calibrated to a record of rainfall-runoff data, yielding optimal parameter values for each model structure. Third, accuracy of each model structure is determined by estimating model prediction errors using independent validation and statistical theory. Fourth, parameter identifiability of each calibrated model structure is estimated by means of Monte Carlo Markov Chain simulation. Finally, an assessment is made about each model structure in terms of its accuracy of mimicking rainfall-runoff processes (step 3), and the uniqueness of its parameters (step 4). The procedure results in the identification of the most complex and accurate model supported by the data, without causing parameter equifinality. As such, it provides insight into the information content of the data for identifying nonlinear rainfall-runoff models. We illustrate the method using rainfall-runoff data records from several MOPEX basins in the US.

  5. Kinetic Parameters of Binary Iron/Oxidant Pyrolants

    NASA Astrophysics Data System (ADS)

    Shamsipur, Mojtaba; Mahdi Pourmortazavi, Seied; Fathollahi, Manochehr

    2012-04-01

    The thermal properties of pyrotechnic mixtures containing iron powder as fuel and KNO3, KClO3, and KClO4 as oxidants are reported. The thermogravimetry-differential thermal analysis results for pure components and corresponding pyrotechnic mixtures revealed that the melting point, decomposition temperature, and rate of oxygen releasing of the oxidants have dominant effects on ignition reaction of the pyrotechnic mixtures. The apparent activation energy and activation parameters for the combustion processes were evaluated from the differential scanning calorimetry experiments. Based on the ignition temperatures obtained and the resulting kinetic data, the thermal reactivity of the pyrotechnic mixtures was found to decrease as in the order Fe + KClO3 > Fe + KNO3 > Fe + KClO4.

  6. 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.

  7. 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.

  8. Parameter Estimation of Ion Current Formulations Requires Hybrid Optimization Approach to Be Both Accurate and Reliable

    PubMed Central

    Loewe, Axel; Wilhelms, Mathias; Schmid, Jochen; Krause, Mathias J.; Fischer, Fathima; Thomas, Dierk; Scholz, Eberhard P.; Dössel, Olaf; Seemann, Gunnar

    2016-01-01

    Computational models of cardiac electrophysiology provided insights into arrhythmogenesis and paved the way toward tailored therapies in the last years. To fully leverage in silico models in future research, these models need to be adapted to reflect pathologies, genetic alterations, or pharmacological effects, however. A common approach is to leave the structure of established models unaltered and estimate the values of a set of parameters. Today’s high-throughput patch clamp data acquisition methods require robust, unsupervised algorithms that estimate parameters both accurately and reliably. In this work, two classes of optimization approaches are evaluated: gradient-based trust-region-reflective and derivative-free particle swarm algorithms. Using synthetic input data and different ion current formulations from the Courtemanche et al. electrophysiological model of human atrial myocytes, we show that neither of the two schemes alone succeeds to meet all requirements. Sequential combination of the two algorithms did improve the performance to some extent but not satisfactorily. Thus, we propose a novel hybrid approach coupling the two algorithms in each iteration. This hybrid approach yielded very accurate estimates with minimal dependency on the initial guess using synthetic input data for which a ground truth parameter set exists. When applied to measured data, the hybrid approach yielded the best fit, again with minimal variation. Using the proposed algorithm, a single run is sufficient to estimate the parameters. The degree of superiority over the other investigated algorithms in terms of accuracy and robustness depended on the type of current. In contrast to the non-hybrid approaches, the proposed method proved to be optimal for data of arbitrary signal to noise ratio. The hybrid algorithm proposed in this work provides an important tool to integrate experimental data into computational models both accurately and robustly allowing to assess the often non

  9. An accurate Fortran code for computing hydrogenic continuum wave functions at a wide range of parameters

    NASA Astrophysics Data System (ADS)

    Peng, Liang-You; Gong, Qihuang

    2010-12-01

    The accurate computations of hydrogenic continuum wave functions are very important in many branches of physics such as electron-atom collisions, cold atom physics, and atomic ionization in strong laser fields, etc. Although there already exist various algorithms and codes, most of them are only reliable in a certain ranges of parameters. In some practical applications, accurate continuum wave functions need to be calculated at extremely low energies, large radial distances and/or large angular momentum number. Here we provide such a code, which can generate accurate hydrogenic continuum wave functions and corresponding Coulomb phase shifts at a wide range of parameters. Without any essential restrict to angular momentum number, the present code is able to give reliable results at the electron energy range [10,10] eV for radial distances of [10,10] a.u. We also find the present code is very efficient, which should find numerous applications in many fields such as strong field physics. Program summaryProgram title: HContinuumGautchi Catalogue identifier: AEHD_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEHD_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 1233 No. of bytes in distributed program, including test data, etc.: 7405 Distribution format: tar.gz Programming language: Fortran90 in fixed format Computer: AMD Processors Operating system: Linux RAM: 20 MBytes Classification: 2.7, 4.5 Nature of problem: The accurate computation of atomic continuum wave functions is very important in many research fields such as strong field physics and cold atom physics. Although there have already existed various algorithms and codes, most of them can only be applicable and reliable in a certain range of parameters. We present here an accurate FORTRAN program for

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

    PubMed

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

    2011-01-01

    In systems biology, experimentally measured parameters are not always available, necessitating the use of computationally based parameter estimation. In order to rely on estimated parameters, it is critical to first determine which parameters can be estimated for a given model and measurement set. This is done with parameter identifiability analysis. A kinetic model of the sucrose accumulation in the sugar cane culm tissue developed by Rohwer et al. was taken as a test case model. What differentiates this approach is the integration of an orthogonal-based local identifiability method into the unscented Kalman filter (UKF), rather than using the more common observability-based method which has inherent limitations. It also introduces a variable step size based on the system uncertainty of the UKF during the sensitivity calculation. This method identified 10 out of 12 parameters as identifiable. These ten parameters were estimated using the UKF, which was run 97 times. Throughout the repetitions the UKF proved to be more consistent than the estimation algorithms used for comparison. PMID:21989173

  11. Kinetic parameters of uracil dosimeter in simulated extraterrestrial UV radiation

    NASA Astrophysics Data System (ADS)

    Kovács, G.; Gróf, P.; Bérces, A.; Patel, M. R.; Lammer, H.; Rontó, Gy.

    Studies of the solar UV environment on Earth 2.0 Gyr to 3.8 Gyr ago suggest that the terrestrial atmosphere was essentially anoxic, resulting in an ozone column abundance insufficient for protecting the planetary surface in the UV-B (280 nm - 315 nm) and the UV-C (200 nm - 280 nm) ranges. Since, short wavelength solar UV radiation in the UV-B and UV-C range penetrated through the atmosphere to the unprotected early Earth's surface, associated biological consequences may be expected. We discuss experimental data obtained as follows: Radiation sources applied were solar simulator and high power deuterium lamp, the wavelength were adjusted by interference filters (210, 230, 250 nm) and the irradiances were measured by OL754 spectroradiometer. The photo-reverse effect depends highly on the wavelength of the exposed radiation. Shorter wavelength UV radiation of about 200 nm is strongly effective in monomerization, while the longer wavelengths prefer the production of dimerization. In case of polychromatic light, like in space or on a planetary surface which is unprotected by an ozone layer the two processes run parallel. We could demonstrate experimentally, for the case of a uracil thin-layer that the photo-reaction process of the nucleotides can be both dimerization and the reverse process: monomerization. These results are important for the study of solar UV effects on organisms in the early terrestrial environment as well as for the search for life on Mars since we can show that biological harmful effects can also be reduced by shorter wavelength UV radiation, which is of importance in reducing DNA damages provoked by wavelengths longer than about 240 nm. Our earlier results showed that dimerization of the pyrimidin base uracil can be described by a first order kinetics, and this reaction gives the possibility to determine the dose of the UV source applied. This work is a theoretical and experimental approach to the relevant parameters of the first order kinetics.

  12. 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.

  13. Accurate optical parameter extraction procedure for broadband near-infrared spectroscopy of brain matter

    PubMed Central

    Najafizadeh, Laleh; Gandjbakhche, Amir H.; Pourrezaei, Kambiz; Daryoush, Afshin

    2013-01-01

    Abstract. Modeling behavior of broadband (30 to 1000 MHz) frequency modulated near-infrared (NIR) photons through a phantom is the basis for accurate extraction of optical absorption and scattering parameters of biological turbid media. Photon dynamics in a phantom are predicted using both analytical and numerical simulation and are related to the measured insertion loss (IL) and insertion phase (IP) for a given geometry based on phantom optical parameters. Accuracy of the extracted optical parameters using finite element method (FEM) simulation is compared to baseline analytical calculations from the diffusion equation (DE) for homogenous brain phantoms. NIR spectroscopy is performed using custom-designed, broadband, free-space optical transmitter (Tx) and receiver (Rx) modules that are developed for photon migration at wavelengths of 680, 780, and 820 nm. Differential detection between two optical Rx locations separated by 0.3 cm is employed to eliminate systemic artifacts associated with interfaces of the optical Tx and Rx with the phantoms. Optical parameter extraction is achieved for four solid phantom samples using the least-square-error method in MATLAB (for DE) and COMSOL (for FEM) simulation by fitting data to measured results over broadband and narrowband frequency modulation. Confidence in numerical modeling of the photonic behavior using FEM has been established here by comparing the transmission mode’s experimental results with the predictions made by DE and FEM for known commercial solid brain phantoms. PMID:23322361

  14. Accurate estimation of motion blur parameters in noisy remote sensing image

    NASA Astrophysics Data System (ADS)

    Shi, Xueyan; Wang, Lin; Shao, Xiaopeng; Wang, Huilin; Tao, Zhong

    2015-05-01

    The relative motion between remote sensing satellite sensor and objects is one of the most common reasons for remote sensing image degradation. It seriously weakens image data interpretation and information extraction. In practice, point spread function (PSF) should be estimated firstly for image restoration. Identifying motion blur direction and length accurately is very crucial for PSF and restoring image with precision. In general, the regular light-and-dark stripes in the spectrum can be employed to obtain the parameters by using Radon transform. However, serious noise existing in actual remote sensing images often causes the stripes unobvious. The parameters would be difficult to calculate and the error of the result relatively big. In this paper, an improved motion blur parameter identification method to noisy remote sensing image is proposed to solve this problem. The spectrum characteristic of noisy remote sensing image is analyzed firstly. An interactive image segmentation method based on graph theory called GrabCut is adopted to effectively extract the edge of the light center in the spectrum. Motion blur direction is estimated by applying Radon transform on the segmentation result. In order to reduce random error, a method based on whole column statistics is used during calculating blur length. Finally, Lucy-Richardson algorithm is applied to restore the remote sensing images of the moon after estimating blur parameters. The experimental results verify the effectiveness and robustness of our algorithm.

  15. 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

  16. Characterization of DuPont photopolymer: determination of kinetic parameters in a diffusion model

    NASA Astrophysics Data System (ADS)

    Moreau, Vincent; Renotte, Yvon; Lion, Yves

    2002-06-01

    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.

  17. A second-order accurate kinetic-theory-based method for inviscid compressible flows

    NASA Technical Reports Server (NTRS)

    Deshpande, Suresh M.

    1986-01-01

    An upwind method for the numerical solution of the Euler equations is presented. This method, called the kinetic numerical method (KNM), is based on the fact that the Euler equations are moments of the Boltzmann equation of the kinetic theory of gases when the distribution function is Maxwellian. The KNM consists of two phases, the convection phase and the collision phase. The method is unconditionally stable and explicit. It is highly vectorizable and can be easily made total variation diminishing for the distribution function by a suitable choice of the interpolation strategy. The method is applied to a one-dimensional shock-propagation problem and to a two-dimensional shock-reflection problem.

  18. Exact kinetic energy enables accurate evaluation of weak interactions by the FDE-vdW method

    SciTech Connect

    Sinha, Debalina; Pavanello, Michele

    2015-08-28

    The correlation energy of interaction is an elusive and sought-after interaction between molecular systems. By partitioning the response function of the system into subsystem contributions, the Frozen Density Embedding (FDE)-vdW method provides a computationally amenable nonlocal correlation functional based on the adiabatic connection fluctuation dissipation theorem applied to subsystem density functional theory. In reproducing potential energy surfaces of weakly interacting dimers, we show that FDE-vdW, either employing semilocal or exact nonadditive kinetic energy functionals, is in quantitative agreement with high-accuracy coupled cluster calculations (overall mean unsigned error of 0.5 kcal/mol). When employing the exact kinetic energy (which we term the Kohn-Sham (KS)-vdW method), the binding energies are generally closer to the benchmark, and the energy surfaces are also smoother.

  19. 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

  20. Precise and accurate assessment of uncertainties in model parameters from stellar interferometry. Application to stellar diameters

    NASA Astrophysics Data System (ADS)

    Lachaume, Regis; Rabus, Markus; Jordan, Andres

    2015-08-01

    In stellar interferometry, the assumption that the observables can be seen as Gaussian, independent variables is the norm. In particular, neither the optical interferometry FITS (OIFITS) format nor the most popular fitting software in the field, LITpro, offer means to specify a covariance matrix or non-Gaussian uncertainties. Interferometric observables are correlated by construct, though. Also, the calibration by an instrumental transfer function ensures that the resulting observables are not Gaussian, even if uncalibrated ones happened to be so.While analytic frameworks have been published in the past, they are cumbersome and there is no generic implementation available. We propose here a relatively simple way of dealing with correlated errors without the need to extend the OIFITS specification or making some Gaussian assumptions. By repeatedly picking at random which interferograms, which calibrator stars, and which are the errors on their diameters, and performing the data processing on the bootstrapped data, we derive a sampling of p(O), the multivariate probability density function (PDF) of the observables O. The results can be stored in a normal OIFITS file. Then, given a model m with parameters P predicting observables O = m(P), we can estimate the PDF of the model parameters f(P) = p(m(P)) by using a density estimation of the observables' PDF p.With observations repeated over different baselines, on nights several days apart, and with a significant set of calibrators systematic errors are de facto taken into account. We apply the technique to a precise and accurate assessment of stellar diameters obtained at the Very Large Telescope Interferometer with PIONIER.

  1. Significance of accurate diffraction corrections for the second harmonic wave in determining the acoustic nonlinearity parameter

    SciTech Connect

    Jeong, Hyunjo; Zhang, Shuzeng; Li, Xiongbing; Barnard, Dan

    2015-09-15

    The accurate measurement of acoustic nonlinearity parameter β for fluids or solids generally requires making corrections for diffraction effects due to finite size geometry of transmitter and receiver. These effects are well known in linear acoustics, while those for second harmonic waves have not been well addressed and therefore not properly considered in previous studies. In this work, we explicitly define the attenuation and diffraction corrections using the multi-Gaussian beam (MGB) equations which were developed from the quasilinear solutions of the KZK equation. The effects of making these corrections are examined through the simulation of β determination in water. Diffraction corrections are found to have more significant effects than attenuation corrections, and the β values of water can be estimated experimentally with less than 5% errors when the exact second harmonic diffraction corrections are used together with the negligible attenuation correction effects on the basis of linear frequency dependence between attenuation coefficients, α{sub 2} ≃ 2α{sub 1}.

  2. Accurate parameters for HD 209458 and its planet from HST spectrophotometry

    NASA Astrophysics Data System (ADS)

    del Burgo, C.; Allende Prieto, C.

    2016-08-01

    We present updated parameters for the star HD 209458 and its transiting giant planet. The stellar angular diameter θ=0.2254±0.0017 mas is obtained from the average ratio between the absolute flux observed with the Hubble Space Telescope and that of the best-fitting Kurucz model atmosphere. This angular diameter represents an improvement in precision of more than four times compared to available interferometric determinations. The stellar radius R⋆=1.20±0.05 R⊙ is ascertained by combining the angular diameter with the Hipparcos trigonometric parallax, which is the main contributor to its uncertainty, and therefore the radius accuracy should be significantly improved with Gaia's measurements. The radius of the exoplanet Rp=1.41±0.06 RJ is derived from the corresponding transit depth in the light curve and our stellar radius. From the model fitting, we accurately determine the effective temperature, Teff=6071±20 K, which is in perfect agreement with the value of 6070±24 K calculated from the angular diameter and the integrated spectral energy distribution. We also find precise values from recent Padova Isochrones, such as R⋆=1.20±0.06 R⊙ and Teff=6099±41 K. We arrive at a consistent picture from these methods and compare the results with those from the literature.

  3. Consistency of VDJ Rearrangement and Substitution Parameters Enables Accurate B Cell Receptor Sequence Annotation

    PubMed Central

    Ralph, Duncan K.; Matsen, Frederick A.

    2016-01-01

    VDJ rearrangement and somatic hypermutation work together to produce antibody-coding B cell receptor (BCR) sequences for a remarkable diversity of antigens. It is now possible to sequence these BCRs in high throughput; analysis of these sequences is bringing new insight into how antibodies develop, in particular for broadly-neutralizing antibodies against HIV and influenza. A fundamental step in such sequence analysis is to annotate each base as coming from a specific one of the V, D, or J genes, or from an N-addition (a.k.a. non-templated insertion). Previous work has used simple parametric distributions to model transitions from state to state in a hidden Markov model (HMM) of VDJ recombination, and assumed that mutations occur via the same process across sites. However, codon frame and other effects have been observed to violate these parametric assumptions for such coding sequences, suggesting that a non-parametric approach to modeling the recombination process could be useful. In our paper, we find that indeed large modern data sets suggest a model using parameter-rich per-allele categorical distributions for HMM transition probabilities and per-allele-per-position mutation probabilities, and that using such a model for inference leads to significantly improved results. We present an accurate and efficient BCR sequence annotation software package using a novel HMM “factorization” strategy. This package, called partis (https://github.com/psathyrella/partis/), is built on a new general-purpose HMM compiler that can perform efficient inference given a simple text description of an HMM. PMID:26751373

  4. Consistency of VDJ Rearrangement and Substitution Parameters Enables Accurate B Cell Receptor Sequence Annotation.

    PubMed

    Ralph, Duncan K; Matsen, Frederick A

    2016-01-01

    VDJ rearrangement and somatic hypermutation work together to produce antibody-coding B cell receptor (BCR) sequences for a remarkable diversity of antigens. It is now possible to sequence these BCRs in high throughput; analysis of these sequences is bringing new insight into how antibodies develop, in particular for broadly-neutralizing antibodies against HIV and influenza. A fundamental step in such sequence analysis is to annotate each base as coming from a specific one of the V, D, or J genes, or from an N-addition (a.k.a. non-templated insertion). Previous work has used simple parametric distributions to model transitions from state to state in a hidden Markov model (HMM) of VDJ recombination, and assumed that mutations occur via the same process across sites. However, codon frame and other effects have been observed to violate these parametric assumptions for such coding sequences, suggesting that a non-parametric approach to modeling the recombination process could be useful. In our paper, we find that indeed large modern data sets suggest a model using parameter-rich per-allele categorical distributions for HMM transition probabilities and per-allele-per-position mutation probabilities, and that using such a model for inference leads to significantly improved results. We present an accurate and efficient BCR sequence annotation software package using a novel HMM "factorization" strategy. This package, called partis (https://github.com/psathyrella/partis/), is built on a new general-purpose HMM compiler that can perform efficient inference given a simple text description of an HMM. PMID:26751373

  5. 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…

  6. Differential scanning calorimetry in determining kinetics parameter of Si oxidation

    NASA Astrophysics Data System (ADS)

    Faruque, Sk. Abdul Kader Md.; Chakraborty, Supratic

    2016-05-01

    Differential scanning calorimetry (DSC) technique is employed here to study the oxidation of silicon by solid-gas reaction at a constant heating rate. The diffusion coefficient of oxygen into silicon at 900 °C is estimated from the kinetic equation of 1-dimensional diffusion controlled growth. The diffusion coefficient, D estimated as 4.5 × 10-5 exp (1.01ev/κBT) m2/s, as is in well agreement with the standard value available in literature.

  7. Accurate analytical method for the extraction of solar cell model parameters

    NASA Astrophysics Data System (ADS)

    Phang, J. C. H.; Chan, D. S. H.; Phillips, J. R.

    1984-05-01

    Single diode solar cell model parameters are rapidly extracted from experimental data by means of the presently derived analytical expressions. The parameter values obtained have a less than 5 percent error for most solar cells, in light of the extraction of model parameters for two cells of differing quality which were compared with parameters extracted by means of the iterative method.

  8. Multiple apolipoprotein kinetics measured in human HDL by high-resolution/accurate mass parallel reaction monitoring.

    PubMed

    Singh, Sasha A; Andraski, Allison B; Pieper, Brett; Goh, Wilson; Mendivil, Carlos O; Sacks, Frank M; Aikawa, Masanori

    2016-04-01

    Endogenous labeling with stable isotopes is used to study the metabolism of proteins in vivo. However, traditional detection methods such as GC/MS cannot measure tracer enrichment in multiple proteins simultaneously, and multiple reaction monitoring MS cannot measure precisely the low tracer enrichment in slowly turning-over proteins as in HDL. We exploited the versatility of the high-resolution/accurate mass (HR/AM) quadrupole Orbitrap for proteomic analysis of five HDL sizes. We identified 58 proteins in HDL that were shared among three humans and that were organized into five subproteomes according to HDL size. For seven of these proteins, apoA-I, apoA-II, apoA-IV, apoC-III, apoD, apoE, and apoM, we performed parallel reaction monitoring (PRM) to measure trideuterated leucine tracer enrichment between 0.03 to 1.0% in vivo, as required to study their metabolism. The results were suitable for multicompartmental modeling in all except apoD. These apolipoproteins in each HDL size mainly originated directly from the source compartment, presumably the liver and intestine. Flux of apolipoproteins from smaller to larger HDL or the reverse contributed only slightly to apolipoprotein metabolism. These novel findings on HDL apolipoprotein metabolism demonstrate the analytical breadth and scope of the HR/AM-PRM technology to perform metabolic research. PMID:26862155

  9. k-Cone analysis: determining all candidate values for kinetic parameters on a network scale.

    PubMed

    Famili, Iman; Mahadevan, Radhakrishnan; Palsson, Bernhard O

    2005-03-01

    The absence of comprehensive measured kinetic values and the observed inconsistency in the available in vitro kinetic data has hindered the formulation of network-scale kinetic models of biochemical reaction networks. To meet this challenge we present an approach to construct a convex space, termed the k-cone, which contains all the allowable numerical values of the kinetic constants in large-scale biochemical networks. The definition of the k-cone relies on the incorporation of in vivo concentration data and a simplified approach to represent enzyme kinetics within an established constraint-based modeling approach. The k-cone approach was implemented to define the allowable combination of numerical values for a full kinetic model of human red blood cell metabolism and to study its correlated kinetic parameters. The k-cone approach can be used to determine consistency between in vitro measured kinetic values and in vivo concentration and flux measurements when used in a network-scale kinetic model. k-Cone analysis was successful in determining whether in vitro measured kinetic values used in the reconstruction of a kinetic-based model of Saccharomyces cerevisiae central metabolism could reproduce in vivo measurements. Further, the k-cone can be used to determine which numerical values of in vitro measured parameters are required to be changed in a kinetic model if in vivo measured values are not reproduced. k-Cone analysis could identify what minimum number of in vitro determined kinetic parameters needed to be adjusted in the S. cerevisiae model to be consistent with the in vivo data. Applying the k-cone analysis a priori to kinetic model development may reduce the time and effort involved in model building and parameter adjustment. With the recent developments in high-throughput profiling of metabolite concentrations at a whole-cell scale and advances in metabolomics technologies, the k-cone approach presented here may hold the promise for kinetic

  10. k-Cone Analysis: Determining All Candidate Values for Kinetic Parameters on a Network Scale

    PubMed Central

    Famili, Iman; Mahadevan, Radhakrishnan; Palsson, Bernhard O.

    2005-01-01

    The absence of comprehensive measured kinetic values and the observed inconsistency in the available in vitro kinetic data has hindered the formulation of network-scale kinetic models of biochemical reaction networks. To meet this challenge we present an approach to construct a convex space, termed the k-cone, which contains all the allowable numerical values of the kinetic constants in large-scale biochemical networks. The definition of the k-cone relies on the incorporation of in vivo concentration data and a simplified approach to represent enzyme kinetics within an established constraint-based modeling approach. The k-cone approach was implemented to define the allowable combination of numerical values for a full kinetic model of human red blood cell metabolism and to study its correlated kinetic parameters. The k-cone approach can be used to determine consistency between in vitro measured kinetic values and in vivo concentration and flux measurements when used in a network-scale kinetic model. k-Cone analysis was successful in determining whether in vitro measured kinetic values used in the reconstruction of a kinetic-based model of Saccharomyces cerevisiae central metabolism could reproduce in vivo measurements. Further, the k-cone can be used to determine which numerical values of in vitro measured parameters are required to be changed in a kinetic model if in vivo measured values are not reproduced. k-Cone analysis could identify what minimum number of in vitro determined kinetic parameters needed to be adjusted in the S. cerevisiae model to be consistent with the in vivo data. Applying the k-cone analysis a priori to kinetic model development may reduce the time and effort involved in model building and parameter adjustment. With the recent developments in high-throughput profiling of metabolite concentrations at a whole-cell scale and advances in metabolomics technologies, the k-cone approach presented here may hold the promise for kinetic

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

    PubMed Central

    Brito, Paula M.; Antunes, Fernando

    2014-01-01

    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 toward 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 underlie the interplay between oxidative stress and redox signaling responses. PMID:25325054

  12. 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…

  13. Validity of repeated initial rise thermoluminescence kinetic parameter determinations

    SciTech Connect

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

    1990-01-01

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

  14. Simultaneous determination of kinetic and thermodynamic parameters from fast-reaction kinetic measurements.

    PubMed

    Trimm, H H; Ushio, H; Patel, R C

    1981-10-01

    A combined stopped-flow temperature-jump apparatus interfaced with a dedicated microcomputer has been used to study the complexation reaction of iron(III) with thiocyanate in aqueous solution. Kinetic rate-constants (k(f) = 143 l.mole(-1) .sec(-1) from T-jump, k(f) = 150 l.mole(-1) .sec(-1) from stopped flow), equilibrium constants (K = 143 from T-jump, K = 150 from stopped flow) and the thermodynamic enthalpy change (DeltaH(c) = -6.7 kJ/mole) could be independently determined from the simultaneous application of the two techniques. PMID:18962997

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

    PubMed

    Huang, Lihan

    2015-02-16

    The objective of this research was to develop a new one-step methodology that uses a dynamic approach to directly construct a tertiary model for prediction of the growth of Clostridium perfringens in cooked beef. This methodology was based on simultaneous numerical analysis and optimization of both primary and secondary models using multiple dynamic growth curves obtained under different conditions. Once the models were constructed, the bootstrap method was used to calculate the 95% confidence intervals of kinetic parameters, and a Monte Carlo simulation method was developed to validate the models using the growth curves not previously used in model development. The results showed that the kinetic parameters obtained from this study accurately matched the common characteristics of C. perfringens, with the optimum temperature being 45.3°C. The results also showed that the predicted growth curves matched accurately with experimental observations used in validation. The mean of residuals of the predictions is -0.02logCFU/g, with a standard deviation of only 0.23logCFU/g. For relative growths <1logCFU/g, the residuals of predictions are <0.4logCFU/g. Overall, 74% of the residuals of predictions are <0.2logCFU/g, 7.7% are >0.4logCFU/g, while only 1.5% are >0.8logCFU/g. In addition, the dynamic model also accurately predicted four isothermal growth curves arbitrarily chosen from the literature. Finally, the Monte Carlo simulation was used to provide the probability of >1 and 2logCFU/g relative growths at the end of cooling. The results of this study will provide a new and accurate tool to the food industry and regulatory agencies to assess the safety of cooked beef in the event of cooling deviation. PMID:25500276

  16. Polynomial Fitting of DT-MRI Fiber Tracts Allows Accurate Estimation of Muscle Architectural Parameters

    PubMed Central

    Damon, Bruce M.; Heemskerk, Anneriet M.; Ding, Zhaohua

    2012-01-01

    Fiber curvature is a functionally significant muscle structural property, but its estimation from diffusion-tensor MRI fiber tracking data may be confounded by noise. The purpose of this study was to investigate the use of polynomial fitting of fiber tracts for improving the accuracy and precision of fiber curvature (κ) measurements. Simulated image datasets were created in order to provide data with known values for κ and pennation angle (θ). Simulations were designed to test the effects of increasing inherent fiber curvature (3.8, 7.9, 11.8, and 15.3 m−1), signal-to-noise ratio (50, 75, 100, and 150), and voxel geometry (13.8 and 27.0 mm3 voxel volume with isotropic resolution; 13.5 mm3 volume with an aspect ratio of 4.0) on κ and θ measurements. In the originally reconstructed tracts, θ was estimated accurately under most curvature and all imaging conditions studied; however, the estimates of κ were imprecise and inaccurate. Fitting the tracts to 2nd order polynomial functions provided accurate and precise estimates of κ for all conditions except very high curvature (κ=15.3 m−1), while preserving the accuracy of the θ estimates. Similarly, polynomial fitting of in vivo fiber tracking data reduced the κ values of fitted tracts from those of unfitted tracts and did not change the θ values. Polynomial fitting of fiber tracts allows accurate estimation of physiologically reasonable values of κ, while preserving the accuracy of θ estimation. PMID:22503094

  17. Accurate Atmospheric Parameters at Moderate Resolution Using Spectral Indices: Preliminary Application to the MARVELS Survey

    NASA Astrophysics Data System (ADS)

    Ghezzi, Luan; Dutra-Ferreira, Letícia; Lorenzo-Oliveira, Diego; Porto de Mello, Gustavo F.; Santiago, Basílio X.; De Lee, Nathan; Lee, Brian L.; da Costa, Luiz N.; Maia, Marcio A. G.; Ogando, Ricardo L. C.; Wisniewski, John P.; González Hernández, Jonay I.; Stassun, Keivan G.; Fleming, Scott W.; Schneider, Donald P.; Mahadevan, Suvrath; Cargile, Phillip; Ge, Jian; Pepper, Joshua; Wang, Ji; Paegert, Martin

    2014-12-01

    Studies of Galactic chemical, and dynamical evolution in the solar neighborhood depend on the availability of precise atmospheric parameters (effective temperature T eff, metallicity [Fe/H], and surface gravity log g) for solar-type stars. Many large-scale spectroscopic surveys operate at low to moderate spectral resolution for efficiency in observing large samples, which makes the stellar characterization difficult due to the high degree of blending of spectral features. Therefore, most surveys employ spectral synthesis, which is a powerful technique, but relies heavily on the completeness and accuracy of atomic line databases and can yield possibly correlated atmospheric parameters. In this work, we use an alternative method based on spectral indices to determine the atmospheric parameters of a sample of nearby FGK dwarfs and subgiants observed by the MARVELS survey at moderate resolving power (R ~ 12,000). To avoid a time-consuming manual analysis, we have developed three codes to automatically normalize the observed spectra, measure the equivalent widths of the indices, and, through a comparison of those with values calculated with predetermined calibrations, estimate the atmospheric parameters of the stars. The calibrations were derived using a sample of 309 stars with precise stellar parameters obtained from the analysis of high-resolution FEROS spectra, permitting the low-resolution equivalent widths to be directly related to the stellar parameters. A validation test of the method was conducted with a sample of 30 MARVELS targets that also have reliable atmospheric parameters derived from the high-resolution spectra and spectroscopic analysis based on the excitation and ionization equilibria method. Our approach was able to recover the parameters within 80 K for T eff, 0.05 dex for [Fe/H], and 0.15 dex for log g, values that are lower than or equal to the typical external uncertainties found between different high-resolution analyses. An additional test was

  18. Accurate atmospheric parameters at moderate resolution using spectral indices: Preliminary application to the marvels survey

    SciTech Connect

    Ghezzi, Luan; Da Costa, Luiz N.; Maia, Marcio A. G.; Ogando, Ricardo L. C.; Dutra-Ferreira, Letícia; Lorenzo-Oliveira, Diego; Porto de Mello, Gustavo F.; Santiago, Basílio X.; De Lee, Nathan; Lee, Brian L.; Ge, Jian; Wisniewski, John P.; González Hernández, Jonay I.; Stassun, Keivan G.; Cargile, Phillip; Pepper, Joshua; Fleming, Scott W.; Schneider, Donald P.; Mahadevan, Suvrath; Wang, Ji; and others

    2014-12-01

    Studies of Galactic chemical, and dynamical evolution in the solar neighborhood depend on the availability of precise atmospheric parameters (effective temperature T {sub eff}, metallicity [Fe/H], and surface gravity log g) for solar-type stars. Many large-scale spectroscopic surveys operate at low to moderate spectral resolution for efficiency in observing large samples, which makes the stellar characterization difficult due to the high degree of blending of spectral features. Therefore, most surveys employ spectral synthesis, which is a powerful technique, but relies heavily on the completeness and accuracy of atomic line databases and can yield possibly correlated atmospheric parameters. In this work, we use an alternative method based on spectral indices to determine the atmospheric parameters of a sample of nearby FGK dwarfs and subgiants observed by the MARVELS survey at moderate resolving power (R ∼ 12,000). To avoid a time-consuming manual analysis, we have developed three codes to automatically normalize the observed spectra, measure the equivalent widths of the indices, and, through a comparison of those with values calculated with predetermined calibrations, estimate the atmospheric parameters of the stars. The calibrations were derived using a sample of 309 stars with precise stellar parameters obtained from the analysis of high-resolution FEROS spectra, permitting the low-resolution equivalent widths to be directly related to the stellar parameters. A validation test of the method was conducted with a sample of 30 MARVELS targets that also have reliable atmospheric parameters derived from the high-resolution spectra and spectroscopic analysis based on the excitation and ionization equilibria method. Our approach was able to recover the parameters within 80 K for T {sub eff}, 0.05 dex for [Fe/H], and 0.15 dex for log g, values that are lower than or equal to the typical external uncertainties found between different high-resolution analyses. An

  19. FAST TRACK COMMUNICATION Accurate estimate of α variation and isotope shift parameters in Na and Mg+

    NASA Astrophysics Data System (ADS)

    Sahoo, B. K.

    2010-12-01

    We present accurate calculations of fine-structure constant variation coefficients and isotope shifts in Na and Mg+ using the relativistic coupled-cluster method. In our approach, we are able to discover the roles of various correlation effects explicitly to all orders in these calculations. Most of the results, especially for the excited states, are reported for the first time. It is possible to ascertain suitable anchor and probe lines for the studies of possible variation in the fine-structure constant by using the above results in the considered systems.

  20. 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)

  1. Accurate nuclear masses from a three parameter Kohn-Sham DFT approach (BCPM)

    SciTech Connect

    Baldo, M.; Robledo, L. M.; Schuck, P.; Vinas, X.

    2012-10-20

    Given the promising features of the recently proposed Barcelona-Catania-Paris (BCP) functional [1], it is the purpose of this work to still improve on it. It is, for instance, shown that the number of open parameters can be reduced from 4-5 to 2-3, i.e. by practically a factor of two without deteriorating the results.

  2. Accurate parameters of the oldest known rocky-exoplanet hosting system: Kepler-10 revisited

    SciTech Connect

    Fogtmann-Schulz, Alexandra; Hinrup, Brian; Van Eylen, Vincent; Christensen-Dalsgaard, Jørgen; Kjeldsen, Hans; Silva Aguirre, Víctor; Tingley, Brandon

    2014-02-01

    Since the discovery of Kepler-10, the system has received considerable interest because it contains a small, rocky planet which orbits the star in less than a day. The system's parameters, announced by the Kepler team and subsequently used in further research, were based on only five months of data. We have reanalyzed this system using the full span of 29 months of Kepler photometric data, and obtained improved information about its star and the planets. A detailed asteroseismic analysis of the extended time series provides a significant improvement on the stellar parameters: not only can we state that Kepler-10 is the oldest known rocky-planet-harboring system at 10.41 ± 1.36 Gyr, but these parameters combined with improved planetary parameters from new transit fits gives us the radius of Kepler-10b to within just 125 km. A new analysis of the full planetary phase curve leads to new estimates on the planetary temperature and albedo, which remain degenerate in the Kepler band. Our modeling suggests that the flux level during the occultation is slightly lower than at the transit wings, which would imply that the nightside of this planet has a non-negligible temperature.

  3. Towards the computations of accurate spectroscopic parameters and vibrational spectra for organic compounds

    NASA Astrophysics Data System (ADS)

    Hochlaf, M.; Puzzarini, C.; Senent, M. L.

    2015-07-01

    We present multi-component computations for rotational constants, vibrational and torsional levels of medium-sized molecules. Through the treatment of two organic sulphur molecules, ethyl mercaptan and dimethyl sulphide, which are relevant for atmospheric and astrophysical media, we point out the outstanding capabilities of explicitly correlated coupled clusters (CCSD(T)-F12) method in conjunction with the cc-pVTZ-F12 basis set for the accurate predictions of such quantities. Indeed, we show that the CCSD(T)-F12/cc-pVTZ-F12 equilibrium rotational constants are in good agreement with those obtained by means of a composite scheme based on CCSD(T) calculations that accounts for the extrapolation to the complete basis set (CBS) limit and core-correlation effects [CCSD(T)/CBS+CV], thus leading to values of ground-state rotational constants rather close to the corresponding experimental data. For vibrational and torsional levels, our analysis reveals that the anharmonic frequencies derived from CCSD(T)-F12/cc-pVTZ-F12 harmonic frequencies and anharmonic corrections (Δν = ω - ν) at the CCSD/cc-pVTZ level closely agree with experimental results. The pattern of the torsional transitions and the shape of the potential energy surfaces along the torsional modes are also well reproduced using the CCSD(T)-F12/cc-pVTZ-F12 energies. Interestingly, this good accuracy is accompanied with a strong reduction of the computational costs. This makes the procedures proposed here as schemes of choice for effective and accurate prediction of spectroscopic properties of organic compounds. Finally, popular density functional approaches are compared with the coupled cluster (CC) methodologies in torsional studies. The long-range CAM-B3LYP functional of Handy and co-workers is recommended for large systems.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  5. Lower bound on reliability for Weibull distribution when shape parameter is not estimated accurately

    NASA Technical Reports Server (NTRS)

    Huang, Zhaofeng; Porter, Albert A.

    1991-01-01

    The mathematical relationships between the shape parameter Beta and estimates of reliability and a life limit lower bound for the two parameter Weibull distribution are investigated. It is shown that under rather general conditions, both the reliability lower bound and the allowable life limit lower bound (often called a tolerance limit) have unique global minimums over a range of Beta. Hence lower bound solutions can be obtained without assuming or estimating Beta. The existence and uniqueness of these lower bounds are proven. Some real data examples are given to show how these lower bounds can be easily established and to demonstrate their practicality. The method developed here has proven to be extremely useful when using the Weibull distribution in analysis of no-failure or few-failures data. The results are applicable not only in the aerospace industry but anywhere that system reliabilities are high.

  6. Lower bound on reliability for Weibull distribution when shape parameter is not estimated accurately

    NASA Technical Reports Server (NTRS)

    Huang, Zhaofeng; Porter, Albert A.

    1990-01-01

    The mathematical relationships between the shape parameter Beta and estimates of reliability and a life limit lower bound for the two parameter Weibull distribution are investigated. It is shown that under rather general conditions, both the reliability lower bound and the allowable life limit lower bound (often called a tolerance limit) have unique global minimums over a range of Beta. Hence lower bound solutions can be obtained without assuming or estimating Beta. The existence and uniqueness of these lower bounds are proven. Some real data examples are given to show how these lower bounds can be easily established and to demonstrate their practicality. The method developed here has proven to be extremely useful when using the Weibull distribution in analysis of no-failure or few-failures data. The results are applicable not only in the aerospace industry but anywhere that system reliabilities are high.

  7. 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.

  8. Accurate Prediction of Severe Allergic Reactions by a Small Set of Environmental Parameters (NDVI, Temperature)

    PubMed Central

    Andrianaki, Maria; Azariadis, Kalliopi; Kampouri, Errika; Theodoropoulou, Katerina; Lavrentaki, Katerina; Kastrinakis, Stelios; Kampa, Marilena; Agouridakis, Panagiotis; Pirintsos, Stergios; Castanas, Elias

    2015-01-01

    Severe allergic reactions of unknown etiology,necessitating a hospital visit, have an important impact in the life of affected individuals and impose a major economic burden to societies. The prediction of clinically severe allergic reactions would be of great importance, but current attempts have been limited by the lack of a well-founded applicable methodology and the wide spatiotemporal distribution of allergic reactions. The valid prediction of severe allergies (and especially those needing hospital treatment) in a region, could alert health authorities and implicated individuals to take appropriate preemptive measures. In the present report we have collecterd visits for serious allergic reactions of unknown etiology from two major hospitals in the island of Crete, for two distinct time periods (validation and test sets). We have used the Normalized Difference Vegetation Index (NDVI), a satellite-based, freely available measurement, which is an indicator of live green vegetation at a given geographic area, and a set of meteorological data to develop a model capable of describing and predicting severe allergic reaction frequency. Our analysis has retained NDVI and temperature as accurate identifiers and predictors of increased hospital severe allergic reactions visits. Our approach may contribute towards the development of satellite-based modules, for the prediction of severe allergic reactions in specific, well-defined geographical areas. It could also probably be used for the prediction of other environment related diseases and conditions. PMID:25794106

  9. An Accurate and Generic Testing Approach to Vehicle Stability Parameters Based on GPS and INS

    PubMed Central

    Miao, Zhibin; Zhang, Hongtian; Zhang, Jinzhu

    2015-01-01

    With the development of the vehicle industry, controlling stability has become more and more important. Techniques of evaluating vehicle stability are in high demand. As a common method, usually GPS sensors and INS sensors are applied to measure vehicle stability parameters by fusing data from the two system sensors. Although prior model parameters should be recognized in a Kalman filter, it is usually used to fuse data from multi-sensors. In this paper, a robust, intelligent and precise method to the measurement of vehicle stability is proposed. First, a fuzzy interpolation method is proposed, along with a four-wheel vehicle dynamic model. Second, a two-stage Kalman filter, which fuses the data from GPS and INS, is established. Next, this approach is applied to a case study vehicle to measure yaw rate and sideslip angle. The results show the advantages of the approach. Finally, a simulation and real experiment is made to verify the advantages of this approach. The experimental results showed the merits of this method for measuring vehicle stability, and the approach can meet the design requirements of a vehicle stability controller. PMID:26690154

  10. An Accurate and Generic Testing Approach to Vehicle Stability Parameters Based on GPS and INS.

    PubMed

    Miao, Zhibin; Zhang, Hongtian; Zhang, Jinzhu

    2015-01-01

    With the development of the vehicle industry, controlling stability has become more and more important. Techniques of evaluating vehicle stability are in high demand. As a common method, usually GPS sensors and INS sensors are applied to measure vehicle stability parameters by fusing data from the two system sensors. Although prior model parameters should be recognized in a Kalman filter, it is usually used to fuse data from multi-sensors. In this paper, a robust, intelligent and precise method to the measurement of vehicle stability is proposed. First, a fuzzy interpolation method is proposed, along with a four-wheel vehicle dynamic model. Second, a two-stage Kalman filter, which fuses the data from GPS and INS, is established. Next, this approach is applied to a case study vehicle to measure yaw rate and sideslip angle. The results show the advantages of the approach. Finally, a simulation and real experiment is made to verify the advantages of this approach. The experimental results showed the merits of this method for measuring vehicle stability, and the approach can meet the design requirements of a vehicle stability controller. PMID:26690154

  11. Accurate motion parameter estimation for colonoscopy tracking using a regression method

    NASA Astrophysics Data System (ADS)

    Liu, Jianfei; Subramanian, Kalpathi R.; Yoo, Terry S.

    2010-03-01

    Co-located optical and virtual colonoscopy images have the potential to provide important clinical information during routine colonoscopy procedures. In our earlier work, we presented an optical flow based algorithm to compute egomotion from live colonoscopy video, permitting navigation and visualization of the corresponding patient anatomy. In the original algorithm, motion parameters were estimated using the traditional Least Sum of squares(LS) procedure which can be unstable in the context of optical flow vectors with large errors. In the improved algorithm, we use the Least Median of Squares (LMS) method, a robust regression method for motion parameter estimation. Using the LMS method, we iteratively analyze and converge toward the main distribution of the flow vectors, while disregarding outliers. We show through three experiments the improvement in tracking results obtained using the LMS method, in comparison to the LS estimator. The first experiment demonstrates better spatial accuracy in positioning the virtual camera in the sigmoid colon. The second and third experiments demonstrate the robustness of this estimator, resulting in longer tracked sequences: from 300 to 1310 in the ascending colon, and 410 to 1316 in the transverse colon.

  12. Accurate solutions, parameter studies and comparisons for the Euler and potential flow equations

    NASA Technical Reports Server (NTRS)

    Anderson, W. Kyle; Batina, John T.

    1988-01-01

    Parameter studies are conducted using the Euler and potential flow equation models for steady and unsteady flows in both two and three dimensions. The Euler code is an implicit, upwind, finite volume code which uses the Van Leer method of flux vector splitting which has been recently extended for use on dynamic meshes and maintain all the properties of the original splitting. The potential flow code is an implicit, finite difference method for solving the transonic small disturbance equations and incorporates both entropy and vorticity corrections into the solution procedures thereby extending its applicability into regimes where shock strength normally precludes its use. Parameter studies resulting in benchmark type calculations include the effects of spatial and temporal refinement, spatial order of accuracy, far field boundary conditions for steady flow, frequency of oscillation, and the use of subiterations at each time step to reduce linearization and factorization errors. Comparisons between Euler and potential flow results are made, as well as with experimental data where available.

  13. Accurate solutions, parameter studies and comparisons for the Euler and potential flow equations

    NASA Technical Reports Server (NTRS)

    Anderson, W. Kyle; Batina, John T.

    1988-01-01

    Parameter studies are conducted using the Euler and potential flow equation models for unsteady and steady flows in both two and three dimensions. The Euler code is an implicit, upwind, finite volume code which uses the Van Leer method of flux-vector-splitting which has been recently extended for use on dynamic meshes and maintain all the properties of the original splitting. The potential flow code is an implicit, finite difference method for solving the transonic small disturbance equations and incorporates both entropy and vorticity corrections into the solution procedures thereby extending its applicability into regimes where shock strength normally precludes its use. Parameter studies resulting in benchmark type calculations include the effects of spatial and temporal refinement, spatial order of accuracy, far field boundary conditions for steady flow, frequency of oscillation, and the use of subiterations at each time step to reduce linearization and factorization errors. Comparisons between Euler and potential flows results are made as well as with experimental data where available.

  14. Can a combination of ultrasonographic parameters accurately evaluate concussion and guide return-to-play decisions?

    PubMed

    Cartwright, Michael S; Dupuis, Janae E; Bargoil, Jessica M; Foster, Dana C

    2015-09-01

    Mild traumatic brain injury, often referred to as concussion, is a common, potentially debilitating, and costly condition. One of the main challenges in diagnosing and managing concussion is that there is not currently an objective test to determine the presence of a concussion and to guide return-to-play decisions for athletes. Traditional neuroimaging tests, such as brain magnetic resonance imaging, are normal in concussion, and therefore diagnosis and management are guided by reported symptoms. Some athletes will under-report symptoms to accelerate their return-to-play and others will over-report symptoms out of fear of further injury or misinterpretation of underlying conditions, such as migraine headache. Therefore, an objective measure is needed to assist in several facets of concussion management. Limited data in animal and human testing indicates that intracranial pressure increases slightly and cerebrovascular reactivity (the ability of the cerebral arteries to auto-regulate in response to changes in carbon dioxide) decreases slightly following mild traumatic brain injury. We hypothesize that a combination of ultrasonographic measurements (optic nerve sheath diameter and transcranial Doppler assessment of cerebrovascular reactivity) into a single index will allow for an accurate and non-invasive measurement of intracranial pressure and cerebrovascular reactivity, and this index will be clinically relevant and useful for guiding concussion diagnosis and management. Ultrasound is an ideal modality for the evaluation of concussion because it is portable (allowing for evaluation in many settings, such as on the playing field or in a combat zone), radiation-free (making repeat scans safe), and relatively inexpensive (resulting in nearly universal availability). This paper reviews the literature supporting our hypothesis that an ultrasonographic index can assist in the diagnosis and management of concussion, and it also presents limited data regarding the

  15. 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 μmol 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

  16. 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…

  17. 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 (σ), volume free energy (ΔGv), critical energy barrier for nucleation (ΔG*), 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.

  18. Accurate Structure and Dynamics of the Metal-Site of Paramagnetic Metalloproteins from NMR Parameters Using Natural Bond Orbitals

    PubMed Central

    2012-01-01

    A natural bond orbital (NBO) analysis of unpaired electron spin density in metalloproteins is presented, which allows a fast and robust calculation of paramagnetic NMR parameters. Approximately 90% of the unpaired electron spin density occupies metal–ligand NBOs, allowing the majority of the density to be modeled by only a few NBOs that reflect the chemical bonding environment. We show that the paramagnetic relaxation rate of protons can be calculated accurately using only the metal–ligand NBOs and that these rates are in good agreement with corresponding rates measured experimentally. This holds, in particular, for protons of ligand residues where the point-dipole approximation breaks down. To describe the paramagnetic relaxation of heavy nuclei, also the electron spin density in the local orbitals must be taken into account. Geometric distance restraints for 15N can be derived from the paramagnetic relaxation enhancement and the Fermi contact shift when local NBOs are included in the analysis. Thus, the NBO approach allows us to include experimental paramagnetic NMR parameters of 15N nuclei as restraints in a structure optimization protocol. We performed a molecular dynamics simulation and structure determination of oxidized rubredoxin using the experimentally obtained paramagnetic NMR parameters of 15N. The corresponding structures obtained are in good agreement with the crystal structure of rubredoxin. Thus, the NBO approach allows an accurate description of the geometric structure and the dynamics of metalloproteins, when NMR parameters are available of nuclei in the immediate vicinity of the metal-site. PMID:22329704

  19. GUIDANCE2: accurate detection of unreliable alignment regions accounting for the uncertainty of multiple parameters

    PubMed Central

    Sela, Itamar; Ashkenazy, Haim; Katoh, Kazutaka; Pupko, Tal

    2015-01-01

    Inference of multiple sequence alignments (MSAs) is a critical part of phylogenetic and comparative genomics studies. However, from the same set of sequences different MSAs are often inferred, depending on the methodologies used and the assumed parameters. Much effort has recently been devoted to improving the ability to identify unreliable alignment regions. Detecting such unreliable regions was previously shown to be important for downstream analyses relying on MSAs, such as the detection of positive selection. Here we developed GUIDANCE2, a new integrative methodology that accounts for: (i) uncertainty in the process of indel formation, (ii) uncertainty in the assumed guide tree and (iii) co-optimal solutions in the pairwise alignments, used as building blocks in progressive alignment algorithms. We compared GUIDANCE2 with seven methodologies to detect unreliable MSA regions using extensive simulations and empirical benchmarks. We show that GUIDANCE2 outperforms all previously developed methodologies. Furthermore, GUIDANCE2 also provides a set of alternative MSAs which can be useful for downstream analyses. The novel algorithm is implemented as a web-server, available at: http://guidance.tau.ac.il. PMID:25883146

  20. X-ray and microwave emissions from the July 19, 2012 solar flare: Highly accurate observations and kinetic models

    NASA Astrophysics Data System (ADS)

    Gritsyk, P. A.; Somov, B. V.

    2016-08-01

    The M7.7 solar flare of July 19, 2012, at 05:58 UT was observed with high spatial, temporal, and spectral resolutions in the hard X-ray and optical ranges. The flare occurred at the solar limb, which allowed us to see the relative positions of the coronal and chromospheric X-ray sources and to determine their spectra. To explain the observations of the coronal source and the chromospheric one unocculted by the solar limb, we apply an accurate analytical model for the kinetic behavior of accelerated electrons in a flare. We interpret the chromospheric hard X-ray source in the thick-target approximation with a reverse current and the coronal one in the thin-target approximation. Our estimates of the slopes of the hard X-ray spectra for both sources are consistent with the observations. However, the calculated intensity of the coronal source is lower than the observed one by several times. Allowance for the acceleration of fast electrons in a collapsing magnetic trap has enabled us to remove this contradiction. As a result of our modeling, we have estimated the flux density of the energy transferred by electrons with energies above 15 keV to be ˜5 × 1010 erg cm-2 s-1, which exceeds the values typical of the thick-target model without a reverse current by a factor of ˜5. To independently test the model, we have calculated the microwave spectrum in the range 1-50 GHz that corresponds to the available radio observations.

  1. Accurate Analytical and Statistical Approaches to Reduce O-C Discrepancies in the Precessional Parameters

    NASA Astrophysics Data System (ADS)

    Martínez, M. J.; Marco, F. J.; López, J. A.

    2009-02-01

    The Hipparcos catalog provides a reference frame at optical wavelengths for the new International Celestial Reference System (ICRS). This new reference system was adopted following the resolution agreed at the 23rd IAU General Assembly held in Kyoto in 1997. Differences in the Hipparcos system of proper motions and the previous materialization of the reference frame, the FK5, are expected to be caused only by the combined effects of the motion of the equinox of the FK5 and the precession of the equator and the ecliptic. Several authors have pointed out an inconsistency between the differences in proper motion of the Hipparcos-FK5 and the correction of the precessional values derived from VLBI and lunar laser ranging (LLR) observations. Most of them have claimed that these discrepancies are due to slightly biased proper motions in the FK5 catalog. The different mathematical models that have been employed to explain these errors have not fully accounted for the discrepancies in the correction of the precessional parameters. Our goal here is to offer an explanation for this fact. We propose the use of independent parametric and nonparametric models. The introduction of a nonparametric model, combined with the inner product in the square integrable functions over the unitary sphere, would give us values which do not depend on the possible interdependencies existing in the data set. The evidence shows that zonal studies are needed. This would lead us to introduce a local nonparametric model. All these models will provide independent corrections to the precessional values, which could then be compared in order to study the reliability in each case. Finally, we obtain values for the precession corrections that are very consistent with those that are currently adopted.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  4. 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

  5. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  7. 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.

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

    PubMed

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

    2012-04-15

    A methodology for modeling photocatalytic reactors for their application in indoor air pollution control is carried out. The methodology implies, firstly, the determination of intrinsic reaction kinetics for the removal of formaldehyde. This is achieved by means of a simple geometry, continuous reactor operating under kinetic control regime and steady state. The kinetic parameters were estimated from experimental data by means of a nonlinear optimization algorithm. The second step was the application of the obtained kinetic parameters to a very different photoreactor configuration. In this case, the reactor is a corrugated wall type using nanosize TiO(2) as catalyst irradiated by UV lamps that provided a spatially uniform radiation field. The radiative transfer within the reactor was modeled through a superficial emission model for the lamps, the ray tracing method and the computation of view factors. The velocity and concentration fields were evaluated by means of a commercial CFD tool (Fluent 12) where the radiation model was introduced externally. The results of the model were compared experimentally in a corrugated wall, bench scale reactor constructed in the laboratory. The overall pollutant conversion showed good agreement between model predictions and experiments, with a root mean square error less than 4%. PMID:22030272

  9. Association between plasma zinc concentration and zinc kinetic parameters in premenopausal women.

    PubMed

    Yokoi, Katsuhiko; Egger, Norman G; Ramanujam, V M Sadagopa; Alcock, Nancy W; Dayal, Hari H; Penland, James G; Sandstead, Harold H

    2003-11-01

    The objective of this study was to measure relationships between plasma zinc (Zn) concentrations and Zn kinetic parameters and to measure relationships of Zn status with taste acuity, food frequency, and hair Zn in humans. The subjects were 33 premenopausal women not taking oral contraceptives and dietary supplements containing iron and Zn. Main outcomes were plasma Zn concentrations, Zn kinetic parameters based on the three-compartment mammillary model using 67Zn as a tracer, electrical taste detection thresholds, and food frequencies. Lower plasma Zn was significantly (P < 0.01) associated with smaller sizes of the central and the lesser peripheral Zn pools, faster disappearance of tracer from plasma, and higher transfer rate constants from the lesser peripheral pool to the central pool and from the central pool to the greater peripheral pool. The break points in the plasma Zn-Zn kinetics relationship were found between 9.94 and 11.5 micromol/l plasma Zn. Smaller size of the lesser peripheral pool was associated with lower frequency of beef consumption and higher frequency of bran breakfast cereal consumption. Hypozincemic women with plasma Zn <10.7 micromol/l or 700 ng/ml had decreased thresholds of electrical stimulation for gustatory nerves. Our results based on Zn kinetics support the conventional cutoff value of plasma Zn (10.7 micromol/l or 700 ng/ml) between normal and low Zn status. PMID:12865259

  10. A Weibull statistics-based lignocellulose saccharification model and a built-in parameter accurately predict lignocellulose hydrolysis performance.

    PubMed

    Wang, Mingyu; Han, Lijuan; Liu, Shasha; Zhao, Xuebing; Yang, Jinghua; Loh, Soh Kheang; Sun, Xiaomin; Zhang, Chenxi; Fang, Xu

    2015-09-01

    Renewable energy from lignocellulosic biomass has been deemed an alternative to depleting fossil fuels. In order to improve this technology, we aim to develop robust mathematical models for the enzymatic lignocellulose degradation process. By analyzing 96 groups of previously published and newly obtained lignocellulose saccharification results and fitting them to Weibull distribution, we discovered Weibull statistics can accurately predict lignocellulose saccharification data, regardless of the type of substrates, enzymes and saccharification conditions. A mathematical model for enzymatic lignocellulose degradation was subsequently constructed based on Weibull statistics. Further analysis of the mathematical structure of the model and experimental saccharification data showed the significance of the two parameters in this model. In particular, the λ value, defined the characteristic time, represents the overall performance of the saccharification system. This suggestion was further supported by statistical analysis of experimental saccharification data and analysis of the glucose production levels when λ and n values change. In conclusion, the constructed Weibull statistics-based model can accurately predict lignocellulose hydrolysis behavior and we can use the λ parameter to assess the overall performance of enzymatic lignocellulose degradation. Advantages and potential applications of the model and the λ value in saccharification performance assessment were discussed. PMID:26121186

  11. 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

  12. [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

  13. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  15. [Determination of kinetic parameters lymphocyte populations in cows with chronic lymphocytic leukemia].

    PubMed

    Kuznetsov, V A; Feofanova, T V; Busol, V A; Nikolaeva, N V

    1995-01-01

    We analyzed changes in the number of lymphocytes in the blood of cows with chronic lymphoid leukemia using the Gomperts equation of population dynamics. The parameters of this equation were determined. Coefficients beta and gamma proved to be the most variable. The former reflects the delay and the latter characterizes the maximum rate of growth of the lymphocyte population. According to these parameters, three groups of animals were distinguished with different kinetics of leucosis and different correlations between immuno-hematological indices. PMID:7670356

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

    PubMed Central

    2013-01-01

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

  17. Optimization of tissue physical parameters for accurate temperature estimation from finite-element simulation of radiofrequency ablation.

    PubMed

    Subramanian, Swetha; Mast, T Douglas

    2015-10-01

    Computational finite element models are commonly used for the simulation of radiofrequency ablation (RFA) treatments. However, the accuracy of these simulations is limited by the lack of precise knowledge of tissue parameters. In this technical note, an inverse solver based on the unscented Kalman filter (UKF) is proposed to optimize values for specific heat, thermal conductivity, and electrical conductivity resulting in accurately simulated temperature elevations. A total of 15 RFA treatments were performed on ex vivo bovine liver tissue. For each RFA treatment, 15 finite-element simulations were performed using a set of deterministically chosen tissue parameters to estimate the mean and variance of the resulting tissue ablation. The UKF was implemented as an inverse solver to recover the specific heat, thermal conductivity, and electrical conductivity corresponding to the measured area of the ablated tissue region, as determined from gross tissue histology. These tissue parameters were then employed in the finite element model to simulate the position- and time-dependent tissue temperature. Results show good agreement between simulated and measured temperature. PMID:26352462

  18. Optimization of tissue physical parameters for accurate temperature estimation from finite-element simulation of radiofrequency ablation

    NASA Astrophysics Data System (ADS)

    Subramanian, Swetha; Mast, T. Douglas

    2015-09-01

    Computational finite element models are commonly used for the simulation of radiofrequency ablation (RFA) treatments. However, the accuracy of these simulations is limited by the lack of precise knowledge of tissue parameters. In this technical note, an inverse solver based on the unscented Kalman filter (UKF) is proposed to optimize values for specific heat, thermal conductivity, and electrical conductivity resulting in accurately simulated temperature elevations. A total of 15 RFA treatments were performed on ex vivo bovine liver tissue. For each RFA treatment, 15 finite-element simulations were performed using a set of deterministically chosen tissue parameters to estimate the mean and variance of the resulting tissue ablation. The UKF was implemented as an inverse solver to recover the specific heat, thermal conductivity, and electrical conductivity corresponding to the measured area of the ablated tissue region, as determined from gross tissue histology. These tissue parameters were then employed in the finite element model to simulate the position- and time-dependent tissue temperature. Results show good agreement between simulated and measured temperature.

  19. Kinetics of Bacterial Phospholipase C Activity at Micellar Interfaces: Effect of Substrate Aggregate Microstructure and a Model for the Kinetic Parameters

    PubMed Central

    Singh, Jasmeet; Ranganathan, Radha; Hajdu, Joseph

    2009-01-01

    Activity at micellar interfaces of bacterial phospholipase C from Bacillus cereus on phospholipids solubilized in micelles was investigated with the goal of elucidating the role of the interface microstructure and developing further an existing kinetic model. Enzyme kinetics and physicochemical characterization of model substrate aggregates were combined; thus enabling the interpretation of kinetics in the context of the interface. Substrates were diacylphosphatidylcholine of different acyl chain lengths in the form of mixed micelles with dodecyldimethylammoniopropanesulfonate. An early kinetic model, reformulated to reflect the interfacial nature of the kinetics, was applied to the kinetic data. A better method of data treatment is proposed, use of which makes the presence of microstructure effects quite transparent. Models for enzyme-micelle binding and enzyme-lipid binding are developed and expressions incorporating the microstructural properties are derived for the enzyme-micelle dissociation constant KS and the interface Michaelis-Menten constant, KM. Use of these expressions in the interface kinetic model brings excellent agreement between the kinetic data and the model. Numerical values for the thermodynamic and kinetic parameters are determined. Enzyme-lipid binding is found to be an activated process with an acyl chain length dependent free energy of activation that decreases with micelle lipid molar fraction with a coefficient of about −15 RT and correlates with the tightness of molecular packing in the substrate aggregate. Thus the physical insight obtained includes a model for the kinetic parameters that shows that these parameters depend on the substrate concentration and acyl chain length of the lipid. Enzyme-micelle binding is indicated to be hydrophobic and solvent mediated with a dissociation constant of 1.2 mM. PMID:19367944

  20. 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.

  1. Kinetic parameters related to sources and sinks of vibrationally excited OH in the nightglow

    SciTech Connect

    McDade, I.C.; Llewellyn, E.J. )

    1987-07-01

    Kinetic parameters related to vibrational deactivation and chemical removal of vibrationally excited OH radicals in the mesosphere are deduced from ground-based measurements of the mean vibrational distribution of the OH Meinel bands in the nightglow. The derived parameters, which rely on a laboratory measured rate coefficient for the removal of OH(v = 9) by O{sub 2} and a set of relative Meinel band transition probabilities, have been obtained for two limiting Meinel band excitation models that differ in the extent to which single-quantum vibrational deactivation and sudden death' collisional removal processes determine the OH vibrational distribution. It is shown that the OH Meinel band emission can be adequately explained with the deduced parameters and the H + O{sub 3} {yields} OH + O{sub 2} reaction as the only chemical source of vibrationally excited OH. Evidence is presented which suggests that the reaction HO{sub 2} + O {leftrightarrow} HO + O{sub 2} may perhaps be involved as a sink of vibrationally excited OH rather than as a potential source. The deduced kinetic parameters should be particularly useful in future Meinel band studies as they have been obtained from an analysis for which there is no assumption about the very uncertain OH radiative lifetimes.

  2. Identification of the crystallization kinetic parameters of a semi-crystalline polymer by using PVTα 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 PVTα apparatus, initially developed in the laboratory for the characterization of thermoset composites, was adapted to identify the crystallization kinetics. The aim of the presented study is to demonstrate the feasibility of the identification. This device allows the molding of a circular sample of 40 mm diameter and 6 mm thick by controlling the applied pressure on the sample and the temperature field on its surfaces. This mold is designed such as heat transfer is 1D within the thickness of the sample. It is equipped with two heat flux sensors to determine the average crystallization rate through the thickness and a displacement sensor for the determination of the volume change. The heat transfer problem between the polymer and the molding cavity is modeled by using a 1D conduction problem with a moving boundary, in which the control volume is a uniform temperature disk with a variable volume, and coupled to a crystallization kinetic model. An inverse method is used to identify the parameters of the crystallization kinetic model by minimizing an objective function based on the difference between the evolutions of the experimental and computed volume of the sample. The first validation of this methodology was to compare the kinetic parameters identified with this apparatus

  3. 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...

  4. Efficient estimation of dynamic cardiac SPECT kinetic parameters using singular value decomposition reconstruction

    SciTech Connect

    Gulberg, G.T.; Huesman, R.H.; Zeng, G.L. |

    1994-05-01

    Error estimates of time activity curves are necessary to obtain efficient estimates of dynamic of dynamic cardiac SPECT kinetic parameters which are determined using weighted least squares fitting that incorporates these error estimates. In cardiac SPECT, iterative algorithms are used to obtain attenuation corrected reconstructions, and the use of an iterative algorithm makes it difficult to estimate the errors of the estimated reconstruction. An alternate approach is to estimate the reconstruction by solving the system of normal equations using singular value decomposition. This method was applied to dynamic data acquired from a canine study. A canine was injected with 25 mCi of Tc-99m-teboroxime and was imaged using a three-detector SPECT system (Picker PRISM 3000). Sequential 5 sec tomographic acquisitions were acquired for 15 min, allowing both the wash-in and wash-out of teboroxime to be measured. The projection data were reconstructed into 64x64 transaxial slices for each 5 sec acquisition using singular value decomposition to calculate the reconstructed estimate, the variance of the estimate, and the covariance between tissue and blood regions-of-interest. One 4096x4096 singular value decomposition was obtained in 71 hours using a 40 mHz Supper SPARC processor. Tissue and blood time-activity curves were generated from the attenuation corrected transaxial reconstructions. The blood activity curve was generated from a region drawn inside the left ventricle. A two-compartment model was fit to the blood and tissue activity curves to give weighted least squares estimates of blood volume fraction and wash-in and wash-out rate constants specifying teboroxime kinetics for regions of the left ventricular myocardium. As expected the weighted least squares estimates of the kinetic parameters had smaller variances than the unweighted estimates, thus demonstrating more efficient parameter estimation.

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

    PubMed

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

    2016-09-01

    Rebutini, VZ, Pereira, G, Bohrer, RCD, Ugrinowitsch, C, and Rodacki, ALF. Plyometric long jump training with progressive loading improves kinetic and kinematic swimming start parameters. J Strength Cond Res 30(9): 2392-2398, 2016-This study was aimed to determine the effects of a plyometric long jump training program on torque around the lower limb joints and kinetic and kinematics parameters during the swimming jump start. Ten swimmers performed 3 identical assessment sessions, measuring hip and knee muscle extensors during maximal voluntary isometric contraction and kinetic and kinematics parameters during the swimming jump start, at 3 instants: INI (2 weeks before the training program, control period), PRE (2 weeks after INI measurements), and POST (24-48 hours after 9 weeks of training). There were no significant changes from INI to PRE measurements. However, the peak torque and rate of torque development increased significantly from PRE to POST measurements for both hip (47 and 108%) and knee (24 and 41%) joints. There were significant improvements to the horizontal force (7%), impulse (9%), and angle of resultant force (19%). In addition, there were significant improvements to the center of mass displacement (5%), horizontal takeoff velocity (16%), horizontal velocity at water entrance (22%), and peak angle velocity for the knee (15%) and hip joints (16%). Therefore, the plyometric long jump training protocol was effective to enhance torque around the lower limb joints and to control the resultant vector direction, to increase the swimming jump start performance. These findings suggest that coaches should use long jump training instead of vertical jump training to improve swimming start performance. PMID:24531431

  6. Accurate characterization of the stellar and orbital parameters of the exoplanetary system WASP-33 b from orbital dynamics

    NASA Astrophysics Data System (ADS)

    Iorio, L.

    2016-01-01

    By using the most recently published Doppler tomography measurements and accurate theoretical modelling of the oblateness-driven orbital precessions, we tightly constrain some of the physical and orbital parameters of the planetary system hosted by the fast rotating star WASP-33. In particular, the measurements of the orbital inclination ip to the plane of the sky and of the sky-projected spin-orbit misalignment λ at two epochs about six years apart allowed for the determination of the longitude of the ascending node Ω and of the orbital inclination I to the apparent equatorial plane at the same epochs. As a consequence, average rates of change dot{Ω }_exp, dot{I}_exp of this two orbital elements, accurate to a ≈10-2 deg yr-1 level, were calculated as well. By comparing them to general theoretical expressions dot{Ω }_{J_2}, dot{I}_{J_2} for their precessions induced by an oblate star whose symmetry axis is arbitrarily oriented, we were able to determine the angle i⋆ between the line of sight the star's spin {S}^{star } and its first even zonal harmonic J_2^{star } obtaining i^{star } = {142}^{+10}_{-11} deg, J_2^{star } = 2.1^{+0.8}_{-0.5}times; 10^{-4}. As a by-product, the angle between {S}^{star } and the orbital angular momentum L is as large as about ψ ≈ 100 ° psi; ^{2008} = 99^{+5}_{-4} deg, ψ ^{{2014}} = 103^{+5}_{-4} deg and changes at a rate dot{ψ }= 0.{7}^{+1.5}_{-1.6} deg {yr}^{-1}. The predicted general relativistic Lense-Thirring precessions, of the order of ≈10-3deg yr-1, are, at present, about one order of magnitude below the measurability threshold.

  7. 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

  8. 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.

  9. Effects of metformin on cell kinetic parameters of MCF-7 breast cancer cells in vitro.

    PubMed

    Topcul, Mehmet; Cetin, Idil

    2015-01-01

    In this study, the antiproliferative effects of the metformin was evaluated on MCF-7 Cells (human breast adenocarcinoma cell line). For this purpose cell kinetic parameters including cell proliferation assay, mitotic index and labelling index analysis were used. 30 μM, 65 μM and 130 μM Metformin doses were applied to cells for 24, 48 and 72 hours. The results showed that there was a significant decrease in cell proliferation, mitotic index and labelling index for all experimental groups (p<0.05) for all applications. PMID:25824763

  10. A Computer Program for the Calculation of Reactivity and Kinetic Parameters by Two-Dimensional Neutron Transport Perturbation Theory.

    1985-02-01

    Version 00 TP2 is a transport theory code, developed to determine reactivity effects and kinetic parameters such as effective delayed neutron fractions and mean generation time by applying the usual perturbation formalism for two-dimensional geometry.

  11. A Computer Code System for the Calculation of Reactivity and Kinetic Parameters by One-Dimensional Neutron Transport Perturbation Theory.

    1985-02-01

    Version 00 TP1 is a transport theory code, developed to determine reactivity effects and kinetic parameters such as effective delayed neutron fractions and mean generation time by applying the usual perturbation formalism for one-dimensional geometry.

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

    PubMed

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

    2016-02-01

    Most of the existing methods for obtaining the frequency factors make use of the trap depth (activation energy) making some assumptions about the order of the kinetics. This causes inconsistencies in the reported values of trapping parameters due that the values of the activation energy obtained by different methods differ appreciably among them. Then, it is necessary to use a method independent of the trap depth making use of the isothermal luminescence decay (ILD) method. The trapping parameters associated with the prominent glow peak of BeO (280°C) are reported using ILD method. As a check, the trap parameters are also calculated by glow curve shape (Chen's) method after isolating the prominent glow peak by thermal cleaning technique. Our results show a very good agreement between the trapping parameters calculated by the two methods. ILD method was used for determining the trapping parameters of BeO. Results obtained applying this method are in good agreement with those obtained using other methods, except in the value of the frequency factor. PMID:26656428

  13. 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

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

    Milekovic, Tomislav; Truccolo, Wilson; Grün, 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

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

    PubMed

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

    2002-05-01

    To optimize the fed-batch processes of glycerol fermentation in different reactor states, typical bioreactors including 500-mL shaking flask, 600-mL and 15-L airlift loop reactor, and 5-L stirred vessel were investigated. It was found that by reestimating the values of only two variable kinetic parameters associated with physical transport phenomena in a reactor, the macrokinetic model of glycerol fermentation proposed in previous work could describe well the batch processes in different reactor states. This variable kinetic parameter (VKP) approach was further applied to model-based optimization of discrete-pulse feed (DPF) strategies of both glucose and corn steep slurry for glycerol fed-batch fermentation. The experimental results showed that, compared with the feed strategies determined just by limited experimental optimization in previous work, the DPF strategies with VKPs adjusted could improve glycerol productivity at least by 27% in the scale-down and scale-up reactor states. The approach proposed appeared promising for further modeling and optimization of glycerol fermentation or the similar bioprocesses in larger scales. PMID:12049203

  17. 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%.

  18. 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.

  19. {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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

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

    PubMed

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

    2010-09-01

    Lineweaver-Burk plot analysis is the most widely used method to determine enzyme kinetic parameters. In the spectrophotometric determination of enzyme activity using the Lineweaver-Burk plot, it is necessary to find a wavelength at which only the substrate or the product has absorbance without any spectroscopic interference of the other reaction components. Moreover, in this method, different initial concentrations of the substrate should be used to obtain the initial velocities required for Lineweaver-Burk plot analysis. In the present work, a multi-wavelength model-based method has been developed and validated to determine Michaelis-Menten constants for some enzyme reactions. In this method, a selective wavelength region and several experiments with different initial concentrations of the substrate are not required. The absorbance data of the kinetic assays are fitted by non-linear regression coupled to the numeric integration of the related differential equation. To indicate the applicability of the proposed method, the Michaelis-Menten constants for the oxidation of phenanthridine, 6-deoxypenciclovir and xanthine by molybdenum hydroxylases were determined using only a single initial concentration of the substrate, regardless of any spectral overlap. PMID:20826949

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

    PubMed

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

    2016-05-01

    This paper reports a study of the anaerobic biodegradation of non-ionic surfactants alkyl polyglucosides applying the method by measurement of the biogas production in digested sludge. Three alkyl polyglucosides with different length alkyl chain and degree of polymerization of the glucose units were tested. The influence of their structural parameters was evaluated, and the characteristics parameters of the anaerobic biodegradation were determined. Results show that alkyl polyglucosides, at the standard initial concentration of 100 mgC L(-1), are not completely biodegradable in anaerobic conditions because they inhibit the biogas production. The alkyl polyglucoside having the shortest alkyl chain showed the fastest biodegradability and reached the higher percentage of final mineralization. The anaerobic process was well adjusted to a pseudo first-order equation using the carbon produced as gas during the test; also, kinetics parameters and a global rate constant for all the involved metabolic process were determined. This modeling is helpful to evaluate the biodegradation or the persistence of alkyl polyglucosides under anaerobic conditions in the environment and in the wastewater treatment. PMID:26820643

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

    SciTech Connect

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

    1996-12-31

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

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

    SciTech Connect

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

    1999-07-19

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

  5. 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

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

    PubMed Central

    2013-01-01

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

  7. Improved centroid moment tensor analyses in the NIED AQUA (Accurate and QUick Analysis system for source parameters)

    NASA Astrophysics Data System (ADS)

    Kimura, H.; Asano, Y.; Matsumoto, T.

    2012-12-01

    The rapid determination of hypocentral parameters and their transmission to the public are valuable components of disaster mitigation. We have operated an automatic system for this purpose—termed the Accurate and QUick Analysis system for source parameters (AQUA)—since 2005 (Matsumura et al., 2006). In this system, the initial hypocenter, the moment tensor (MT), and the centroid moment tensor (CMT) solutions are automatically determined and posted on the NIED Hi-net Web site (www.hinet.bosai.go.jp). This paper describes improvements made to the AQUA to overcome limitations that became apparent after the 2011 Tohoku Earthquake (05:46:17, March 11, 2011 in UTC). The improvements included the processing of NIED F-net velocity-type strong motion records, because NIED F-net broadband seismographs are saturated for great earthquakes such as the 2011 Tohoku Earthquake. These velocity-type strong motion seismographs provide unsaturated records not only for the 2011 Tohoku Earthquake, but also for recording stations located close to the epicenters of M>7 earthquakes. We used 0.005-0.020 Hz records for M>7.5 earthquakes, in contrast to the 0.01-0.05 Hz records employed in the original system. The initial hypocenters determined based on arrival times picked by using seismograms recorded by NIED Hi-net stations can have large errors in terms of magnitude and hypocenter location, especially for great earthquakes or earthquakes located far from the onland Hi-net network. The size of the 2011 Tohoku Earthquake was initially underestimated in the AQUA to be around M5 at the initial stage of rupture. Numerous aftershocks occurred at the outer rise east of the Japan trench, where a great earthquake is anticipated to occur. Hence, we modified the system to repeat the MT analyses assuming a larger size, for all earthquakes for which the magnitude was initially underestimated. We also broadened the search range of centroid depth for earthquakes located far from the onland Hi

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

    NASA Technical Reports Server (NTRS)

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

    1996-01-01

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

  9. 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.

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

    PubMed

    Bonowski, Felix; Kitanovic, Ana; Ruoff, Peter; Holzwarth, Jinda; Kitanovic, Igor; Bui, Van Ngoc; Lederer, Elke; Wölfl, Stefan

    2010-01-01

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

  11. GGOS and the EOP - the key role of SLR for a stable estimation of highly accurate Earth orientation parameters

    NASA Astrophysics Data System (ADS)

    Bloßfeld, Mathis; Panzetta, Francesca; Müller, Horst; Gerstl, Michael

    2016-04-01

    The GGOS vision is to integrate geometric and gravimetric observation techniques to estimate consistent geodetic-geophysical parameters. In order to reach this goal, the common estimation of station coordinates, Stokes coefficients and Earth Orientation Parameters (EOP) is necessary. Satellite Laser Ranging (SLR) provides the ability to study correlations between the different parameter groups since the observed satellite orbit dynamics are sensitive to the above mentioned geodetic parameters. To decrease the correlations, SLR observations to multiple satellites have to be combined. In this paper, we compare the estimated EOP of (i) single satellite SLR solutions and (ii) multi-satellite SLR solutions. Therefore, we jointly estimate station coordinates, EOP, Stokes coefficients and orbit parameters using different satellite constellations. A special focus in this investigation is put on the de-correlation of different geodetic parameter groups due to the combination of SLR observations. Besides SLR observations to spherical satellites (commonly used), we discuss the impact of SLR observations to non-spherical satellites such as, e.g., the JASON-2 satellite. The goal of this study is to discuss the existing parameter interactions and to present a strategy how to obtain reliable estimates of station coordinates, EOP, orbit parameter and Stokes coefficients in one common adjustment. Thereby, the benefits of a multi-satellite SLR solution are evaluated.

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

    PubMed Central

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

    2014-01-01

    The sorption of cadmium (Cd) and lead (Pb) by calcium alginate beads (CAB) from aqueous solutions in batch systems was investigated. The kinetic and thermodynamic parameters, as well as the sorption capacities of CAB in each system at different temperatures, were evaluated. The rate of sorption for both metals was rapid in the first 10 minutes and reached a maximum in 50 minutes. Sorption kinetic data were fitted to Lagergren, pseudo-second-order and Elovich models and it was found that the second-order kinetic model describes these data for the two metals; comparing kinetic parameters for Cd and Pb sorption a higher kinetic rate (K2) for Pb was observed, indicating that the interaction between lead cations and alginate beads was faster than for cadmium. Similarly, isotherm data were fitted to different models reported in literature and it was found that the Langmuir-Freundlich (L-F) and Dubinin-Radushkevich (D-R) models describe the isotherms in all cases. CAB sorption capacity for cadmium was 27.4 mg/g and 150.4 mg/g for lead, at 25°C. Sorption capacities of Cd and Pb increase as temperature rises. According to the thermodynamic parameters, the cadmium and lead adsorption process was spontaneous and endothermic. It was also found that pH has an important effect on the adsorption of these metals by CAB, as more were removed at pH values between 6 and 7. PMID:24587740

  13. Numerical parameter constraints for accurate PIC-DSMC simulation of breakdown from arc initiation to stable arcs

    NASA Astrophysics Data System (ADS)

    Moore, Christopher; Hopkins, Matthew; Moore, Stan; Boerner, Jeremiah; Cartwright, Keith

    2015-09-01

    Simulation of breakdown is important for understanding and designing a variety of applications such as mitigating undesirable discharge events. Such simulations need to be accurate through early time arc initiation to late time stable arc behavior. Here we examine constraints on the timestep and mesh size required for arc simulations using the particle-in-cell (PIC) method with direct simulation Monte Carlo (DMSC) collisions. Accurate simulation of electron avalanche across a fixed voltage drop and constant neutral density (reduced field of 1000 Td) was found to require a timestep ~ 1/100 of the mean time between collisions and a mesh size ~ 1/25 the mean free path. These constraints are much smaller than the typical PIC-DSMC requirements for timestep and mesh size. Both constraints are related to the fact that charged particles are accelerated by the external field. Thus gradients in the electron energy distribution function can exist at scales smaller than the mean free path and these must be resolved by the mesh size for accurate collision rates. Additionally, the timestep must be small enough that the particle energy change due to the fields be small in order to capture gradients in the cross sections versus energy. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DOE's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

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

    NASA Astrophysics Data System (ADS)

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

    2011-07-01

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

  15. [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

  16. Influence of the mutable kinetic parameters on the adhesion and debonding of thin viscoelastic films.

    PubMed

    Ghosh, Abir; Bandyopadhyay, Dipankar; Sharma, Ashutosh

    2016-09-01

    Detachment of a surface from a viscoelastic layer, such as a film of glue, engenders bridges between the surfaces until separation. Such surface instabilities arising during contact and detachment of viscoelastic films with rigid contactors have been theoretically explored by linear stability analysis and nonlinear simulations. The contact instabilities of viscoelastic materials are found to manifest in either a 'critical' or a 'dominant' mode in which the former is preferred when the contactor is slowly brought near the film while the latter manifests when the film is 'hard-pressed' against it. The nonlinear analysis considers the movement of contactor during adhesion-debonding cycle, which uncovers that the kinetic parameters can overshadow the thermodynamically predicted area of contact, average force for pull-off, energy of contactor-film separation, and pathways of debonding. Three distinct pathways of debonding - peeling, catastrophic column collapse, and column coalescence, are found to manifest with the variation in the ratio of the elastic to viscous compliances of the viscoelastic film. The study also reveals that in the dominant mode of instability, a smaller length scale with a larger area contact between the contactor and film can develop patterns having aspect ratio ∼10 times larger than the same obtained from elastic film. PMID:27254253

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

    PubMed

    Király, Róbert; Thangaraju, Kiruphagaran; Nagy, Zsófia; Collighan, Russell; Nemes, Zoltán; Griffin, Martin; Fésüs, László

    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 γ-glutamyl-ε-lysine isopeptide crosslinks between proteins and γ-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

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

    PubMed

    Lizama, H M; Suzuki, I

    1989-11-01

    Rate equations and kinetic parameters were obtained for various reactions involved in the bacterial oxidation of pyrite. The rate constants were 3.5 muM Fe per min per FeS(2) percent pulp density for the spontaneous pyrite dissolution, 10 muM Fe per min per mM Fe for the indirect leaching with Fe, 90 muM O(2) per min per mg of wet cells per ml for the Thiobacillus ferrooxidans oxidation of washed pyrite, and 250 muM O(2) per min per mg of wet cells per ml for the T. ferrooxidans oxidation of unwashed pyrite. The K(m) 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 K(i) value of 0.13 mg of wet cells per ml. T. ferrooxidans cells also increased the rate of Fe production from Fe plus pyrite. PMID:16348054

  19. 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

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

    NASA Astrophysics Data System (ADS)

    Zhao, G. Q.; Wu, D. J.; Wang, C. B.

    2014-10-01

    Solar extreme-ultraviolet (EUV) lines emitted by highly charged ions have been extensively studied to discuss the issue of coronal heating and solar wind acceleration. Based on observations of the polar corona by the SUMER/SOHO spectrometer, this paper investigates the relation between the line widths and kinetic parameters of ions. It is shown that there exists a strongly linear correlation between two variables ( σ/ λ)2 and M -1, where σ, λ and M are the half-width of the observed line profile at , the wavelength and the ion mass, respectively. The Pearson product-moment correlation coefficients exceed 0.9. This finding tends to suggest that the ions from a given height of polar corona have a common temperature and a common non-thermal velocity in terms of existing equation. The temperature and non-thermal velocity are obtained by linear least-square fit. The temperature is around 2.8 MK at heights of 57″ and 102″. The non-thermal velocity is typical 21.6 km s-1 at height of 57″ and 25.2 km s-1 at height of 102″.

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

    SciTech Connect

    Casoli, P.; Authier, N.; Chapelle, A.

    2012-07-01

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

  2. Quantification of kinetic parameters for heterotrophic bacteria via respirometry in a hybrid reactor.

    PubMed

    Trapani, Daniele Di; Mannina, Giorgio; Torregrossa, Michele; Viviani, Gaspare

    2010-01-01

    Over the last decade new technologies are emerging even more for wastewater treatment. Among the new technologies, a recent possible solution regards Moving Bed Biofilm Reactors (MBBRs) that represent an effective alternative to conventional processes. More specifically such systems consist in the introduction of plastic elements inside the aerobic reactor as carrier material for the growth of attached biomass. Recently, one of the mostly used alternatives is to couple the Moving Bed Biofilm Reactor (MBBR) process with the conventional activated sludge process, and the resulting process is usually called HMBBR (Hybrid MBBR). In the MBBR process the biofilm grows attached on small plastic elements that are kept in constant motion throughout the entire volume of the reactor. Indeed, in such a system, a competition between the two biomasses, suspended and attached, can arise for the availability of the substrates, leading, as a consequence, to a modification in the biokinetic parameters of the two biomasses, compared to that of a pure suspended or attached biomass process. This paper presents the first results of a study aimed at estimating the kinetic heterotrophic constants in a HMBBR pilot plant using respirometric techniques. The pilot plant was built at the Acqua dei Corsari (Palermo) wastewater treatment plant and consisted of two parallel lines realized in a pre-anoxic scheme, in one of which the carrier material was added to the aerobic reactor with a filling ratio of 30%. PMID:20371934

  3. 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)

  4. A non-empirical, parameter-free, hybrid functional for accurate calculations of optoelectronic properties of finite systems

    NASA Astrophysics Data System (ADS)

    Brawand, Nicholas; Vörös, Márton; Govoni, Marco; Galli, Giulia

    The accurate prediction of optoelectronic properties of molecules and solids is a persisting challenge for current density functional theory (DFT) based methods. We propose a hybrid functional where the mixing fraction of exact and local exchange is determined by a non-empirical, system dependent function. This functional yields ionization potentials, fundamental and optical gaps of many, diverse systems in excellent agreement with experiments, including organic and inorganic molecules and nanocrystals. We further demonstrate that the newly defined hybrid functional gives the correct alignment between the energy level of the exemplary TTF-TCNQ donor-acceptor system. DOE-BES: DE-FG02-06ER46262.

  5. Modeling the sorption kinetic of metsulfuron-methyl on Andisols and Ultisols volcanic ash-derived soils: kinetics parameters and solute transport mechanisms.

    PubMed

    Cáceres, Lizethly; Escudey, Mauricio; Fuentes, Edwar; Báez, María E

    2010-07-15

    Metsulfuron-methyl sorption kinetic was studied in Andisol and Ultisol soils in view of their distinctive physical and chemical properties: acidic pH and variable surface charge. Different kinetic models were applied to the experimental results. The pseudo-second-order model fitted sorption kinetics data better than the pseudo-first-order model. The rate constant and the initial rate constant values obtained through this model demonstrated the different behavior of metsulfuron-methyl in both kinds of soils, both parameters being the highest for Andisol. The application of Elovich equation, intraparticle diffusion model and a two-site nonequilibrium model (TSNE) allowed to conclude that: (i) the high organic matter content is the governing factor for Andisols where mass transfer across the boundary layer, and in a lesser degree, intraparticle diffusion were the two processes controlling sorption kinetic and (ii) the mineral composition was more relevant in Ultisols where rate was controlled almost exclusively by intraparticle diffusion into macropores and micropores. The slower sorption rate on Ultisols, the mechanism involved and the lower sorption capacity of this kind of soils must be taken into account to assess leaching behavior of this herbicide. PMID:20399011

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

    NASA Astrophysics Data System (ADS)

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

    2006-03-01

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

  7. Kinetic and mass transfer parameters of maltotriose hydrolysis catalyzed by glucoamylase immobilized on macroporous silica and wrapped in pectin gel.

    PubMed

    Gonçalves, L R; Suzuki, G S; Giordano, R C; Giordano, R L

    2001-01-01

    Kinetic and mass transport parameters were estimated for maltotriose hydrolysis using glucoamylase immobilized on macroporous silica and wrapped in pectin gel at 30 degrees C. Free enzyme assays were used to obtain the intrinsic kinetic parameters of a Michaelis-Menten equation, with product inhibition by glucose. The uptake method, based on transient experimental data, was employed in the estimation of mass transfer parameters. Effective diffusivities of maltotriose in pectin gel were estimated by fitting a classical diffusion model to experimental data of maltotriose diffusion into particles of pectin gel in the absence of silica. The effective diffusivities of maltotriose in silica were obtained after fitting a bidisperse model to experimental data of maltotriose hydrolysis using glucoamylase immobilized in silica and wrapped in pectin gel. PMID:11963897

  8. Evaluation of kinetic parameters for enzymatic interesterification synthesis of L-ascorbyl lactate by response surface methodology.

    PubMed

    Gao, Jing; Jiang, Yanjun; Huang, Zhihong; Zhou, Liya

    2007-02-01

    The kinetics of lipase-catalyzed interesterification synthesis of L-ascorbyl lactate was studied. To determine the enzyme kinetic constants of the interesterification, a three-factor and five-level central composite design was used. The factors studied were ethyl lactate concentration, reaction temperature (T), and water content (w). Moreover, a statistical approach called the response surface method (RSM) was used to predict the kinetic constants. Finally, the relationships between the kinetic constants (Vm and Km) and the reaction parameters (T and w) were obtained. To assess the accuracy of the RSM approach for determining Vm and Km, detailed validation experiments were carried out by the conventional approach at four different reaction parameters(35 degrees C, 10 microL; 45 degrees C, 20 microL; 55 degrees C, 15 microL; 65 degrees C, 18 microL). The results indicated that the RSM approach gave reasonable results for the determination of Vm and Km in the range of tested parameters. PMID:17496337

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

    PubMed

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

    2014-01-01

    Availability of inorganic nutrients, particularly nitrogen and phosphorous, is often a primary control on crude oil hydrocarbon degradation in marine systems. Many studies have empirically determined optimum levels of inorganic N and P for stimulation of hydrocarbon degradation. Nevertheless, there is a paucity of information on fundamental kinetic parameters for nutrient enhanced crude oil biodegradation that can be used to model the fate of crude oil in bioremediation programmes that use inorganic nutrient addition to stimulate oil biodegradation. Here we report fundamental kinetic parameters (Ks and qmax) for nitrate- and phosphate-stimulated crude oil biodegradation under nutrient limited conditions and with respect to crude oil, under conditions where N and P are not limiting. In the marine sediments studied, crude oil degradation was limited by both N and P availability. In sediments treated with 12.5 mg/g of oil but with no addition of N and P, hydrocarbon degradation rates, assessed on the basis of CO2 production, were 1.10 ± 0.03 μmol CO2/g wet sediment/day which were comparable to rates of CO2 production in sediments to which no oil was added (1.05 ± 0.27 μmol CO2/g wet sediment/day). When inorganic nitrogen was added alone maximum rates of CO2 production measured were 4.25 ± 0.91 μmol CO2/g wet sediment/day. However, when the same levels of inorganic nitrogen were added in the presence of 0.5% P w/w of oil (1.6 μmol P/g wet sediment) maximum rates of measured CO2 production increased more than four-fold to 18.40 ± 1.04 μmol CO2/g wet sediment/day. Ks and qmax estimates for inorganic N (in the form of sodium nitrate) when P was not limiting were 1.99 ± 0.86 μmol/g wet sediment and 16.16 ± 1.28 μmol CO2/g wet sediment/day respectively. The corresponding values for P were 63 ± 95 nmol/g wet sediment and 12.05 ± 1.31 μmol CO2/g wet sediment/day. The qmax values with respect to N and P were not significantly different (P < 0.05). When N and P

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

    PubMed Central

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

    2014-01-01

    Availability of inorganic nutrients, particularly nitrogen and phosphorous, is often a primary control on crude oil hydrocarbon degradation in marine systems. Many studies have empirically determined optimum levels of inorganic N and P for stimulation of hydrocarbon degradation. Nevertheless, there is a paucity of information on fundamental kinetic parameters for nutrient enhanced crude oil biodegradation that can be used to model the fate of crude oil in bioremediation programmes that use inorganic nutrient addition to stimulate oil biodegradation. Here we report fundamental kinetic parameters (Ks and qmax) for nitrate- and phosphate-stimulated crude oil biodegradation under nutrient limited conditions and with respect to crude oil, under conditions where N and P are not limiting. In the marine sediments studied, crude oil degradation was limited by both N and P availability. In sediments treated with 12.5 mg/g of oil but with no addition of N and P, hydrocarbon degradation rates, assessed on the basis of CO2 production, were 1.10 ± 0.03 μmol CO2/g wet sediment/day which were comparable to rates of CO2 production in sediments to which no oil was added (1.05 ± 0.27 μmol CO2/g wet sediment/day). When inorganic nitrogen was added alone maximum rates of CO2 production measured were 4.25 ± 0.91 μmol CO2/g wet sediment/day. However, when the same levels of inorganic nitrogen were added in the presence of 0.5% P w/w of oil (1.6 μmol P/g wet sediment) maximum rates of measured CO2 production increased more than four-fold to 18.40 ± 1.04 μmol CO2/g wet sediment/day. Ks and qmax estimates for inorganic N (in the form of sodium nitrate) when P was not limiting were 1.99 ± 0.86 μmol/g wet sediment and 16.16 ± 1.28 μmol CO2/g wet sediment/day respectively. The corresponding values for P were 63 ± 95 nmol/g wet sediment and 12.05 ± 1.31 μmol CO2/g wet sediment/day. The qmax values with respect to N and P were not significantly different (P < 0.05). When N and P

  11. Towards an accurate specific reaction parameter density functional for water dissociation on Ni(111): RPBE versus PW91.

    PubMed

    Jiang, Bin; Guo, Hua

    2016-08-01

    In search for an accurate description of the dissociative chemisorption of water on the Ni(111) surface, we report a new nine-dimensional potential energy surface (PES) based on a large number of density functional theory points using the RPBE functional. Seven-dimensional quantum dynamical calculations have been carried out on the RPBE PES, followed by site averaging and lattice effect corrections, yielding sticking probabilities that are compared with both the previous theoretical results based on a PW91 PES and experiment. It is shown that the RPBE functional increases the reaction barrier, but has otherwise a minor impact on the PES topography. Better agreement with experimental results is obtained with the new PES, but the agreement is still not quantitative. Possible sources of the remaining discrepancies are discussed. PMID:27436348

  12. An accurate and simple technique of determination of the maximum power point and measurement of some solar cell parameters

    NASA Astrophysics Data System (ADS)

    Deb, S.; Maitra, K.; Roychoudhuri, A.

    1985-06-01

    In the wake of the energy crisis, attempts are being made to develop a variety of energy conversion devices, such as solar cells. The single most important operational characteristic for a conversion element generating electricity is the V against I curve. Three points on this characteristic curve are of paramount importance, including the short-circuit, the open-circuit, and the maximum power point. The present paper has the objective to propose a new simple and accurate method of determining the maximum power point (Vm, Im) of the V against I characteristics, based on a geometrical interpretation. The method is general enough to be applicable to any energy conversion device having a nonlinear V against I characteristic. The paper provides also a method for determining the fill factor (FF), the series resistance (Rs), and the diode ideality factor (A) from a single set of connected observations.

  13. 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.

  14. 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.

  15. Accurate determination of interface trap state parameters by admittance spectroscopy in the presence of a Schottky barrier contact: Application to ZnO-based solar cells

    NASA Astrophysics Data System (ADS)

    Marin, Andrew T.; Musselman, Kevin P.; MacManus-Driscoll, Judith L.

    2013-04-01

    This work shows that when a Schottky barrier is present in a photovoltaic device, such as in a device with an ITO/ZnO contact, equivalent circuit analysis must be performed with admittance spectroscopy to accurately determine the pn junction interface recombination parameters (i.e., capture cross section and density of trap states). Without equivalent circuit analysis, a Schottky barrier can produce an error of ˜4-orders of magnitude in the capture cross section and ˜50% error in the measured density of trap states. Using a solution processed ZnO/Cu2O photovoltaic test system, we apply our analysis to clearly separate the contributions of interface states at the pn junction from the Schottky barrier at the ITO/ZnO contact so that the interface state recombination parameters can be accurately characterized. This work is widely applicable to the multitude of photovoltaic devices, which use ZnO adjacent to ITO.

  16. Investigation of thermoluminescence and kinetic parameters of CaMgB2O5: Dy3+ nanophosphor

    NASA Astrophysics Data System (ADS)

    Manhas, M.; Kumar, Vinay; Ntwaeaborwa, O. M.; Swart, H. C.

    2016-05-01

    In this paper, thermoluminescence (TL) properties of Dy3+ (1.5 mol %) doped CaMgB2O5 nanophosphor after being exposed to ultraviolet (UV) radiations (λ=254nm) were investigated. In UV exposed samples, the thermoluminescence glow curve consists of a broad glow peak located at 380 K with a small shoulder at 507 K. A shift in glow peak temperature from 367 K to 380 K after the UV exposure for 80 min was observed, which clearly shows that glow peaks follow the second order kinetics. The TL intensity of the peaks increases with an increase in the exposure time of UV rays (10-180 min). The TL Anal program was used to analyze the glow curve. The kinetic parameters such as activation energy (E), the frequency factor (s) and the order of kinetics (b) were calculated for CaMgB2O5: Dy3+ nanophosphors.

  17. A review of uncertainties in atmospheric modeling of mercury chemistry I. Uncertainties in existing kinetic parameters - Fundamental limitations and the importance of heterogeneous chemistry

    NASA Astrophysics Data System (ADS)

    Subir, Mahamud; Ariya, Parisa A.; Dastoor, Ashu P.

    2011-10-01

    Mercury and its related compounds are widely recognized as global pollutants. The accurate atmospheric modeling of its transport and fate has been the subject of much research throughout the last decade. Atmospheric gas, aqueous and heterogeneous chemistry are expected to occur for Hg-containing species and accurate implementation of their chemical parameters is essential for realistic modeling of mercury cycling. Although significant progress has been made, the current state of knowledge of mercury chemistry exhibits numerous uncertainties. The objective of this two-part review is to explore the sources of uncertainty from the viewpoint of mercury chemistry. In this first part, we assess the discrepancy that exists in the currently available mercury kinetic parameters for the gas and aqueous phases. Theoretical and experimental approaches of rate constant determination exhibit various levels of limitation and accuracy. We present an overview of the available techniques and the assumptions and shortcomings associated with these methods in order to assist the atmospheric modellers. We review specific mercury oxidation and reduction reactions that have been investigated and are commonly implemented in mercury models with respect to the uncertainties associated with them. We reveal that for most of these mercury reactions our current state of knowledge reflects a lack of proper understanding of their mechanisms. Atmospheric heterogeneity is a topic of great importance and we elaborate upon it in part II of this review.

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

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  19. Petermann I and II spot size: Accurate semi analytical description involving Nelder-Mead method of nonlinear unconstrained optimization and three parameter fundamental modal field

    NASA Astrophysics Data System (ADS)

    Roy Choudhury, Raja; Roy Choudhury, Arundhati; Kanti Ghose, Mrinal

    2013-01-01

    A semi-analytical model with three optimizing parameters and a novel non-Gaussian function as the fundamental modal field solution has been proposed to arrive at an accurate solution to predict various propagation parameters of graded-index fibers with less computational burden than numerical methods. In our semi analytical formulation the optimization of core parameter U which is usually uncertain, noisy or even discontinuous, is being calculated by Nelder-Mead method of nonlinear unconstrained minimizations as it is an efficient and compact direct search method and does not need any derivative information. Three optimizing parameters are included in the formulation of fundamental modal field of an optical fiber to make it more flexible and accurate than other available approximations. Employing variational technique, Petermann I and II spot sizes have been evaluated for triangular and trapezoidal-index fibers with the proposed fundamental modal field. It has been demonstrated that, the results of the proposed solution identically match with the numerical results over a wide range of normalized frequencies. This approximation can also be used in the study of doped and nonlinear fiber amplifier.

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

    PubMed Central

    2012-01-01

    Background Compared with static imaging, dynamic emission computed tomographic imaging with compartment modeling can quantify in vivo physiologic processes, providing useful information about molecular disease processes. Dynamic imaging involves estimation of kinetic rate parameters. For multi-compartment models, kinetic parameter estimation can be computationally demanding and problematic with local minima. Methods This paper offers a new perspective to the compartment model fitting problem where Fourier linear system theory is applied to derive closed-form formulas for estimating kinetic parameters for the two-compartment model. The proposed Fourier domain estimation method provides a unique solution, and offers very different noise response as compared to traditional non-linear chi-squared minimization techniques. Results The unique feature of the proposed Fourier domain method is that only low frequency components are used for kinetic parameter estimation, where the DC (i.e., the zero frequency) component in the data is treated as the most important information, and high frequency components that tend to be corrupted by statistical noise are discarded. Computer simulations show that the proposed method is robust without having to specify the initial condition. The resultant solution can be fine tuned using the traditional iterative method. Conclusions The proposed Fourier-domain estimation method has closed-form formulas. The proposed Fourier-domain curve-fitting method does not require an initial condition, it minimizes a quadratic objective function and a closed-form solution can be obtained. The noise is easier to control, simply by discarding the high frequency components, and emphasizing the DC component. PMID:22995548

  1. Coupling 1D Navier Stokes equation with autoregulation lumped parameter networks for accurate cerebral blood flow modeling

    NASA Astrophysics Data System (ADS)

    Ryu, Jaiyoung; Hu, Xiao; Shadden, Shawn C.

    2014-11-01

    The cerebral circulation is unique in its ability to maintain blood flow to the brain under widely varying physiologic conditions. Incorporating this autoregulatory response is critical to cerebral blood flow modeling, as well as investigations into pathological conditions. We discuss a one-dimensional nonlinear model of blood flow in the cerebral arteries that includes coupling of autoregulatory lumped parameter networks. The model is tested to reproduce a common clinical test to assess autoregulatory function - the carotid artery compression test. The change in the flow velocity at the middle cerebral artery (MCA) during carotid compression and release demonstrated strong agreement with published measurements. The model is then used to investigate vasospasm of the MCA, a common clinical concern following subarachnoid hemorrhage. Vasospasm was modeled by prescribing vessel area reduction in the middle portion of the MCA. Our model showed similar increases in velocity for moderate vasospasms, however, for serious vasospasm (~ 90% area reduction), the blood flow velocity demonstrated decrease due to blood flow rerouting. This demonstrates a potentially important phenomenon, which otherwise would lead to false-negative decisions on clinical vasospasm if not properly anticipated.

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

    PubMed

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

    2014-11-17

    Microorganisms rarely live in isolation but are most often found in a consortium. This provides the potential for cross-feeding and nutrient competition among the microbial species, which make it challenging to predict the growth kinetics in coculture. In this paper we developed a mathematical model to describe substrate consumption and subsequent microbial growth and metabolite production for bacteria grown in monoculture. The model characterized substrate utilization kinetics of 18 Bifidobacterium strains. Some bifidobacterial strains demonstrated preferential degradation of oligofructose in that sugars with low degree of polymerization (DP) (DP≤3 or 4) were metabolized before sugars of higher DP, or vice versa. Thus, we expanded the model to describe the preferential degradation of oligofructose. In addition, we adapted the model to describe the competition between human colonic bacteria Bacteroides thetaiotaomicron LMG 11262 and Bifidobacterium longum LMG 11047 or Bifidobacterium breve Yakult for inulin as well as cross-feeding of breakdown products from the extracellular hydrolysis of inulin by B. thetaiotaomicron LMG 11262. We found that the coculture growth kinetics could be predicted based on the respective monoculture growth kinetics. Using growth kinetics from monoculture experiments to predict coculture dynamics will reduce the number of in vitro experiments required to parameterize multi-culture models. PMID:25282609

  3. Effects of Multiple-Bond Ruptures on Kinetic Parameters Extracted from Force Spectroscopy Measurements: Revisiting Biotin-Streptavidin Interactions

    PubMed Central

    Guo, Senli; Ray, Chad; Kirkpatrick, Andrea; Lad, Nimit; Akhremitchev, Boris B.

    2008-01-01

    Force spectroscopy measurements of the rupture of the molecular bond between biotin and streptavidin often results in a wide distribution of rupture forces. We attribute the long tail of high rupture forces to the nearly simultaneous rupture of more than one molecular bond. To decrease the number of possible bonds, we employed hydrophilic polymeric tethers to attach biotin molecules to the atomic force microscope probe. It is shown that the measured distributions of rupture forces still contain high forces that cannot be described by the forced dissociation from a deep potential well. We employed a recently developed analytical model of simultaneous rupture of two bonds connected by polymer tethers with uneven length to fit the measured distributions. The resulting kinetic parameters agree with the energy landscape predicted by molecular dynamics simulations. It is demonstrated that when more than one molecular bond might rupture during the pulling measurements there is a noise-limited range of probe velocities where the kinetic parameters measured by force spectroscopy correspond to the true energy landscape. Outside this range of velocities, the kinetic parameters extracted by using the standard most probable force approach might be interpreted as artificial energy barriers that are not present in the actual energy landscape. Factors that affect the range of useful velocities are discussed. PMID:18621812

  4. Accurate Calculation of Hydration Free Energies using Pair-Specific Lennard-Jones Parameters in the CHARMM Drude Polarizable Force Field

    PubMed Central

    Baker, Christopher M.; Lopes, Pedro E. M.; Zhu, Xiao; Roux, Benoît; MacKerell, Alexander D.

    2010-01-01

    Lennard-Jones (LJ) parameters for a variety of model compounds have previously been optimized within the CHARMM Drude polarizable force field to reproduce accurately pure liquid phase thermodynamic properties as well as additional target data. While the polarizable force field resulting from this optimization procedure has been shown to satisfactorily reproduce a wide range of experimental reference data across numerous series of small molecules, a slight but systematic overestimate of the hydration free energies has also been noted. Here, the reproduction of experimental hydration free energies is greatly improved by the introduction of pair-specific LJ parameters between solute heavy atoms and water oxygen atoms that override the standard LJ parameters obtained from combining rules. The changes are small and a systematic protocol is developed for the optimization of pair-specific LJ parameters and applied to the development of pair-specific LJ parameters for alkanes, alcohols and ethers. The resulting parameters not only yield hydration free energies in good agreement with experimental values, but also provide a framework upon which other pair-specific LJ parameters can be added as new compounds are parametrized within the CHARMM Drude polarizable force field. Detailed analysis of the contributions to the hydration free energies reveals that the dispersion interaction is the main source of the systematic errors in the hydration free energies. This information suggests that the systematic error may result from problems with the LJ combining rules and is combined with analysis of the pair-specific LJ parameters obtained in this work to identify a preliminary improved combining rule. PMID:20401166

  5. Kinetic Analysis of Human PrimPol DNA Polymerase Activity Reveals a Generally Error-Prone Enzyme Capable of Accurately Bypassing 7,8-Dihydro-8-oxo-2′-deoxyguanosine

    PubMed Central

    2015-01-01

    Recent studies have identified human PrimPol as a new RNA/DNA primase and translesion DNA synthesis polymerase (TLS pol) that contributes to nuclear and mitochondrial DNA replication. We investigated the mechanism of PrimPol polymerase activity on both undamaged and damaged DNA substrates. With Mg2+ as a cofactor, PrimPol binds primer-template DNA with low affinity Kd,DNA values (∼200–1200 nM). DNA binding is enhanced 34-fold by Mn2+ (Kd,DNA = 27 nM). The pol activity of PrimPol is increased 400–1000-fold by Mn2+ compared to Mg2+ based on steady-state kinetic parameters. PrimPol makes a mistake copying undamaged DNA once every ∼100–2500 insertions events, which is comparable to other TLS pols, and the fidelity of PrimPol is ∼1.7-fold more accurate when Mg2+ is the cofactor compared to Mn2+. PrimPol inserts dCMP opposite 8-oxo-dG with 2- (Mn2+) to 6-fold (Mg2+) greater efficiency than dAMP misinsertion. PrimPol-catalyzed dCMP insertion opposite 8-oxo-dG proceeds at ∼25% efficiency relative to unmodified template dG, and PrimPol readily extends from dC:8-oxo-dG base pairs (bps) with ∼2-fold greater efficiency than dA:8-oxo-dG bps. A tetrahydrofuran (THF) abasic-site mimic decreases PrimPol activity to ∼0.04%. In summary, PrimPol exhibits the fidelity typical of other TLS pols, is rather unusual in the degree of activation afforded by Mn2+, and accurately bypasses 8-oxo-dG, a DNA lesion of special relevance to mitochondrial DNA replication and transcription. PMID:25255211

  6. 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

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

    PubMed

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

    2015-09-25

    Application of model-based design is appealing to support the development of protein chromatography in the biopharmaceutical industry. However, the required efforts for parameter estimation are frequently perceived as time-consuming and expensive. In order to speed-up this work, a new parameter estimation approach for modelling ion-exchange chromatography in linear conditions was developed. It aims at reducing the time and protein demand for the model calibration. The method combines the estimation of kinetic and thermodynamic parameters based on the simultaneous variation of the gradient slope and the residence time in a set of five linear gradient elutions. The parameters are estimated from a Yamamoto plot and a gradient-adjusted Van Deemter plot. The combined approach increases the information extracted per experiment compared to the individual methods. As a proof of concept, the combined approach was successfully applied for a monoclonal antibody on a cation-exchanger and for a Fc-fusion protein on an anion-exchange resin. The individual parameter estimations for the mAb confirmed that the new approach maintained the accuracy of the usual Yamamoto and Van Deemter plots. In the second case, offline size-exclusion chromatography was performed in order to estimate the thermodynamic parameters of an impurity (high molecular weight species) simultaneously with the main product. Finally, the parameters obtained from the combined approach were used in a lumped kinetic model to simulate the chromatography runs. The simulated chromatograms obtained for a wide range of gradient lengths and residence times showed only small deviations compared to the experimental data. PMID:26306913

  8. 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

  9. Open channel noise. VI. Analysis of amplitude histograms to determine rapid kinetic parameters.

    PubMed Central

    Heinemann, S H; Sigworth, F J

    1991-01-01

    Recently we reported that rapid fluctuations of ion currents flowing through open gramicidin A channels exceed the expected level of pure transport noise at low ion concentrations (Heinemann, S. H. and F. J. Sigworth. 1990. Biophys. J. 57:499-514). Based on comparisons with kinetic ion transport models we concluded that this excess noise is likely caused by current interruptions lasting approximately 1 microsecond. Here we introduce a method using the higher-order cumulants of the amplitude distribution to estimate the kinetics of channel closing events far below the actual time resolution of the recording system. Using this method on data recorded with 10 kHz bandwidth, estimates for gap time constants on the order of 1 microsecond were obtained, similar to the earlier predictions. PMID:1718467

  10. Relevance of thermodynamic and kinetic parameters of chemical vapor deposition precursors.

    PubMed

    Selvakumar, J; Nagaraja, K S; Sathiyamoorthy, D

    2011-09-01

    We have studied various metallorganic and organometallic compounds by simultaneous nonisothermal thermogravimetric and differential thermogravimetric analyses to confirm their volatility and thermal stability. The equilibrium vapor pressures of the metallorganic and organometallic compounds were determined by horizontal dual arm single furnace thermoanalyzer as transpiration apparatus. Antoine coefficients were calculated from the temperature dependence equilibrium vapor pressure data. The model-fitting solid-state kinetic analyses of Al(acac)3, (acac = acetylacetonato), Cr(CO)6, Fe(Cp)2, (Cp-cyclopentadienyl), Ga(acac)3, Mn(tmhd)3, and Y(tmhd)3 (tmhd = 2,2,6,6,-tetramethyl-3,5-heptanedionato) revealed that the processes follow diffusion controlled, contracting area and zero order model sublimation or evaporation kinetics. The activation energy for the sublimation/evaporation processes were calculated by model-free kinetic methods. Thin films of nickel and lanthanum-strontium-manganite (LSM) are grown on silicon substrate at 573 K using selected metallorganic complexes of Ni[(acac)2en], La(tmhd)3, Sr(tmhd)2 and Mn(tmhd)3 as precursors by plasma assisted liquid injection chemical vapor deposition (PA-LICVD). The deposited films were characterized by scanning electron microscopy and energy dispersive X-ray analysis for their composition and morphology. PMID:22097553

  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. Applicability of fluorescence-based sensors to the determination of kinetic parameters for O2 in oxygenases

    PubMed Central

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

    2015-01-01

    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 constitute a convenient alternative to the widely-used Clark-type electrode, especially in cases where chemical interference is expected to be problematic. PMID:25637681

  13. TOPICAL REVIEW: Kinetic phenomena in charged particle transport in gases, swarm parameters and cross section data

    NASA Astrophysics Data System (ADS)

    Petrovic, Z. Lj; Suvakov, M.; Nikitovic, Z.; Dujko, S.; Sasic, O.; Jovanovic, J.; Malovic, G.; Stojanovic, V.

    2007-02-01

    In this review we discuss the current status of the physics of charged particle swarms, mainly electrons. The whole field is analysed mainly through its relationship to plasma modelling and illustrated by some recent examples developed mainly by our group. The measurements of the swarm coefficients and the availability of the data are briefly discussed. More time is devoted to the development of complete electron molecule cross section sets along with recent examples such as NO, CF4 and HBr. We extend the discussion to the availability of ion and fast neutral data and how swarm experiments may serve to provide new data. As a point where new insight into the kinetics of charge particle transport is provided, the role of kinetic phenomena is discussed and recent examples are listed. We focus here on giving two examples on how non-conservative processes make dramatic effects in transport, the negative absolute mobility and the negative differential conductivity for positrons in argon. Finally we discuss the applicability of swarm data in plasma modelling and the relationship to other fields where swarm experiments and analysis make significant contributions. Based on the general invited lecture presented by the first author at ESCAMPIG 2006 at Lecce in Italy.

  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 29.49-147.25k J/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 71.77 kJ/mol to 207.03 kJ/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 19.5 MJ/kg, considered a relevant result for bioenergy production. PMID:26773950

  15. 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

  16. An identification algorithm of model kinetic parameters of the interfacial layer growth in fiber composites

    NASA Astrophysics Data System (ADS)

    Zubov, V.; Lurie, S.; Solyaev, Y.

    2016-04-01

    This paper considers the identification algorithm of parameters included in a parabolic law that is often used to predict the time dependence of the thickness of the interfacial layers in the structure of composite materials based on a metal matrix. The incubation period of the process and the speed of reaction and pressure are taken into account. The proposed algorithm of identification is based on the introduction of a minimized objective function of a special kind. The problem of identification of unknown parameters in the parabolic law is formulated in a variational form. The authors of the paper have determined the desired parameters, under which the objective function has a minimum value. It is shown that on the basis of four known experimental values of the interfacial layer thickness, corresponding to different values of temperature, pressure and the time of the interfacial layer growth, it is possible to identified four model parameters. They are the activation energy, a pre-exponential parameter, the delay time of the start of the interfacial layer formation, and the parameter determining the pressure effect on the rate of interfacial layer growth. The stability of the proposed identification algorithm is also studied.

  17. 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.

  18. Using kinetic parameter analysis of dynamic FDOPA-PET for brain tissue classification

    NASA Astrophysics Data System (ADS)

    Lin, Hong-Dun; Lin, Kang-Ping; Chung, Being-Tau; Yu, Chin-Lung; Wang, Rong-Fa; Wu, Liang-Chi; Liu, Ren-Shyan

    2002-04-01

    In clinically, structural image based brain tissue segmentation as a preprocess plays an important and essential role on a number of image preprocessing, such as image visualization, object recognition, image registration, and so forth. However, when we need to classify the tissues according to their physiological functions, those strategies are not satisfactory. In this study, we incorporated both tissue time-activity curves (TACs) and derived kinetic parametric curves (KPCs) information to segment brain tissues, such as striatum, gray and white matters, in dynamic FDOPA-PET studies. Four common clustering techniques, K-mean (KM), Fuzzy C-mean (FCM), Isodata (ISO), Markov Random Fields (MRF), and our method were compared to evaluate its precision. The results show 41% and 48% less mean errors in mean difference for KPCs and TACs, respectively, than other methods. Combined KPCs and TACs based clustering method provide the ability to define brain structure effectively.

  19. 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

  20. Action of human pancreatic and salivary alpha-amylases on maltooligosaccharides: evaluation of kinetic parameters.

    PubMed

    Saito, N; Horiuchi, T; Yoshida, M; Imai, T

    1979-10-01

    The kinetic studies on the reactions of human pancreatic and salivary alpha-amylases with several maltooligosaccharides (maltotetraose, maltopentaose, maltohexaose, and maltoheptaose) were carried out. The susceptibility to hydrolysis with human pancreatic alpha-amylase decreased in the order of maltopentaose, maltohexaose, maltotetraose, and maltoheptaose, while with human salivary alpha-amylase maltopentaose was hydrolysed slightly slower than maltohexaose but fairly faster than maltotetraose or maltoheptaose from a viewpoint of the rates of reactions based on the amount of substrate changed. The relative rates of production of substrates, utilized in the coupled yeast alpha-glucosidase reaction, increased in the order of maltoheptaose, maltohexaose, maltotetraose, and maltopentaose with human pancreatic alpha-amylase, while with human salivary alpha-amylase in the order of maltoheptaose, maltotetraose, maltohexaose, and maltopentaose. Thus, maltopentaose was considered to be the best substrate over maltotetraose, maltohexaose or maltoheptaose for the alpha-glucosidase coupled method of alpha-amylase determination. PMID:385176

  1. HCV-NS3 inhibitors: determination of their kinetic parameters and mechanism.

    PubMed

    Flores, María Victoria; Strawbridge, Joanne; Ciaramella, Giuseppe; Corbau, Romuald

    2009-10-01

    Existing HCV protease inhibitors fall into two categories: reversible and non-covalent, such as BILN-2061, and covalent and reversible, exemplified by SCH-503034 and VX-950. In this work, the characterization of the kinetics of these three inhibitors is presented. SCH-503034 and VX-950 initially bind to the genotype 1b HCV NS3/4A protease to form a low affinity complex, with K(i) values of 5 and 5.8 microM respectively. The ability of those two compounds to form a second covalent complex (EI) results in a potency increase, with overall K(i) values of 20 and 45 nM, respectively. The increase in potency can be explained by their slow dissociation rate, forming complexes with half-lives of 2 h (VX-950) and 5 h (SCH-503034). Although BILN-2061 has been described as a fast reversible, non-covalent inhibitor, our results show a slow binding two-step mechanism. Contrary to SCH-503034 and VX-950, BILN-2061 can form a high affinity first complex with a K(i) value of 3.9 nM, and an overall K(i) of 0.14 nM. The half-life of the BILN-2061 EI complex is shorter (t(1/2) approximately 0.7 h) than that of the other two compounds. The potency of these compounds is genotype dependent, and a kinetic analysis using NS3/4A from genotype 3a indicates that the loss of potency of SCH-503034 and VX-950 relative to genotype 1 is mainly due to the slow on-rate and faster off-rate for the formation of the EI complex. In the case of BILN-2061, a better fit is obtained using a one-step model, indicating that the loss of potency is due to an increase in the off-rate of the EI complex. PMID:19505593

  2. 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

  3. Photochemical parameters of atmospheric source gases: accurate determination of OH reaction rate constants over atmospheric temperatures, UV and IR absorption spectra

    NASA Astrophysics Data System (ADS)

    Orkin, V. L.; Khamaganov, V. G.; Martynova, L. E.; Kurylo, M. J.

    2012-12-01

    The emissions of halogenated (Cl, Br containing) organics of both natural and anthropogenic origin contribute to the balance of and changes in the stratospheric ozone concentration. The associated chemical cycles are initiated by the photochemical decomposition of the portion of source gases that reaches the stratosphere. Reactions with hydroxyl radicals and photolysis are the main processes dictating the compound lifetime in the troposphere and release of active halogen in the stratosphere for a majority of halogen source gases. Therefore, the accuracy of photochemical data is of primary importance for the purpose of comprehensive atmospheric modeling and for simplified kinetic estimations of global impacts on the atmosphere, such as in ozone depletion (i.e., the Ozone Depletion Potential, ODP) and climate change (i.e., the Global Warming Potential, GWP). The sources of critically evaluated photochemical data for atmospheric modeling, NASA/JPL Publications and IUPAC Publications, recommend uncertainties within 10%-60% for the majority of OH reaction rate constants with only a few cases where uncertainties lie at the low end of this range. These uncertainties can be somewhat conservative because evaluations are based on the data from various laboratories obtained during the last few decades. Nevertheless, even the authors of the original experimental works rarely estimate the total combined uncertainties of the published OH reaction rate constants to be less than ca. 10%. Thus, uncertainties in the photochemical properties of potential and current atmospheric trace gases obtained under controlled laboratory conditions still may constitute a major source of uncertainty in estimating the compound's environmental impact. One of the purposes of the presentation is to illustrate the potential for obtaining accurate laboratory measurements of the OH reaction rate constant over the temperature range of atmospheric interest. A detailed inventory of accountable sources of

  4. 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.

  5. Kinetic parameters and relative turnovers of some important catabolic reactions in digesting sludge.

    PubMed Central

    Kaspar, H F; Wuhrmann, K

    1978-01-01

    The kinetics of propionate degradation, acetate splitting, and hydrogen consumption in digesting sludge were investigated in a lab-scale digester. At natural steady-state conditions, the acetate-splitting systems in well-digested sludge were about half saturated. Propionate-degrading systems were saturated to only 10 to 15%, and hydrogen removal was less than 1% of the maximum possible rate. It was concluded that acetate splitting rather than "methanogenesis from fatty acids" is the rate-limiting reaction in the anaerobic degradation of dissolved organic matter and that a methoanogenic anaerobic ecosystem is stabilized by its large unused capacity of hydrogen consumption which is "buffering" the partial pressure of dissolved hydrogen in the system at sufficiently low values to permit rapid fatty acid oxidation. A tentative scheme of the substrate flow in sludge digestion is presented. It suggests that acid formation coupled with hydrogen formation via pyridine dinucleotide oxidation yields the immediate substrates, namely acetate and hydrogen, for about 54% of the total methanogenesis. PMID:697354

  6. Quantifiable patterns of limb loading and unloading during hemiparetic gait: Relation to kinetic and kinematic parameters

    PubMed Central

    Raja, Bhavana; Neptune, Richard R.; Kautz, Steven A.

    2016-01-01

    Persons with poststroke hemiparesis are characterized by asymmetry in limb loading (LL) and limb unloading (LU), which has been reported in static and quasi-static tasks but has not been quantified during walking. The purpose of this study was to determine the asymmetry in magnitude and duration of LL and LU in individuals with hemiparesis and its relationship with functional walking status and specific kinematic and kinetic variables during walking. Forty-four participants with chronic hemiparesis walked at their self-selected speeds and eighteen nondisabled control subjects of similar ages walked at predetermined matched speeds while three-dimensional ground reaction forces and body-segment kinematics were recorded. Magnitude of paretic LL was reduced, while duration was increased compared with the nonparetic leg and nondisabled controls walking at matched speeds. The paretic LL and LU was significantly correlated with average leg angle, while the nonparetic leg significantly correlated with average knee angle. Three different patterns of LL and LU were identified (concave, convex, and linear). Individuals with hemiparesis make several biomechanical adjustments that minimize LL of the paretic leg. LL deviations were more pronounced with increased lateral placement of the paretic foot and with decreased functional gait speed. Characterization of these deviations may inspire new strategies for rehabilitation. PMID:23408212

  7. Influence of process parameters on the reaction kinetics of the chromium-catalyzed trimerization of ethylene.

    PubMed

    Wöhl, Anina; Müller, Wolfgang; Peitz, Stephan; Peulecke, Normen; Aluri, Bhaskar R; Müller, Bernd H; Heller, Detlef; Rosenthal, Uwe; Al-Hazmi, Mohammed H; Mosa, Fuad M

    2010-07-12

    In this paper we report the results of an extensive experimental kinetic study carried out on the novel ethylene trimerization catalyst system, comprising the chromium source [CrCl(3)(thf)(3)] (thf=tetrahydrofuran), a Ph(2)P-N(iPr)-P(Ph)-N(iPr)H (PNPNH) ligand (Ph=phenyl, iPr=isopropyl), and triethylaluminum (AlEt(3)) as activator. It could be shown that the initial activity shows a first-order dependency on the ethylene concentration. Also, a first-order dependency was found for the catalyst concentration. The initial activity follows a typical Arrhenius behavior with an experimentally determined activation energy of 52.6 kJ mol(-1). At elevated temperatures (ca. 80 degrees C), a significant deactivation was observed, which can be tentatively traced back to a ligand rearrangement in the presence of AlEt(3). After a fast initial phase, a pronounced 'kink' in the ethylene-uptake curve is observed, followed by a slow, almost linear, further increase of the total ethylene consumption. The catalyst composition, in particular the ligand/chromium and the cocatalyst/chromium molar ratio, has a strong impact on the catalytic performance of the trimerization of ethylene. PMID:20512824

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  9. 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.

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

    PubMed Central

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

    2012-01-01

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

  11. 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

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

    PubMed

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

    2016-05-01

    Nanosecond pulsed electric field (nsPEF) is a novel method to increase cell proliferation rate. The phenomenon is based on the microporation of cellular organelles and membranes. However, we have limited information on the effects of nsPEF on cell physiology. Several studies have attempted to describe the effects of this process, however no real time measurements have been conducted to date. In this study we designed a model system which allows the measurement of cellular processes before, during and after nsPEF treatment in real time. The system employs a Vabrema Mitoplicator(TM) nsPEF field generating instrument connected to a BD Accuri C6 cytometer with a silicon tube led through a peristaltic pump. This model system was applied to observe the effects of nsPEF in mammalian C6 glioblastoma (C6 glioma) and HEK-293 cell lines. Viability (using DRAQ7 dye), intracellular calcium levels (using Fluo-4 dye) and scatter characteristics were measured in a kinetic manner. Data were analyzed using the FACSKin software. The viability and morphology of the investigated cells was not altered upon nsPEF treatment. The response of HEK-293 cells to ionomycin as positive control was significantly lower in the nsPEF treated samples compared to non-treated cells. This difference was not observed in C6 cells. FSC and SSC values were not altered significantly by the nsPEF treatment. Our results indicate that this model system is capable of reliably investigating the effects of nsPEF on cellular processes in real time. © 2016 International Society for Advancement of Cytometry. PMID:26990601

  13. The Effect of Data Acquisition-Probeware and Digital Video Analysis on Accurate Graphical Representation of Kinetics in a High School Physics Class

    ERIC Educational Resources Information Center

    Struck, William; Yerrick, Randy

    2010-01-01

    The effects of two types of two well-established microcomputer-based teaching methods were examined for their effect on teaching high school students kinetics. The use of data acquisition probeware and digital video analysis were studied for their impact on students' conceptions and ability to interpret graphical relationships to real world…

  14. 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

  15. 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.

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

    PubMed

    Patra, Braja N; Majhi, Deola

    2015-06-25

    Polyaniline was synthesized by the oxidative polymerization method by using ammonium persulfate as an oxidant. The positive charge in the backbone of the polymer was generated by using Potash alum as a dopant. Scanning electron microscopy (SEM), Fourier transform infrared (FTIR), X-ray fluorescence (XRF), and X-ray diffraction (XRD) techniques were used for characterization of doped polyaniline. The doped polyaniline can be used for selective adsorption of various dyes (selectively sulfonated dyes) from aqueous solution. Adsorption studies regarding the effect of contact time, initial dye concentration, pH, doses of adsorbent, and temperature on adsorption kinetics were investigated. The influence of other anions like Cl(-), NO3(-), and SO4(2-) on the adsorption density of dyes onto doped polyaniline was also explored. Langmuir isotherm and pseudo-second-order kinetics were found to be the most appropriate models to describe the removal of anionic dyes from water through adsorption. Thermodynamic parameters such as free energy (ΔG(0)), enthalpy (ΔH(0)), and entropy (ΔS(0)) changes were also evaluated. The interaction of dyes with doped polyaniline was also investigated by FTIR and UV spectroscopy. PMID:26079693

  17. Photooxidative degradation of Acid Red 27 (AR27): modeling of reaction kinetic and influence of operational parameters.

    PubMed

    Daneshvar, Nezameddin; Rabbani, Mohammad; Modirshahla, Nasser; Behnajady, Mohammad-Ali

    2004-01-01

    The decolorization and mineralization of Acid Red 27 (AR27), an anionic monoazo dye of acid class, were studied by UV/H202 process in laboratory and real samples. Effects of different process parameters such as initial H2O2 and AR27 concentrations, pH and EtOH as an electron scavenger have been studied. H2O2 and UV light have a negligible effect when they were used on their own. The decolorization rate follows pseudo-first order kinetic with respect to the dye concentration. The rate constant of the attack of *OH radicals to the AR27 has been estimated through the adoption of a simplified kinetic model (1.03 x 10(8)M(-1)s(-1)). This model allows predicting the pseudo-first order rate constant and concentration of AR27 in different illumination times for different initial concentrations of H2O2. Mineralization studies showed, the formation of sulfate ions, the decrease of pH and 85% of COD reduction occur in less than 60 min. In the real wastewater color removal could be achieved after only 75 min, whereas 45% of COD reduction occurs after 105 min of illumination. PMID:15478925

  18. Micropollutant biotransformation kinetics associate with WWTP process parameters and microbial community characteristics.

    PubMed

    Helbling, Damian E; Johnson, David R; Honti, Mark; Fenner, Kathrin

    2012-10-01

    The objective of this work was to identify relevant wastewater treatment plant (WWTP) parameters and underlying microbial processes that influence the biotransformation of a diverse set of micropollutants. To do this, we determined biotransformation rate constants for ten organic micropollutants in batch reactors seeded with activated sludge from ten diverse WWTPs. The estimated biotransformation rate constants for each compound ranged between one and four orders of magnitude among the ten WWTPs. The biotransformation rate constants were tested for statistical associations with various WWTP process parameters, amoA transcript abundance, and acetylene-inhibited monooxygenase activity. We determined that (i) ammonia removal associates with oxidative micropollutant biotransformation reaction rates; (ii) archaeal but not bacterial amoA transcripts associate with both ammonia removal and oxidative micropollutant biotransformation reaction rates; and (iii) the activity of acetylene-inhibited monooxygenases (including ammonia monooxygenase) associates with ammonia removal and the biotransformation rate of isoproturon, but does not associate with all oxidative micropollutant biotransformations. In combination, these results lead to the conclusion that ammonia removal and amoA transcript abundance can potentially be predictors of oxidative micropollutant biotransformation reactions, but that the biochemical mechanism is not necessarily linked to ammonia monooxygenase activity. PMID:22938719

  19. The kinetic Sunyaev-Zel'dovich signal from inhomogeneous reionization: a parameter space study

    NASA Astrophysics Data System (ADS)

    Mesinger, Andrei; McQuinn, Matthew; Spergel, David N.

    2012-05-01

    Inhomogeneous reionization acts as a source of arcminute-scale anisotropies in the cosmic microwave background (CMB), the most important of which is the kinetic Sunyaev-Zel'dovich (kSZ) effect. Observational efforts with the Atacama Cosmology Telescope (ACT) and the South Pole Telescope (SPT) are poised to detect this signal for the first time, with projected 1 μ K2-level sensitivity to the dimensionless kSZ power spectrum around a multipole of l= 3000, [Δl3000]2. Indeed, recent SPT measurements place a bound of [Δl3000 ]2 < 2.8 μ K2 at 95 per cent confidence level, which degrades to [Δl3000 ]2 < 6 μ K2 if a significant correlation between the thermal Sunyaev-Zel'dovich (tSZ) effect and the cosmic infrared background (CIB) is allowed. To interpret these and upcoming observations, we compute the kSZ signal from a suite of ≈100 reionization models using the publicly available code 21CMFAST. Our physically motivated reionization models are parametrized by the ionizing efficiency of high-redshift galaxies, the minimum virial temperature of haloes capable of hosting stars, and the ionizing photon mean free path - a parametrization motivated by previous theoretical studies of reionization. We predict the contribution of patchy reionization to the l= 3000 kSZ power to be ? 1.5-3.5 μ K2. Therefore, even when adopting the lowest estimate in the literature for the post-reionization signal of ?, none of our models are consistent with the aggressive 2σ SPT bound that does not include correlations. This implies the following: (i) the early stages of reionization occurred in a much more homogeneous manner than suggested by the stellar-driven scenarios we explore, such as would be the case if, e.g. very high energy X-rays or exotic particles contributed significantly and/or (ii) that there is a significant correlation between the CIB and the tSZ. The later is perhaps not surprising, as massive haloes should host both hot gas and star-forming galaxies. On the other hand

  20. Modelling Escherichia coli concentration in a wastewater reservoir using an operational parameter MRT%FE and first order kinetics.

    PubMed

    Cirelli, Giuseppe Luigi; Consoli, Simona; Juanicó, Marcelo

    2009-01-01

    The operational parameter MRT%FE, representing the mean residence time of different ages fractions of effluent within a completely mixed reactor, was evaluated and integrated with first order kinetics. The parameter was used to model Escherichia coli concentrations in a municipal wastewater reservoir managed under different operating conditions (continuous and discontinuous). The study was conducted during 2004-2005 in a reservoir receiving effluents from the activated sludge treatment plant of Caltagirone (Eastern Sicily - Italy). The analytical approach is applied to the hydraulic state variables of the system (daily stored volumes, inlet and outlet flows), and the physical-chemical (pH, temperature, EC, TSS, BOD(5), COD) and bacteriological wastewater parameters (E. coli, FC, FS). In order to evaluate the reliability of the proposed approach, predicted E. coli concentrations within the reservoir were compared with measured ones by the correlation coefficient, F-test and Sperman's index. The study included the evaluation of die-off coefficient K(T) (d(-1)), light extinction coefficient K (m(-1)) and their relationships with climatic factors. Results of the study confirm that E. coli removal is related to the fractions of fresh effluent remaining each day within the reservoir with MRT%FE of about 5-8d, significantly lower than the nominal detention time (about 27d). The E. coli die-off coefficient (K(T)) was higher during system discontinuous operations and correlated with incident solar radiation and water temperature. PMID:18222594

  1. 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.

  2. Morphological Manipulation of Solvothermal Prepared CdSe Nanostructures by Controlling the Growth Rate of Nanocrystals as a Kinetic Parameter

    NASA Astrophysics Data System (ADS)

    Zarghami, V.; Mohammadi, M. R.; Fray, D. J.

    2012-11-01

    The morphological manipulation, structural characterization, and optical properties of different cadmium selenide (CdSe) nanostructures are reported. Two different CdSe nanostructures, i.e., nanorods and nanoparticles, were grown by controlling the concentration of precursors (i.e., cadmium nitrate and selenium dioxide) in ethanolamine solvent. By manipulating the kinetic parameter of the process (i.e., growth rate) under constant growth driving force (i.e., degree of supersaturation), the morphology of CdSe nanostructures can be tailored from nanorods to nanoparticles. The optical properties of CdSe nanostructures were investigated using ultraviolet-visible (UV-vis) spectroscopy. The absorption edge of the samples showed a blue-shift. CdSe nanostructures prepared under optimized conditions showed good microstructural and optical properties for solar cell applications.

  3. 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

  4. Effects of 10-week eccentric overload training on kinetic parameters during change of direction in football players.

    PubMed

    de Hoyo, Moisés; Sañudo, Borja; Carrasco, Luis; Mateo-Cortes, Jesús; Domínguez-Cobo, Sergio; Fernandes, Orlando; Del Ojo, Juan J; Gonzalo-Skok, Oliver

    2016-07-01

    The aim of the current study was to analyse the effect of 10-week eccentric overload training on kinetic parameters during change of direction (COD) in U-19 football players. The outcome measured included relative peak braking (rPB) and propulsive force (rPF), contact time (CT), time spent during braking (BT) and propulsive phase (PT), relative total (rTOT_IMP), braking (rB_IMP) and propulsive (rP_IMP) impulses. Between-group results showed a substantial better improvement (likely) in CT (ES: 0.72) and BT (ES: 0.74) during side-step cutting, and in rPB (ES: 0.84) and rB_IMP (ES: 0.72) during crossover cutting, in the experimental group (EXP) in comparison to control group (CON). Within-group analysis showed a substantially better performance (likely to almost certain) in CT (ES: 1.19), BT (ES: 1.24), PT (ES: 0.70), rPB (ES: 0.75), rPF (ES: 0.68), rTOT_IMP (ES: 0.48) and rB_IMP (ES: 0.50) in EXP during side-step cutting. Regarding crossover cutting, within-group analysis showed a substantial better performance (likely to almost certain) in CT (ES: 0.75), rPB (ES: 0.75), rPF (ES: 1.34), rTOT_IMP (ES: 0.61), rB_IMP (ES: 0.76) and rP_IMP (ES: 0.46) in EXP. In conclusion, the eccentric overload-based programme led to an improvement in kinetic parameters during COD football tasks. PMID:26963941

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  6. On the utility of spectroscopic imaging as a tool for generating geometrically accurate MR images and parameter maps in the presence of field inhomogeneities and chemical shift effects.

    PubMed

    Bakker, Chris J G; de Leeuw, Hendrik; van de Maat, Gerrit H; van Gorp, Jetse S; Bouwman, Job G; Seevinck, Peter R

    2013-01-01

    Lack of spatial accuracy is a recognized problem in magnetic resonance imaging (MRI) which severely detracts from its value as a stand-alone modality for applications that put high demands on geometric fidelity, such as radiotherapy treatment planning and stereotactic neurosurgery. In this paper, we illustrate the potential and discuss the limitations of spectroscopic imaging as a tool for generating purely phase-encoded MR images and parameter maps that preserve the geometry of an object and allow localization of object features in world coordinates. Experiments were done on a clinical system with standard facilities for imaging and spectroscopy. Images were acquired with a regular spin echo sequence and a corresponding spectroscopic imaging sequence. In the latter, successive samples of the acquired echo were used for the reconstruction of a series of evenly spaced images in the time and frequency domain. Experiments were done with a spatial linearity phantom and a series of test objects representing a wide range of susceptibility- and chemical-shift-induced off-resonance conditions. In contrast to regular spin echo imaging, spectroscopic imaging was shown to be immune to off-resonance effects, such as those caused by field inhomogeneity, susceptibility, chemical shift, f(0) offset and field drift, and to yield geometrically accurate images and parameter maps that allowed object structures to be localized in world coordinates. From these illustrative examples and a discussion of the limitations of purely phase-encoded imaging techniques, it is concluded that spectroscopic imaging offers a fundamental solution to the geometric deficiencies of MRI which may evolve toward a practical solution when full advantage will be taken of current developments with regard to scan time reduction. This perspective is backed up by a demonstration of the significant scan time reduction that may be achieved by the use of compressed sensing for a simple phantom. PMID:22898694

  7. 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 (48.9±2.7) and the lowest value of lipid peroxidation (2.7±0.8) were achieved by inclusion of 3mM concentration of melatonin in the semen extender and the highest activity of catalase (0.7±0.1) 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

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

    PubMed

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

    2016-07-01

    Quantifying turbulence velocity fluctuation is important because it indicates the fluid energy dissipation of the blood flow, which is closely related to the pressure drop along the blood vessel. This study aims to evaluate the effects of scan parameters and the target vessel size of 4D phase-contrast (PC)-MRI on quantification of turbulent kinetic energy (TKE). Comprehensive 4D PC-MRI measurements with various velocity-encoding (VENC), echo time (TE), and voxel size values were carried out to estimate TKE distribution in stenotic flow. The total TKE (TKEsum), maximum TKE (TKEmax), and background noise level (TKEnoise) were compared for each scan parameter. The feasibility of TKE estimation in small vessels was also investigated. Results show that the optimum VENC for stenotic flow with a peak velocity of 125cm/s was 70cm/s. Higher VENC values overestimated the TKEsum by up to six-fold due to increased TKEnoise, whereas lower VENC values (30cm/s) underestimated it by 57.1%. TE and voxel size did not significantly influence the TKEsum and TKEnoise, although the TKEmax significantly increased as the voxel size increased. TKE quantification in small-sized vessels (3-5-mm diameter) was feasible unless high-velocity turbulence caused severe phase dispersion in the reference image. PMID:26968139

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

    PubMed

    Drüen, S; Böddeker, 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

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

    SciTech Connect

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

    2015-09-21

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

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

    SciTech Connect

    Bunting, Bruce G

    2012-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-05-01

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

  13. 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

  14. A More Accurate Kinetic Monte Carlo Approach to a Monodimensional Surface Reaction: The Interaction of Oxygen with the RuO2(110) Surface.

    PubMed

    Pogodin, Sergey; López, Núria

    2014-07-01

    The theoretical study of catalysis would substantialy benefit from the use of atomistic simulations that can provide information beyond mean-field approaches. To date, the nanoscale understanding of surface reactions has been only qualitatively achieved by means of kinetic Monte Carlo coupled to density functional theory, KMC-DFT. Here, we examine a widely employed model for oxygen interaction with the RuO2(110) surface, a highly anisotropic system. Our analysis reveals several covert problems that render as questionable the model's predictions. We suggest an advanced approach that considers all the relevant elementary steps and configurations while smoothing the intrinsic errors in the DFT description of oxygen. Under these conditions, KMC provides quantitative agreement to temperature-programmed desorption experiments. These results illustrate how KMC-based simulations can be pushed forward so that they evolve toward being the standard methodology to study complex chemistry at the nanoscale. PMID:25061545

  15. A More Accurate Kinetic Monte Carlo Approach to a Monodimensional Surface Reaction: The Interaction of Oxygen with the RuO2(110) Surface

    PubMed Central

    2014-01-01

    The theoretical study of catalysis would substantialy benefit from the use of atomistic simulations that can provide information beyond mean-field approaches. To date, the nanoscale understanding of surface reactions has been only qualitatively achieved by means of kinetic Monte Carlo coupled to density functional theory, KMC-DFT. Here, we examine a widely employed model for oxygen interaction with the RuO2(110) surface, a highly anisotropic system. Our analysis reveals several covert problems that render as questionable the model’s predictions. We suggest an advanced approach that considers all the relevant elementary steps and configurations while smoothing the intrinsic errors in the DFT description of oxygen. Under these conditions, KMC provides quantitative agreement to temperature-programmed desorption experiments. These results illustrate how KMC-based simulations can be pushed forward so that they evolve toward being the standard methodology to study complex chemistry at the nanoscale. PMID:25061545

  16. Calibration of DFT Functionals for the Prediction of 57Fe Mössbauer Spectral Parameters in Iron-Nitrosyl and Iron-Sulfur Complexes: Accurate Geometries Prove Essential

    PubMed Central

    Sandala, Gregory M.; Hopmann, Kathrin H.; Ghosh, Abhik

    2011-01-01

    structure. Significant improvements to the isomer shift calibrations are obtained for B3LYP and B3LYP* when geometries obtained with the OLYP functional are used. In addition, greatly improved performance of these functionals is found if the complete test set is grouped separately into Fe–NO and Fe–S complexes. Calibration fits including only Fe–NO complexes are found to be excellent, while those containing the non-nitrosyl Fe–S complexes alone are found to demonstrate less accurate correlations. Similar trends are also found with OLYP, OPBE, PW91, and BP86. Correlations between experimental and calculated QSs were also investigated. Generally, universal and separate Fe–NO and Fe–S fit parameters obtained to determine QSs are found to be of good to excellent quality for every density functional examined, especially if [Fe4(NO)4(μ3-S)4]− is removed from the test set. PMID:22039359

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

    PubMed Central

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

    2006-01-01

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

  18. 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 = 69 mV and Epc = 4 mV. 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,α, was calculated and found to be 1.20 s(-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) mol cm(-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

  19. 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.

  20. 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.

  1. Effect of the adsorbate (Bromacil) equilibrium concentration in water on its adsorption on powdered activated carbon. Part 2: Kinetic parameters.

    PubMed

    Al Mardini, Fadi; Legube, Bernard

    2009-10-30

    The application of several monosolute equilibrium models has previously shown that Bromacil adsorption on SA-UF (Norit) powdered activated carbon (PAC) is probably effective on two types of sites. High reactivity sites were found to be 10-20 less present in a carbon surface than lower reactivity sites, according to the q(m) values calculated by isotherm models. The aims of this work were trying, primarily, to identify the kinetic-determinant stage of the sorption of Bromacil at a wide range of initial pesticide concentrations (approximately 5 to approximately 500 microg L(-1) at pH 7.8), and secondly, to specify the rate constants and other useful design parameters for the application in water treatment. It was therefore not possible to specify a priori whether the diffusion or surface reaction is the key step. It shows that many of the tested models which describe the stage of distribution or the surface reaction are correctly applied. However, the diffusivity values (D and D(0)) were found to be constant only constants for some specific experimental concentrations. The HSDM model of surface diffusion in pores was also applied but the values of the diffusion coefficient of surface (D(s)) were widely scattered and reduce significantly with the initial concentration or the equilibrium concentration in Bromacil. The model of surface reaction of pseudo-second order fitted particularly well and led to constant values which are independent of the equilibrium concentration, except for the low concentrations where the constants become significantly more important. This last observation confirms perfectly the hypothesis based on two types of sites as concluded by the equilibrium data (part 1). PMID:19560269

  2. Influence of Different Parameters on a Dual-Fractal Analysis for Antigen-Antibody Binding Kinetics for Biosensor Applications

    PubMed

    Milum; Sadana

    1997-03-01

    The diffusion-limited binding kinetics of antigen (or antibody) in solution to antibody (or antigen) immobilized on a biosensor surface is analyzed within a fractal framework. The fit obtained by a dual-fractal analysis is compared with that obtained from a single-fractal analysis. In some cases, the dual-fractal analysis provides an improved fit when compared with a single-fractal analysis. This was indicated by the regression analysis provided by Sigmaplot (46). It is of interest to note that the state of disorder (or the fractal dimension) and the binding rate coefficient both increase as the reaction progresses on the biosensor surface. For example, for the binding of HIV-1 p24 in solution to monoclonal antibody (MAb) 18 covalently attached to a biosensor surface (49), an increase in the fractal dimension by 59% from a value of Df1 equal to 1.91 to Df2 equal to 2.95 leads to an increase in the binding rate coefficient by a factor of 15 from k1 equal to 21.1 to k2 equal to 339. Also, the binding of MAb 6301 and 6303 in solution to insulin growth factor binding protein-1 (IGFBP-1) covalently attached to the sensor surface is adequately described by a single-fractal analysis (48). The binding of MAb 6302 to IGFBP-1, however, requires dual fractals. This indicates a difference in the binding mechanisms of these MAbs. The different examples analyzed and presented together provide a means by which the antigen-antibody reactions may be better controlled by noting the magnitude of the changes in the fractal dimension and in the binding rate coefficient as the reaction progresses on the biosensor surface. Also, the magnitude of the changes in the binding rate coefficients (k1 and k2) and in the fractal dimensions (Df1 and Df2) as different parameters are changed for the different biosensor applications are of particular value. PMID:9245322

  3. Construct a new method accurately extracting parameters associate with absorption and scattering coefficients of epithelium and stroma: using perpendicular and oblique fiber bundle probes

    NASA Astrophysics Data System (ADS)

    Hsieh, H. P.; Sung, K. B.; Hsu, F. W.

    2014-05-01

    Diffuse reflectance spectroscopy has been applied as a non-invasive method to measure tissue optical properties, which are associate with anatomical information. The algorithm widely used to extract, optical parameters from reflectance spectra is the regression method, which is time-consuming and frequently converge to local maxima. In this study, the effects of parameters changes on spectra are analyzed in different fiber geometries, source-detector separations and wavelengths. In the end of this paper, a new fitting algorithm is proposed base on parameters features found. The new algorithm is expected to enhance the accuracy of parameters extracted and save 75% of the process time.

  4. Generalized transition state theory calculations for the reactions D+H2 and H+D2 using an accurate potential energy surface: Explanation of the kinetic isotope effect

    NASA Astrophysics Data System (ADS)

    Garrett, Bruce C.; Truhlar, Donald G.

    1980-03-01

    Rate constants are calculated for the reactions D+H2→DH+H and H+D2→HD+D and compared to measured values. An accurate potential energy surface, based on the ab initio calculations of Liu and Siegbahn, was used. Rates were calculated using both conventional transition state theory and canonical variational theory. In the former, the generalized transition state dividing surface is located at the saddle point; in the latter it is located to maximize the generalized free energy of activation. We show that, in the absence of tunneling corrections, locating the generalized-transition-state dividing surface variationally has an important quantitative effect on the predicted rate constants for these systems and that, when tunneling is included, most of the effect of using a better dividing surface can be included in conventional transition state theory for these systems by using a consistent transmission coefficient for quantal scattering by the vibrationally adiabatic potential energy curve. Tunneling effects are important for these reactions even for temperatures larger than 400 K. We show how to separate classical recrossing effects from quantal corrections on reaction-coordinate motion in both the transmission coefficients and the kinetic isotope effects. Our most complete calculations are in excellent agreement with most of the measured rate constants and kinetic isotope effects.

  5. Photon kinetic modeling of laser pulse propagation in underdense plasma

    SciTech Connect

    Reitsma, A. J. W.; Trines, R. M. G. M.; Bingham, R.; Cairns, R. A.; Mendonca, J. T.; Jaroszynski, D. A.

    2006-11-15

    This paper discusses photon kinetic theory, which is a description of the electromagnetic field in terms of classical particles in coordinate and wave number phase space. Photon kinetic theory is applied to the interaction of laser pulses with underdense plasma and the transfer of energy and momentum between the laser pulse and the plasma is described in photon kinetic terms. A comparison is made between a one-dimensional full wave and a photon kinetic code for the same laser and plasma parameters. This shows that the photon kinetic simulations accurately reproduce the pulse envelope evolution for photon frequencies down to the plasma frequency.

  6. A new approach to relate kinetic parameters, composition and temperatures of igneous minerals: the case of Villarrica Volcano 1971 eruption

    NASA Astrophysics Data System (ADS)

    Contreras, C.; Parada, M. A.; Morgado, E. E.; Castruccio, A.

    2014-12-01

    This contribution provides a new approach to calculate the plagioclase composition of a given igneous rock based on kinetics parameters of crystallization obtained from CSD analyses of plagioclase. The procedure we use includes the following steps: 1) determination of the effective rates of crystal growth and nucleation based on the maximum time interval of mineral crystallization obtained from the CSD segment with the minimum slope and extrapolated to rest of the segments; 2) calculation of the total crystallization time; 3) determination of the time-dependent variation of plagioclase volume fraction based on crystal population density and CSD slopes; 4) calculation of the ideal rates of crystal growth and nucleation; 5) determination of temperature of plagioclase crystallization as a function of the ideal crystal growth rate; 6) determination of plagioclase composition as a function of the ideal crystal growth rate. We apply our model for plagioclase of 17 samples of The Villarrica Volcano 1971 eruption lava flow. All CSD show two segments with a break at 0.3 mm. The first segment is interpreted as the syn-eruptive crystallization and the second as the within-reservoir crystallization. An interval of 1.5 years as a maximum crystallization time for the syn-eruptive stage was estimated from Cashman's (1993) expression. Crystal growth rates in the reservoir stage took place during two stages. The first stage varies from 10^-8.9 to 10^-9.4 mm s-1 and the second one varied from 10^-9.4 to 10^-9.1 mm s-1. Finally, the crystal growth rate as high as 10^-7.8 mm s-1 were estimated for the syn-eruptive stage. Nucleation rates varies exponentially from 10^-13 to 10^-8 s-1 in the reservoir stage and from 10^-8 to 10^-1 s^-1 in the syn-eruptive stage. The total crystallization interval varies from 120 to 390 years. A mean total volume fraction of plagioclase of 0.55 was obtained (0.98 for all minerals) whereas a mean value of 0.054 was obtained at the onset of the eruption (0

  7. Application of the genetic algorithm to estimate the parameters related to the kinetics of the reduction of the iron ore, coal mixture

    SciTech Connect

    Kumar, A.; Roy, G.G.

    2005-12-01

    A novel methodology has been developed to calculate the kinetic parameters associated with reduction of ore-coal composite mixtures and to describe the time course of reduction of hematite to iron. The empirical parameters, namely, the three sets of activation energies and frequency factors, have been estimated by employing an evolutionary optimization tool, the genetic algorithm (GA). The model prediction matches well with the experimental literature data. The estimated activation energies are higher than the corresponding intrinsic values, indicating the role of heat transfer in the process.

  8. 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.

  9. 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 δ(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 μm; Vmax = 165.1 ± 6.3 nmol min(-1 ) mg(-1) ). However, isotopic discrimination (ε = [(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 ε-values among RubisCOs from primary producers is likely reflected in δ(13) C values of oceanic biomass. Currently, δ(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 δ(13) C measurements requires an accurate ε-value, and a mass

  10. Accurate fundamental parameters of CoRoT asteroseismic targets. The solar-like stars HD 49933, HD 175726, HD 181420, and HD 181906

    NASA Astrophysics Data System (ADS)

    Bruntt, H.

    2009-10-01

    Context: The CoRoT satellite has provided high-quality light curves of several solar-like stars. Analysis of these light curves provides oscillation frequencies that make it possible to probe the interior of the stars. However, additional constraints on the fundamental parameters of the stars are important for the theoretical modelling to be successful. Aims: We estimate the fundamental parameters (mass, radius, and luminosity) of the first four solar-like targets to be observed in the asteroseismic field. In addition, we determine their effective temperature, metallicity, and detailed abundance patterns. Methods: To constrain the stellar mass, radius and age we used the shotgun software, which compares the location of the stars in the Hertzsprung-Russell diagram with theoretical evolution models. This method takes the uncertainties of the observed parameters into account, including the large separation determined from the solar-like oscillations. We determined the effective temperatures and abundance patterns in the stars from the analysis of high-resolution spectra obtained with the HARPS, NARVAL, ELODIE and FEROS spectrographs. Results: We determined the mass, radius, and luminosity of the four CoRoT targets to within 5{-}10%, 2{-}4% and 5{-}13%, respectively. The quality of the stellar spectra determines how well we can constrain the effective temperature. For the two best spectra we get 1-σ uncertainties below 60 K and 100{-}150 K for the other two. The uncertainty on the surface gravity is less than 0.08 dex for three stars, while it is 0.15 dex for HD 181906. The reason for the larger uncertainty is that the spectrum has two components with a luminosity ratio of L_p/Ls = 0.50±0.15. While Hipparcos astrometric data strongly suggest it is a binary star, we find evidence that the fainter star may be a background star, since it is less luminous but hotter.

  11. Accurate calculations on 12 Λ-S and 28 Ω states of BN+ cation: potential energy curves, spectroscopic parameters and spin-orbit coupling.

    PubMed

    Shi, Deheng; Liu, Qionglan; Sun, Jinfeng; Zhu, Zunlue

    2014-03-25

    The potential energy curves (PECs) of 28 Ω states generated from the 12 states (X(4)Σ(-), 1(2)Π, 1(2)Σ(-), 1(2)Δ, 1(2)Σ(+), 2(2)Π, A(4)Π, B(4)Σ(-), 3(2)Π, 1(6)Σ(-), 2(2)Σ(-) and 1(6)Π) of the BN(+) cation are studied for the first time for internuclear separations from about 0.1 to 1.0 nm using an ab initio quantum chemical method. All the Λ-S states correlate to the first four dissociation channels. The 1(6)Σ(-), 3(2)Π and A(4)Π states are found to be the inverted ones. The 1(2)Σ(+), 2(2)Π, 3(2)Π and 2(2)Σ(-) states are found to possess the double well. The PECs are calculated by the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction approach with the Davidson correction. Core-valence correlation correction is included by a cc-pCV5Z basis set. Scalar relativistic correction is calculated by the third-order Douglas-Kroll Hamiltonian approximation at the level of a cc-pV5Z basis set. The convergent behavior of present calculations is discussed with respect to the basis set and level of theory. The spin-orbit coupling is accounted for by the state interaction approach with the Breit-Pauli Hamiltonian using the all-electron cc-pCV5Z basis set. All the PECs are extrapolated to the complete basis set limit. The spectroscopic parameters are obtained, and the vibrational properties of 1(2)Σ(+), 2(2)Π, 3(2)Π and 2(2)Σ(-) states are evaluated. Analyses demonstrate that the spectroscopic parameters reported here can be expected to be reliably predicted ones. The conclusion is gained that the effect of spin-orbit coupling on the spectroscopic parameters are not obvious almost for all the Λ-S states involved in the present paper. PMID:24334021

  12. Accurate calculations on 9 Λ-S and 28 Ω states of NSe radical in the gas phase: potential energy curves, spectroscopic parameters and spin-orbit couplings.

    PubMed

    Shi, Deheng; Li, Peiling; Sun, Jinfeng; Zhu, Zunlue

    2014-01-01

    The potential energy curves (PECs) of 28 Ω states generated from 9 Λ-S states (X(2)Π, 1(4)Π, 1(6)Π, 1(2)Σ(+), 1(4)Σ(+), 1(6)Σ(+), 1(4)Σ(-), 2(4)Π and 1(4)Δ) are studied for the first time using an ab initio quantum chemical method. All the 9 Λ-S states correlate to the first two dissociation limits, N((4)Su)+Se((3)Pg) and N((4)Su)+Se((3)Dg), of NSe radical. Of these Λ-S states, the 1(6)Σ(+), 1(4)Σ(+), 1(6)Π, 2(4)Π and 1(4)Δ are found to be rather weakly bound states. The 1(2)Σ(+) is found to be unstable and has double wells. And the 1(6)Σ(+), 1(4)Σ(+), 1(4)Π and 1(6)Π are found to be the inverted ones with the SO coupling included. The PEC calculations are made by the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction approach with the Davidson modification. The spin-orbit coupling is accounted for by the state interaction approach with the Breit-Pauli Hamiltonian. The convergence of the present calculations is discussed with respect to the basis set and the level of theory. Core-valence correlation corrections are included with a cc-pCVTZ basis set. Scalar relativistic corrections are calculated by the third-order Douglas-Kroll Hamiltonian approximation at the level of a cc-pV5Z basis set. All the PECs are extrapolated to the complete basis set limit. The variation with internuclear separation of spin-orbit coupling constants is discussed in brief for some Λ-S states with one shallow well on each PEC. The spectroscopic parameters of 9 Λ-S and 28 Ω states are determined by fitting the first ten vibrational levels whenever available, which are calculated by solving the rovibrational Schrödinger equation with Numerov's method. The splitting energy in the X(2)Π Λ-S state is determined to be about 864.92 cm(-1), which agrees favorably with the measurements of 891.80 cm(-1). Moreover, other spectroscopic parameters of Λ-S and Ω states involved here are

  13. 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

  14. Is scoring system of computed tomography based metric parameters can accurately predicts shock wave lithotripsy stone-free rates and aid in the development of treatment strategies?

    PubMed Central

    Badran, Yasser Ali; Abdelaziz, Alsayed Saad; Shehab, Mohamed Ahmed; Mohamed, Hazem Abdelsabour Dief; Emara, Absel-Aziz Ali; Elnabtity, Ali Mohamed Ali; Ghanem, Maged Mohammed; ELHelaly, Hesham Abdel Azim

    2016-01-01

    Objective: The objective was to determine the predicting success of shock wave lithotripsy (SWL) using a combination of computed tomography based metric parameters to improve the treatment plan. Patients and Methods: Consecutive 180 patients with symptomatic upper urinary tract calculi 20 mm or less were enrolled in our study underwent extracorporeal SWL were divided into two main groups, according to the stone size, Group A (92 patients with stone ≤10 mm) and Group B (88 patients with stone >10 mm). Both groups were evaluated, according to the skin to stone distance (SSD) and Hounsfield units (≤500, 500–1000 and >1000 HU). Results: Both groups were comparable in baseline data and stone characteristics. About 92.3% of Group A rendered stone-free, whereas 77.2% were stone-free in Group B (P = 0.001). Furthermore, in both group SWL success rates was a significantly higher for stones with lower attenuation <830 HU than with stones >830 HU (P < 0.034). SSD were statistically differences in SWL outcome (P < 0.02). Simultaneous consideration of three parameters stone size, stone attenuation value, and SSD; we found that stone-free rate (SFR) was 100% for stone attenuation value <830 HU for stone <10 mm or >10 mm but total number SWL sessions and shock waves required for the larger stone group were higher than in the smaller group (P < 0.01). Furthermore, SFR was 83.3% and 37.5% for stone <10 mm, mean HU >830, SSD 90 mm and SSD >120 mm, respectively. On the other hand, SFR was 52.6% and 28.57% for stone >10 mm, mean HU >830, SSD <90 mm and SSD >120 mm, respectively. Conclusion: Stone size, stone density (HU), and SSD is simple to calculate and can be reported by radiologists to applying combined score help to augment predictive power of SWL, reduce cost, and improving of treatment strategies. PMID:27141192

  15. The Araucaria Project: accurate stellar parameters and distance to evolved eclipsing binary ASAS J180057-2333.8 in Sagittarius Arm

    NASA Astrophysics Data System (ADS)

    Suchomska, K.; Graczyk, D.; Smolec, R.; Pietrzyński, G.; Gieren, W.; Stȩpień, K.; Konorski, P.; Pilecki, B.; Villanova, S.; Thompson, I. B.; Górski, M.; Karczmarek, P.; Wielgórski, P.; Anderson, R. I.

    2015-07-01

    We have analyzed the double-lined eclipsing binary system ASAS J180057-2333.8 from the All Sky Automated Survey (ASAS) catalogue. We measure absolute physical and orbital parameters for this system based on archival V-band and I-band ASAS photometry, as well as on high-resolution spectroscopic data obtained with ESO 3.6 m/HARPS and CORALIE spectrographs. The physical and orbital parameters of the system were derived with an accuracy of about 0.5-3 per cent. The system is a very rare configuration of two bright well-detached giants of spectral types K1 and K4 and luminosity class II. The radii of the stars are R1 = 52.12 ± 1.38 and R2 = 67.63 ± 1.40 R⊙ and their masses are M1 = 4.914 ± 0.021 and M2 = 4.875 ± 0.021 M⊙. The exquisite accuracy of 0.5 per cent obtained for the masses of the components is one of the best mass determinations for giants. We derived a precise distance to the system of 2.14 ± 0.06 kpc (stat.) ± 0.05 (syst.) which places the star in the Sagittarius-Carina arm. The Galactic rotational velocity of the star is Θs = 258 ± 26 km s-1 assuming Θ0 = 238 km s-1. A comparison with PARSEC isochrones places the system at the early phase of core helium burning with an age of slightly larger than 100 million years. The effect of overshooting on stellar evolutionary tracks was explored using the MESA star code.

  16. Kinetic isotope effect of the (16)O + (36)O2 and (18)O + (32)O2 isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study.

    PubMed

    Sun, Zhigang; Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-01

    The O + O2 isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the (18)O + (32)O2 and (16)O + (36)O2 reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the "reef" structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients. PMID:25956105

  17. Kinetic isotope effect of the 16O + 36O2 and 18O + 32O2 isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study

    NASA Astrophysics Data System (ADS)

    Sun, Zhigang; Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-01

    The O + O2 isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the 18O + 32O2 and 16O + 36O2 reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the "reef" structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients.

  18. Accurate calculations on the 22 electronic states and 54 spin-orbit states of the O2 molecule: potential energy curves, spectroscopic parameters and spin-orbit coupling.

    PubMed

    Liu, Hui; Shi, Deheng; Sun, Jinfeng; Zhu, Zunlue; Shulin, Zhang

    2014-04-24

    The potential energy curves (PECs) of 54 spin-orbit states generated from the 22 electronic states of O2 molecule are investigated for the first time for internuclear separations from about 0.1 to 1.0nm. Of the 22 electronic states, the X(3)Σg(-), A(')(3)Δu, A(3)Σu(+), B(3)Σu(-), C(3)Πg, a(1)Δg, b(1)Σg(+), c(1)Σu(-), d(1)Πg, f(1)Σu(+), 1(5)Πg, 1(3)Πu, 2(3)Σg(-), 1(5)Σu(-), 2(1)Σu(-) and 2(1)Δg are found to be bound, whereas the 1(5)Σg(+), 2(5)Σg(+), 1(1)Πu, 1(5)Δg, 1(5)Πu and 2(1)Πu are found to be repulsive ones. The B(3)Σu(-) and d(1)Πg states possess the double well. And the 1(3)Πu, C(3)Πg, A'(3)Δu, 1(5)Δg and 2(5)Σg(+) states are the inverted ones when the spin-orbit coupling is included. The PEC calculations are done by the complete active space self-consistent field (CASSCF) method, which is followed by the internally contracted multireference configuration interaction (icMRCI) approach with the Davidson correction. Core-valence correlation and scalar relativistic corrections are taken into account. The convergence of present calculations is evaluated with respect to the basis set and level of theory. The vibrational properties are discussed for the 1(5)Πg, 1(3)Πu, d(1)Πg and 1(5)Σu(-) states and for the second well of the B(3)Σu(-) state. The spin-orbit coupling effect is accounted for by the state interaction method with the Breit-Pauli Hamiltonian. The PECs of all the electronic states and spin-orbit states are extrapolated to the complete basis set limit. The spectroscopic parameters are obtained, and compared with available experimental and other theoretical results. Analyses demonstrate that the spectroscopic parameters reported here can be expected to be reliably predicted ones. The conclusion is obtained that the effect of spin-orbit coupling on the spectroscopic parameters are small almost for all the electronic states involved in this paper except for the 1(5)Σu(-), 1(5)Πg and 1(3)Πu. PMID:24486866

  19. Accurate calculations on the 12 electronic states and 23 Ω states of the SiBr+ cation: potential energy curves, spectroscopic parameters and spin-orbit coupling

    NASA Astrophysics Data System (ADS)

    Shi, De-Heng; Liu, Qionglan; Yu, Wei; Sun, Jinfeng; Zhu, Zunlue

    2014-05-01

    The potential energy curves (PECs) of 23 Ω states generated from the 12 electronic states (X1 Σ +, 21 Σ +, 11 Σ -, 11 Π, 21 Π, 11 Δ, 13 Σ +, 23 Σ +, 13 Σ -, a3 Π, 23 Π and 13 Δ) are studied for the first time. All the states correlate to the first dissociation channel of the SiBr+ cation. Of these electronic states, the 23 Σ + is the repulsive one without the spin-orbit coupling, whereas it becomes the bound one with the spin-orbit coupling added. On the one hand, without the spin-orbit coupling, the 11 Π, 21 Π and 23 Π are the rather weakly bound states, and only the 11 Π state possesses the double well; on the other hand, with the spin-orbit coupling included, the a3 Π and 11 Π states possess the double well, and the 13 Σ + and 13 Σ - are the inverted states. The PECs are calculated by the CASSCF method, which is followed by the internally contracted MRCI approach with the Davidson modification. Scalar relativistic correction is calculated by the third-order Douglas-Kroll Hamiltonian approximation with a cc-pVTZ-DK basis set. Core-valence correlation correction is included with a cc-pCVTZ basis set. The spin-orbit coupling is accounted for by the state interaction method with the Breit-Pauli Hamiltonian using the all-electron aug-cc-pCVTZ basis set. All the PECs are extrapolated to the complete basis set limit. The variation with internuclear separation of the spin-orbit coupling constant is discussed in brief. The spectroscopic parameters are evaluated for the 11 bound electronic states and the 23 bound Ω states, and are compared with available measurements. Excellent agreement has been found between the present results and the experimental data. It demonstrates that the spectroscopic parameters reported here can be expected to be reliably predicted ones. The Franck-Condon factors and radiative lifetimes of the transitions from the a3 Π 0 + and a3 Π 1 states to the X1 Σ + 0+ state are calculated for several low vibrational levels, and

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

    SciTech Connect

    Dominguez, H.; Nunez, M.J.; Lema, J.M. ); Chamy, R. )

    1993-05-01

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

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

    PubMed

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

    2016-06-01

    Biochemical reactions occurring during anaerobic digestion have been modelled using reaction kinetic equations such as first-order, Contois and Monod which are then combined to form mechanistic models. This work considers models which include between one and three biochemical reactions to investigate if the choice of the reaction rate equation, complexity of the model structure as well as the inclusion of inhibition plays a key role in the ability of the model to describe the methane production from the semi-continuous anaerobic digestion of green waste (GW) and food waste (FW). A parameter estimation method was used to investigate the most important phenomena influencing the biogas production process. Experimental data were used to numerically estimate the model parameters and the quality of fit was quantified. Results obtained reveal that the model structure (i.e. number of reactions, inhibition) has a much stronger influence on the quality of fit compared with the choice of kinetic rate equations. In the case of GW there was only a marginal improvement when moving from a one to two reaction model, and none with inclusion of inhibition or three reactions. However, the behaviour of FW digestion was more complex and required either a two or three reaction model with inhibition functions for both ammonia and volatile fatty acids. Parameter values for the best fitting models are given for use by other authors. PMID:26961220

  2. Determination of pyrolysis kinetic parameters of San Miguel (Texas) lignite. Final report. [650 to 800/sup 0/C; atmospheric pressure

    SciTech Connect

    Mann, U.; Selim, S.; Jih, J.

    1982-06-01

    The thermal decomposition of lignite in the absence of oxygen (pyrolysis) is important as a part of processes for converting lignite to more desirable fuels or for recovery of energy from deep basin lignite. The pyrolysis reaction kinetics of San Miguel (Texas) lignite has been experimentally studied in the temperature range 650 to 800/sup 0/C at atmospheric pressure. Gas and tar produced were collected and measured, and weight change as a function of time was measured. Lignite decomposition into gas, tar, and char can be described by three parallel first order reactions. In the temperature range investigated, the rates of pyrolysis are controlled by intraparticle transport phenomena. A simplified kinetic-transport model was used to estimate the individual reaction rate constants and activation energies. The gas produced was found to consist primarily of carbon dioxide, carbon monoxide, and hydrogen, with some methane, ethane, ethylene, and a trace C/sub 3/ compounds. Sample temperature increases and theoretical calculations indicate that oxygen from the lignite structure may be oxidizing lignite or pyrolysis products. It is recommended that, after suitable equipment modifications, the investigation be extended to study combined oxidation and pyrolysis of lignite.

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

    DOE PAGESBeta

    Bhagavatula, Abhijit; Huffman, Gerald; Shah, Naresh; Honaker, Rick

    2014-01-01

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

  4. 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.

  5. Applying thermodynamic and kinetic parameters to predict the physical stability of two differently prepared amorphous forms of simvastatin.

    PubMed

    Graeser, Kirsten A; Patterson, James E; Rades, Thomas

    2009-08-01

    Converting drugs from the crystalline to the amorphous state has gained increasing interest in the past decades as a potential method to overcome solubility issues of poorly water soluble drugs. A variety of techniques exist to convert the crystalline state of a drug to its amorphous form, including solution based, heat based and solid - solid conversion based methods. Inherent to the amorphous state, regardless of its preparation technique, is its physical instability and tendency to recrystallize. In this study, quench-cooled and cryo-milled simvastatin were compared with regards to their configurational thermodynamic parameters (entropy, enthalpy and Gibbs free energy) and mobility (relaxation times calculated using the Adam-Gibbs and Kohlrausch-Williams-Watts method). Stability studies showed quench-cooled simvastatin to be more stable than cryo-milled simvastatin. This was reflected in the calculated parameters although their absolute values did not agree with the stability behaviour. Relaxation time parameters of tau = 6.9 x 10(4) s for quench-cooled and tau = 1.7 x 10(4) s for cryo-milled simvastatin were calculated. The results from this study suggested that differences in the physical stability of amorphous forms prepared by different techniques are reflected in their mobility and thermodynamic parameters. Even though the predictive capabilities of these parameters for a set of different drugs may be limited, they can serve as a predictive tool for physical stability assessment if differently prepared amorphous forms of the same drug are investigated. PMID:19534709

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

    SciTech Connect

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

    2013-12-05

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

  7. Microbial maximal specific growth rate as a square-root function of biomass yield and two kinetic parameters.

    PubMed

    Wong, Wilson W; Liao, James C

    2009-11-01

    Understanding how growth rates changes under different perturbations is fundamental to many aspect of microbial physiology. In this work, we experimentally showed that maximal specific growth rate is a square-root function of the biomass yield, the substrate turnover number, and the maximum synthesis rate of the substrate transporter under that condition. We used Escherichia coli cultures in lactose minimal medium as a model system by introducing genetic modifications, in vitro evolution, and ethanol stress to the cell. Deletion of crr affected all three parameters in different directions while deletion of ptsG decreased only the biomass yield. Ethanol stress negatively impacted all three parameters, while anaerobicity decreased biomass yield and transporter synthesis rate. In addition, laboratory evolution increased the growth rate in lactose mostly through enhancing the expression rate of the lac operon. Despite all these changes, the growth rate of the perturbed strain was successfully related to the three parameters by the square-root equation. Thus, this square-root relationship provides insight into how growth rate is altered by different physiological parameters. PMID:19712746

  8. 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.

  9. 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.

  10. Parasitic analysis and π-type Butterworth-Van Dyke model for complementary-metal-oxide-semiconductor Lamb wave resonator with accurate two-port Y-parameter characterizations.

    PubMed

    Wang, Yong; Goh, Wang Ling; Chai, Kevin T-C; Mu, Xiaojing; Hong, Yan; Kropelnicki, Piotr; Je, Minkyu

    2016-04-01

    The parasitic effects from electromechanical resonance, coupling, and substrate losses were collected to derive a new two-port equivalent-circuit model for Lamb wave resonators, especially for those fabricated on silicon technology. The proposed model is a hybrid π-type Butterworth-Van Dyke (PiBVD) model that accounts for the above mentioned parasitic effects which are commonly observed in Lamb-wave resonators. It is a combination of interdigital capacitor of both plate capacitance and fringe capacitance, interdigital resistance, Ohmic losses in substrate, and the acoustic motional behavior of typical Modified Butterworth-Van Dyke (MBVD) model. In the case studies presented in this paper using two-port Y-parameters, the PiBVD model fitted significantly better than the typical MBVD model, strengthening the capability on characterizing both magnitude and phase of either Y11 or Y21. The accurate modelling on two-port Y-parameters makes the PiBVD model beneficial in the characterization of Lamb-wave resonators, providing accurate simulation to Lamb-wave resonators and oscillators. PMID:27131699

  11. Parasitic analysis and π-type Butterworth-Van Dyke model for complementary-metal-oxide-semiconductor Lamb wave resonator with accurate two-port Y-parameter characterizations

    NASA Astrophysics Data System (ADS)

    Wang, Yong; Goh, Wang Ling; Chai, Kevin T.-C.; Mu, Xiaojing; Hong, Yan; Kropelnicki, Piotr; Je, Minkyu

    2016-04-01

    The parasitic effects from electromechanical resonance, coupling, and substrate losses were collected to derive a new two-port equivalent-circuit model for Lamb wave resonators, especially for those fabricated on silicon technology. The proposed model is a hybrid π-type Butterworth-Van Dyke (PiBVD) model that accounts for the above mentioned parasitic effects which are commonly observed in Lamb-wave resonators. It is a combination of interdigital capacitor of both plate capacitance and fringe capacitance, interdigital resistance, Ohmic losses in substrate, and the acoustic motional behavior of typical Modified Butterworth-Van Dyke (MBVD) model. In the case studies presented in this paper using two-port Y-parameters, the PiBVD model fitted significantly better than the typical MBVD model, strengthening the capability on characterizing both magnitude and phase of either Y11 or Y21. The accurate modelling on two-port Y-parameters makes the PiBVD model beneficial in the characterization of Lamb-wave resonators, providing accurate simulation to Lamb-wave resonators and oscillators.

  12. Relationship Between the Structure Parameters of a Solid Body and the Kinetics of Donor-Acceptor Interaction in Heterogeneous Systems

    NASA Astrophysics Data System (ADS)

    Khentov, V. Ya.; Khussein, Kh. Kh.

    2016-05-01

    Interaction of an organic ligand molecule with the surface of a d-metal or of disperse particles of chemical compounds containing covalent bonds in a nonaqueous solvent (direct synthesis of complex compounds) is determined by the structure parameters of the solid body. The relationships of the rate and energy of activation of the donor-acceptor interaction of the metal with the Grüneisen coefficient and the Debye temperature of the metal have been established.

  13. Relationship Between the Structure Parameters of a Solid Body and the Kinetics of Donor-Acceptor Interaction in Heterogeneous Systems

    NASA Astrophysics Data System (ADS)

    Khentov, V. Ya.; Khussein, Kh. Kh.

    2016-06-01

    Interaction of an organic ligand molecule with the surface of a d-metal or of disperse particles of chemical compounds containing covalent bonds in a nonaqueous solvent (direct synthesis of complex compounds) is determined by the structure parameters of the solid body. The relationships of the rate and energy of activation of the donor-acceptor interaction of the metal with the Grüneisen coefficient and the Debye temperature of the metal have been established.

  14. 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

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

    PubMed

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

    2016-02-15

    Nanostructured SrSO4:Eu phosphors with high thermoluminescence (TL) emission temperatures have been synthesized through a controlled chemical precipitation method. Structural analysis and TL studies under both γ-ray and X-ray excitations were done. The phosphors were characterized using Powder X-ray diffraction, X-ray photoelectron spectroscopy, SEM, TEM, thermogravimetry, UV-VIS and photoluminescence studies. The average crystallite size estimated using PXRD data is found to be around 40nm. XPS and PL studies reveal that Eu(2+) ions are the luminescence emission centres in the phosphor. The phosphor is found to be highly TL sensitive to both γ-rays and X-rays with very high emission temperature which is not reported so far. The emission behaviour is suitable for environmental radiation dosimetry applications. The TL glow curve shows well-defined isolated high temperature emission peak at 312°C under 2Gy γ-excitation and 284°C for low energy diagnostic X-ray irradiation and 271°C for high energy therapeutic X-rays. Chen's peak shape method is applied to obtain the kinetic parameters behind the TL emission. The TL mechanism is found to follow second order kinetics, suggesting the probability of re-trapping of charge carriers. PMID:26562181

  16. 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.

  17. A structured model for simulation of cultures of the cyanobacterium Spirulina platensis in photobioreactors: II. Identification of kinetic parameters under light and mineral limitations.

    PubMed

    Cornet, J F; Dussap, C G; Cluzel, P; Dubertret, G

    1992-10-01

    A structured model for the culture of cyanobacteria in photobioreactors is developed on the basis of Schuster's approximations for radiative light transfer. This model is therefore limited to monodimensional geometries and kinetic aspects.Light-harvesting pigments play a crucial role in defining the profile of radiative transfer inside the culture medium and in controlling the metabolism, particularly the metabolic deviations induced by mineral limitations. Modeling therefore requires the biomass to be divided into several compartments, among which the light-harvesting compartment allows a working illuminated volume to be defined within the photobioreactor. This volume may change during batch cultures, largely decreasing as pigment concentration increases during growth but increasing as pigments are consumed during mineral limitation. This approach enables, in photobioreactors of simple parallelepipedic, geometries, kinetic parameters to be determined with high accuracy; this may then be extended to vessels of more complex geometries, such as cylindrical photobioreactors.The model is applied to controlled batch cultures of the cyanobacterium Spirulina platensis in parallelepipedic photobioreactors to assess its ability to predict the behavior of these microorganisms in conditions of light and mineral limitations. Results allowed the study of optimal operating condition for continuous cultures to be approached. PMID:18601186

  18. 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

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

    PubMed

    Mulquiney, P J; Kuchel, P W

    1999-09-15

    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

  20. 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

  1. 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)

    Pöschl, 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

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

    PubMed

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

    2012-10-01

    This work focuses on assessing the impact of two types of waste pretreatment: addition of bottom ashes and aerobic pretreatment on both the onset and kinetics of methanogenesis and the evolution of different parameters in the leachate. It also studies the correlation between methane production and the different parameters measured in the leachate produced. A total of six 68-L pilots were thus used with fresh municipal solid waste (MSW) shredded to a 40-mm size. After 14 months of landfilling, the control has produced less than 10 NLkg(-1)DM, which corresponds to around 7% of its biochemical methane potential (BMP). Nevertheless, on one hand for aerobically pretreated waste, the lag phase before the onset of methanogenesis is significantly reduced to 0.9 month compared to more than 1 year for the control. In addition to that, on average 110 NLkg(-1)DM (90% of the BMP) is produced within around 6.5 months. On the other hand, the waste with added bottom ash shows a slight improvement of the lag phase over the control for one of the duplicate: 6.1 months of lag phase. At this stage, on average of 26 NLkg(-1)DM waste are detected (22% of the BMP) no final conclusion concerning the impact of bottom ashes could be made. The data obtained for the leachate parameters agrees with the observations on methane production. Statistical correlation study shows that the two components of the corrected PCA interpret 76% of the variability of the data: SUVA (specific UV absorbance at 254 nm) and HPI(*) (% of hydrophilic compounds) are identified as interesting parameters for following up the biodegradation in landfill conditions. PMID:22640801

  3. Kinetics of the reaction of the heaviest hydrogen atom with H2, the 4Heμ + H2 → 4HeμH + H reaction: experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass.

    PubMed

    Fleming, Donald G; Arseneau, Donald J; Sukhorukov, Oleksandr; Brewer, Jess H; Mielke, Steven L; Truhlar, Donald G; Schatz, George C; Garrett, Bruce C; Peterson, Kirk A

    2011-11-14

    The neutral muonic helium atom (4)Heμ, in which one of the electrons of He is replaced by a negative muon, may be effectively regarded as the heaviest isotope of the hydrogen atom, with a mass of 4.115 amu. We report details of the first muon spin rotation (μSR) measurements of the chemical reaction rate constant of (4)Heμ with molecular hydrogen, (4)Heμ + H(2) → (4)HeμH + H, at temperatures of 295.5, 405, and 500 K, as well as a μSR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, k(Heμ), are compared with the predictions of accurate quantum mechanical (QM) dynamics calculations carried out on a well converged Born-Huang (BH) potential energy surface, based on complete configuration interaction calculations and including a Born-Oppenheimer diagonal correction. At the two highest measured temperatures the agreement between the quantum theory and experiment is good to excellent, well within experimental uncertainties that include an estimate of possible systematic error, but at 295.5 K the quantum calculations for k(Heμ) are below the experimental value by 2.1 times the experimental uncertainty estimates. Possible reasons for this discrepancy are discussed. Variational transition state theory calculations with multidimensional tunneling have also been carried out for k(Heμ) on the BH surface, and they agree with the accurate QM rate constants to within 30% over a wider temperature range of 200-1000 K. Comparisons between theory and experiment are also presented for the rate constants for both the D + H(2) and Mu + H(2) reactions in a novel study of kinetic isotope effects for the H + H(2) reactions over a factor of 36.1 in isotopic mass of the atomic reactant. PMID:22088068

  4. Evolution of a mini-scale biphasic dissolution model: Impact of model parameters on partitioning of dissolved API and modelling of in vivo-relevant kinetics.

    PubMed

    Locher, Kathrin; Borghardt, Jens M; Frank, Kerstin J; Kloft, Charlotte; Wagner, Karl G

    2016-08-01

    Biphasic dissolution models are proposed to have good predictive power for the in vivo absorption. The aim of this study was to improve our previously introduced mini-scale dissolution model to mimic in vivo situations more realistically and to increase the robustness of the experimental model. Six dissolved APIs (BCS II) were tested applying the improved mini-scale biphasic dissolution model (miBIdi-pH-II). The influence of experimental model parameters including various excipients, API concentrations, dual paddle and its rotation speed was investigated. The kinetics in the biphasic model was described applying a one- and four-compartment pharmacokinetic (PK) model. The improved biphasic dissolution model was robust related to differing APIs and excipient concentrations. The dual paddle guaranteed homogenous mixing in both phases; the optimal rotation speed was 25 and 75rpm for the aqueous and the octanol phase, respectively. A one-compartment PK model adequately characterised the data of fully dissolved APIs. A four-compartment PK model best quantified dissolution, precipitation, and partitioning also of undissolved amounts due to realistic pH profiles. The improved dissolution model is a powerful tool for investigating the interplay between dissolution, precipitation and partitioning of various poorly soluble APIs (BCS II). In vivo-relevant PK parameters could be estimated applying respective PK models. PMID:27297570

  5. 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.

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

    NASA Astrophysics Data System (ADS)

    Bisetti, Fabrizio; El Morsli, Mbark

    2014-01-01

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

  7. 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)

    Pöschl, 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

  8. Kinetics of the Reaction of the Heaviest Hydrogen Atom with H2, the 4Heμ + H2 -> 4HeμΗ + H Reaction: Experiments, Accurate Quantal Calculations, and Variational Transition State Theory, including Kinetic Isotope Effects for a Factor of 36.1 in Isotopic Mass

    SciTech Connect

    Fleming, Donald G.; Arseneau, Donald J.; Sukhorukov, Oleksandr; Brewer, Jess H.; Mielke, Steven L.; Truhlar, Donald G.; Schatz, George C.; Garrett, Bruce C.; Peterson, Kirk A.

    2011-11-14

    The neutral muonic helium atom {sup 4}He{mu}, in which one of the electrons of He is replaced by a negative muon, may be effectively regarded as the heaviest isotope of the hydrogen atom, with a mass of 4.115 amu. We report details of the first muon spin rotation ({mu}SR) measurements of the chemical reaction rate constant of {sup 4}He{mu} with molecular hydrogen, {sup 4}He{mu} + H{sub 2} {yields} {sup 4}He{mu}H + H, at temperatures of 295.5, 405, and 500 K, as well as a {mu}SR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, k{sub He{mu}}, are compared with the predictions of accurate quantum mechanical (QM) dynamics calculations carried out on a well converged Born-Huang (BH) potential energy surface, based on complete configuration interaction calculations and including a Born-Oppenheimer diagonal correction. At the two highest measured temperatures the agreement between the quantum theory and experiment is good to excellent, well within experimental uncertainties that include an estimate of possible systematic error, but at 295.5 K the quantum calculations for k{sub He{mu}} are below the experimental value by 2.1 times the experimental uncertainty estimates. Possible reasons for this discrepancy are discussed. Variational transition state theory calculations with multidimensional tunneling have also been carried out for k{sub He{mu}} on the BH surface, and they agree with the accurate QM rate constants to within 30% over a wider temperature range of 200-1000 K. Comparisons between theory and experiment are also presented for the rate constants for both the D + H{sub 2} and Mu + H{sub 2} reactions in a novel study of kinetic isotope effects for the H + H{sub 2} reactions over a factor of 36.1 in isotopic mass of the atomic reactant.

  9. Effect of genetic and physiological manipulations onthe kinetic and binding parameters of the adenine nucleotide translocator in Saccharomyces cervisiae and Candida utilis.

    PubMed

    Lauquin, G; Lunardi, J; Vignais, P V

    1976-01-01

    1. Ghe kinetic and binding parameters of adenine-nucleotide transport have been studied in mitochondria isolated from yeast cells in which the mitochondrial protein-synthetizing system had been inhibited by growth in the presence of erythromycin. These parameters have also been studied in promitochondria isolated from yeast grown in anaerobiosis aesence of ethidium bromide results in a loss of cytochromes b, alpha and alpha 3, but it does not affect the rate constant of ADP transport in isolated mitochondria, nor the number of binding sites for atractyloside, bongkrekic acid and ADP. 3. Promitochondria from S. cerevisiae grown in anaerobiosis, mitochondria from a qo mutant (qo mitochondria) and mitochondria from S. cerevisiae grown in the presence of erythromycin (ERY-mitochondria) are able to transport ADP by the same exchange-diffusion mechanism, sensitive to carboxy-atractyloside, and with the same rate constant as the wild type mitochondria. Promitochondria, qo mitochondria and ERY-mitochondria bind atractyloside, bongkrekic acid and ADP with the same high affinity as the wild type mitochondria. They only differ from the wild type mitochondria by a lower number of binding sites for ADP and for specific inhibitors of ADP transport. 4. Mitochondria isolated from the nuclear mutant p9 of S. cerevisae, called also op1, are characterized by a much lower affinity for bongkrekic acid than mitochondria from the wild type (20 times less). 5. Manipulation of the fatty acid composition of the mitochondrial membranes in the desaturase auxotroph mutant KD115 does not modify the number of sites, no their affinity of bongkrekic acid. 6. The above results are interpreted to mean that the structure and function of the mitochondrial adN translocator are not affected by any change in the mitochondrial protein synthetizing system. PMID:795470

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

    PubMed

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

    2016-10-01

    Thermodynamics and kinetics of sewage sludge (SS) and water hyacinth (WH) co-combustion as a blend fuel (SW) for bioenergy production were studied through thermogravimetric analysis. In CO2/O2 atmosphere, the combustion performance of SS added with 10-40wt.% WH was improved 1-1.97 times as revealed by the comprehensive combustion characteristic index (CCI). The conversion of SW in different atmospheres was identified and their thermodynamic parameters (ΔH,ΔS,ΔG) were obtained. As the oxygen concentration increased from 20% to 70%, the ignition temperature of SW decreased from 243.1°C to 240.3°C, and the maximum weight loss rate and CCI increased from 5.70%·min(-1) to 7.26%·min(-1) and from 4.913%(2)·K(-3)·min(-2) to 6.327%(2)·K(-3)·min(-2), respectively, which corresponded to the variation in ΔS and ΔG. The lowest activation energy (Ea) of SW was obtained in CO2/O2=7/3 atmosphere. PMID:27416513

  11. Effect of L-lactic acid, short-chain fatty acids, and pH in cecal infusate on morphometric and cell kinetic parameters of rat cecum.

    PubMed

    Ichikawa, H; Sakata, T

    1997-08-01

    We studied the influences of cecal infusion of NaCl, short-chain fatty acids (SCFA), and L-lactic acid at pH 5.0 or 7.0 for seven days on morphometric and cell kinetic parameters of the rat cecum. SCFA increased relative weight of the mucosa and submucosa, crypt size, and mitotic index in the cecum. L-Lactic acid stimulated mitosis only at pH 5.0. Crypt size correlated positively to epithelial proliferative activity only when NaCl or L-lactic acid was infused. SCFA should have changed the balance between production and loss of the cecal epithelial cells. The infusate pH by itself had no effect, but modified the effects of SCFA and L-lactic acid in different ways. Crypt size correlated positively to the logarithm of daily proton load of infusates. The above results indicate that epithelial cell proliferation in the cecum is influenced by both SCFA and L-lactic acid, although differently, and by proton load. PMID:9286223

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

    PubMed

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

    2013-07-01

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

  13. 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

  14. Biohydrogen production based on the evaluation of kinetic parameters of a mixed microbial culture using glucose and fruit-vegetable waste as feedstocks.

    PubMed

    Garcia-Peña, E I; Canul-Chan, M; Chairez, I; Salgado-Manjarez, E; Aranda-Barradas, J

    2013-09-01

    Hydrogen (H2) production from the organic fraction of solid waste such as fruit and vegetable waste (FVW) is a novel and feasible energy technology. Continuous application of this process would allow for the simultaneous treatment of organic residues and energy production. In this study, batch experiments were conducted using glucose as substrate, and data of H2 production obtained were successfully adjusted by a logistic model. The kinetic parameters (μ max = 0.101 h(-1), K s = 2.56 g/L) of an H2-producing microbial culture determined by the Monod and Haldane-Andrews growth models were used to establish the continuous culture conditions. This strategy led to a productive steady state in continuous culture. Once the steady state was reached in the continuous reactor, a maximum H2 production of 700 mL was attained. The feasibility of producing H2 from the FVW obtained from a local market in Mexico City was also evaluated using batch conditions. The effect of the initial FVW concentration on the H2 production and waste organic material degradation was determined. The highest H2 production rate (1.7 mmol/day), the highest cumulative H2 volume (310 mL), and 25 % chemical oxygen demand (COD) removal were obtained with an initial substrate (FVW) concentration of 37 g COD/L. The lowest H2 production rates were obtained with relatively low initial substrate concentrations of 5 and 11 g COD/L. The H2 production rates with FVW were also characterized by the logistic model. Similar cumulative H2 production was obtained when glucose and FVW were used as substrates. PMID:23832860

  15. 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

  16. New kinetic parameters for rat liver arginase measured at near-physiological steady-state concentrations of arginine and Mn2+.

    PubMed Central

    Maggini, S; Stoecklin-Tschan, F B; Mörikofer-Zwez, S; Walter, P

    1992-01-01

    A cytosolic cell-free system from rat liver containing the last three enzymes of the urea cycle, a number of cofactors and the substrates aspartate and citrulline was shown to synthesize urea at near-physiological rates ranging between 0.40 and 1.25 mumol/min per g of liver. This system was used to determine the kinetic parameters for arginase. With saturating amounts of Mn2+ (30 microM), arginine remained at a steady-state concentration of 5-35 microM depending on the aspartate and citrulline supply. Vmax. at micromolar arginine concentrations was between 1.10 and 1.25 mumol/min per g of liver, the K0.5 (arginine) between 6.0 and 6.5 microM and positive co-operativity was observed (Hill coefficient 2). Omission of Mn2+ caused a significant accumulation of arginine during the incubation, suggesting a regulatory effect of arginase. Under these conditions, Vmax. was 1.10-1.65 mumol/min per g of liver and the Km (arginine) increased up to 14.4-21.1 microM. The apparent Ka for Mn2+ in the presence of physiological concentrations of ATP, Mg2+ and arginine was calculated to be maximally 8 microM. Initial-velocity experiments with millimolar arginine concentrations as the direct substrate gave the following results, which are in good agreement with literature data. In the absence of Mn2+, Vmax. was 71.3 mumol/min per g of liver and the Km (arginine) 1.58 mM. With 30 microM-Mn2+, Vmax. was 69.4 mumol/min per g of liver and the Km (arginine) decreased to 0.94 mM. On the basis of our results, we propose the presence of high-affinity and low-affinity sites for arginine on rat liver arginase and postulate that alterations in arginase activity arising from changes in the concentration of arginine and of the cofactor Mn2+ may contribute to the regulation of ureagenesis in vivo. PMID:1590754

  17. Kinetics of improved 1,4-alpha-D-glucan glucohydrolase biosynthesis from a newly isolated Aspergillus oryzae IIB-6 and parameter significance analysis by 2-factorial design.

    PubMed

    Fatima, Bilqees; Ali, Sikander

    2012-01-01

    Sixteen different mould cultures viz. Aspergillus, Alternaria, Arthroderma, Trichoderma, Fusarium, Penicillium, Rhizopus and Chochliobolus were isolated from the soil samples of Qatar by serial dilution method. The preliminary screening of isolates was done by selecting initial colonies showing relatively bigger zones of starch hydrolysis on nutrient agar plates. The isolates were then subjected to secondary screening by submerged fermentation (SmF). The 1,4-α-D-glucan glucohydrolase (GGH) activity ranged from 1.906-12.675 U/ml/min. The product yield was analysed in dependence of mycelial morphology, biomass level and protein content. The isolate Aspergillus oryzae llB-6 which gave maximum enzyme production was incubated in M3 medium containing 20 g/l starch, 10 g/l lactose, 8.5 g/l yeast extract, 6 g/l corn steep liquor (CSL), 1.2 g/l MgSO4.7H2O, 1.3 g/l NH4Cl, 0.6 g/l CaCl2.2H2O, pH 5 at 30±2°C and 200 rpm. On the basis of kinetic variables, notably Qp (0.058±0.01(a) U/g/h), Yp/s (0.308±0.03(ab) U/g) and qp (0.210±0.032(abc) U/g fungal biomass/h), A. oryzae IIB-6 was found to be a hyper producer of GGH (LSD 0.0345) compared to A. kawachii IIB-2. A noticeable enhancement in enzyme activity of over 30% was observed (13.917±1.01 U/ml/min) when the process parameters viz. cultural conditions (pH 5, incubation period 72 h) and nutritional requirements (6 g/l CSL, 9.5 g/l yeast extract, 10 g/l starch, 20 g/l lactose) were further optimized using a 2-factorial Plackett-Burman design. The model terms were found to be highly significant (HS, p≤0.05), indicating the potential utility of the culture (dof~3). PMID:23961361

  18. Sensitivity of kinetic macro parameters to changes in dopamine synthesis, storage, and metabolism: a simulation study for [¹⁸F]FDOPA PET by a model with detailed dopamine pathway.

    PubMed

    Matsubara, Keisuke; Watabe, Hiroshi; Kumakura, Yoshitaka; Hayashi, Takuya; Endres, Christopher J; Minato, Kotaro; Iida, Hidehiro

    2011-08-01

    Quantitative interpretation of brain [¹⁸F]FDOPA PET data has been made possible by several kinetic modeling approaches, which are based on different assumptions about complex [¹⁸F]FDOPA metabolic pathways in brain tissue. Simple kinetic macro parameters are often utilized to quantitatively evaluate metabolic and physiological processes of interest, which may include DDC activity, vesicular storage, and catabolism from (18) F-labeled dopamine to DOPAC and HVA. A macro parameter most sensitive to the changes of these processes would be potentially beneficial to identify impaired processes in a neurodegenerative disorder such as Parkinson's disease. The purpose of this study is a systematic comparison of several [¹⁸F]FDOPA macro parameters in terms of sensitivities to process-specific changes in simulated time-activity curve (TAC) data of [¹⁸F]FDOPA PET. We introduced a multiple-compartment kinetic model to simulate PET TACs with physiological changes in the dopamine pathway. TACs in the alteration of dopamine synthesis, storage, and metabolism were simulated with a plasma input function obtained by a non-human primate [¹⁸F]FDOPA PET study. Kinetic macro parameters were calculated using three conventional linear approaches (Gjedde-Patlak, Logan, and Kumakura methods). For simulated changes in dopamine storage and metabolism, the slow clearance rate (k(loss) ) as calculated by the Kumakura method showed the highest sensitivity to these changes. Although k(loss) performed well at typical ROI noise levels, there was large bias at high noise level. In contrast, for simulated changes in DDC activity it was found that K(i) and V(T), estimated by Gjedde-Patlak and Logan method respectively, have better performance than k(loss). PMID:21190220

  19. Calculation of the geometrical three-point parameter constant appearing in the second order accurate effective medium theory expression for the B-term diffusion coefficient in fully porous and porous-shell random sphere packings.

    PubMed

    Deridder, Sander; Desmet, Gert

    2012-02-01

    Using computational fluid dynamics (CFD), the effective B-term diffusion constant γ(eff) has been calculated for four different random sphere packings with different particle size distributions and packing geometries. Both fully porous and porous-shell sphere packings are considered. The obtained γ(eff)-values have subsequently been used to determine the value of the three-point geometrical constant (ζ₂) appearing in the 2nd-order accurate effective medium theory expression for γ(eff). It was found that, whereas the 1st-order accurate effective medium theory expression is accurate to within 5% over most part of the retention factor range, the 2nd-order accurate expression is accurate to within 1% when calculated with the best-fit ζ₂-value. Depending on the exact microscopic geometry, the best-fit ζ₂-values typically lie in the range of 0.20-0.30, holding over the entire range of intra-particle diffusion coefficients typically encountered for small molecules (0.1 ≤ D(pz)/D(m) ≤ 0.5). These values are in agreement with the ζ₂-value proposed by Thovert et al. for the random packing they considered. PMID:22236565

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

    PubMed

    Andreozzi, Stefano; Miskovic, Ljubisa; Hatzimanikatis, Vassily

    2016-01-01

    Accurate determination of physiological states of cellular metabolism requires detailed information about metabolic fluxes, metabolite concentrations and distribution of enzyme states. Integration of fluxomics and metabolomics data, and thermodynamics-based metabolic flux analysis contribute to improved understanding of steady-state properties of metabolism. However, knowledge about kinetics and enzyme activities though essential for quantitative understanding of metabolic dynamics remains scarce and involves uncertainty. Here, we present a computational methodology that allow us to determine and quantify the kinetic parameters that correspond to a certain physiology as it is described by a given metabolic flux profile and a given metabolite concentration vector. Though we initially determine kinetic parameters that involve a high degree of uncertainty, through the use of kinetic modeling and machine learning principles we are able to obtain more accurate ranges of kinetic parameters, and hence we are able to reduce the uncertainty in the model analysis. We computed the distribution of kinetic parameters for glucose-fed E. coli producing 1,4-butanediol and we discovered that the observed physiological state corresponds to a narrow range of kinetic parameters of only a few enzymes, whereas the kinetic parameters of other enzymes can vary widely. Furthermore, this analysis suggests which are the enzymes that should be manipulated in order to engineer the reference state of the cell in a desired way. The proposed approach also sets up the foundations of a novel type of approaches for efficient, non-asymptotic, uniform sampling of solution spaces. PMID:26474788

  1. Nodal analysis for reactor kinetics and stability. [PWR; BWR

    SciTech Connect

    Park, J.K.; Becker, M.; Park, G.C.

    1983-07-01

    General space kinetics models have been developed for more accurate stability analysis utilizing nodal analysis, a commonly used technique for analyzing power distributions in large power reactors. Kinetics parameters for use in these kinetics models have been properly derived by utilizing self-consistent nodal data and power distributions. The procedure employed in the nodal code SIMULATE has been utilized for power distribution, since that methodology is general and includes various commonly used nodal methods as special cases. Cross sections are correlated as functions of void fraction and exposure. A computer program investigating thermo-hydrodynamic stability, NUFREQ has been modified to accommodate general spatial kinetics models with an improved thermal-hydraulics model. Stability analyses have been performed for density wave oscillations for a representative operating BWR system. Spatial coupling effects on the stability margins were found to be significant.

  2. Metastable Solution Thermodynamic Properties and Crystal Growth Kinetics

    NASA Technical Reports Server (NTRS)

    Kim, Soojin; Myerson, Allan S.

    1996-01-01

    The crystal growth rates of NH4H2PO4, KH2PO4, (NH4)2SO4, KAl(SO4)2 central dot 12H2O, NaCl, and glycine and the nucleation rates of KBr, KCl, NaBr central dot 2H2O, (NH4)2Cl, and (NH4)2SO4 were expressed in terms of the fundamental driving force of crystallization calculated from the activity of supersaturated solutions. The kinetic parameters were compared with those from the commonly used kinetic expression based on the concentration difference. From the viewpoint of thermodynamics, rate expressions based on the chemical potential difference provide accurate kinetic representation over a broad range of supersaturation. The rates estimated using the expression based on the concentration difference coincide with the true rates of crystallization only in the concentration range of low supersaturation and deviate from the true kinetics as the supersaturation increases.

  3. 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

  4. Kinetics and Activation Parameters for Oxidations of Styrene by Compounds I from Cytochrome P450BM-3 (CYP102A1) Heme Domain and from CYP119†

    PubMed Central

    Yuan, Xinting; Wang, Qin; Horner, John H.; Sheng, Xin; Newcomb, Martin

    2009-01-01

    Cytochrome P450 (CYP or P450) enzymes are ubiquitous in nature where they catalyze a vast array of oxidation reactions. The active oxidants in P450s have long been assumed to be iron(IV)-oxo porphyrin radical cations termed Compounds I, but P450 Compounds I have proven difficult to prepare. The recent development of an entry to these transients by photo-oxidation of the corresponding iron(IV)-oxo neutral porphyrin species (Compounds II) permits spectroscopic and kinetic studies. We report here application of the photo-oxidation method for production of Compound I from the heme domain of CYP102A1 (cytochrome P450BM-3), and product and kinetic studies of reactions of styrene with this Compound I transient and also Compound I from CYP119. The studies were performed at low temperatures in 1:1 (v:v) mixtures of glycerol--phosphate buffer. Single turnover reactions at 0 °C gave styrene oxide in good yields. In kinetic studies conducted between −10 and −50 °C, both Compounds I displayed saturation kinetics permitting determinations of binding constants and first-order oxidation rate constants. Temperature-dependent functions for the binding constants and rate constants were determined for both Compounds I. In the temperature range studied, the Compound I transient from CYP102A1 heme domain bound styrene more strongly than Compound I from CYP119, but the rate constants for oxidations of styrene by the latter were somewhat larger than those for the former. The temperature dependent functions for the first-order oxidation reactions are log k = 13.2 – 15.2/2.303RT and log k = 13.3 – 14.6/2.303RT (kcal/mol) for Compounds I from CYP102A1 heme domain and CYP119, respectively. PMID:19708688

  5. 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.

  6. Kinetic description of metal nanocrystal oxidation: a combined theoretical and experimental approach for determining morphology and diffusion parameters in hollow nanoparticles by the nanoscale Kirkendall effect

    NASA Astrophysics Data System (ADS)

    Watanabe, Yoshiki; Mowbray, Ryan W.; Rice, Katherine P.; Stoykovich, Mark P.

    2014-10-01

    The oxidation of colloidal metal nanocrystals to form hollow shells via the nanoscale Kirkendall effect has been investigated using a combined theoretical and experimental approach. A generalized kinetic model for the formation of hollow nanoparticles describes the phenomenon and, unlike prior models, is applicable to any material system and accounts for the effect of surface energies. Phase diagrams of the ultimate oxidized nanoparticle morphology and the time to achieve complete oxidation are calculated, and are found to depend significantly upon consideration of surface energy effects that destabilize the initial formation of small voids. For the oxidation of Cu nanocrystals to Cu2O nanoparticles, we find that the diffusion coefficients dictate the morphological outcomes: the ratio of ? to ? controls the void size, ? determines the time of oxidation and ? is largely irrelevant in the kinetics of oxidation. The kinetic model was used to fit experimental measurements of 11 nm diameter Cu nanocrystals oxidized in air from which temperature-dependent diffusivities of ? and ? for 100 ≤ T ≤ 200 °C were determined. In contrast to previous interpretations of the nanoscale Kirkendall effect in the Cu/Cu2O system, these results are obtained without any a priori assumptions about the relative magnitudes of ? and ?. The theoretical and experimental approaches presented here are broadly applicable to any nanoparticle system undergoing oxidation, and can be used to precisely control the final nanoparticle morphology for applications in catalysis or optical materials.

  7. Grading More Accurately

    ERIC Educational Resources Information Center

    Rom, Mark Carl

    2011-01-01

    Grades matter. College grading systems, however, are often ad hoc and prone to mistakes. This essay focuses on one factor that contributes to high-quality grading systems: grading accuracy (or "efficiency"). I proceed in several steps. First, I discuss the elements of "efficient" (i.e., accurate) grading. Next, I present analytical results…

  8. 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

  9. Kinetics of destruction and regeneration of the haemopoietic system after administration of busulphan and cyclophosphamide followed by bone marrow transplantation. Peripheral blood parameters.

    PubMed

    Szczylik, C; Ratajczak, M Z; Urbanowska, E; Jedrzejczak, W W

    1989-01-01

    The kinetics of restoration of haemopoiesis was studied in 10 patients prepared for allogenic bone marrow transplantation with busulphan combined with cyclophosphamide. The morphology of peripheral blood after administration of these drugs and transplantation of allogenic bone marrow was similar to that reported elsewhere after irradiation, cyclophosphamide administration and bone marrow transplantation, the cell counts falling almost to zero within several days after the end of the pharmacological preparation, and later rising to normal values within the period from several weeks to several months after transplantation. PMID:2519630

  10. Kinetic parameters and mechanisms of the batch biosorption of Cr(VI) and Cr(III) onto Leersia hexandra Swartz biomass.

    PubMed

    Li, Jianping; Lin, Qingyu; Zhang, Xuehong; Yan, Yan

    2009-05-01

    The hyperaccumulative plant species Leersia hexandra Swartz, particularly, has been considered for its detoxification mechanism for phytoremediation of chromium-contaminated water environments. This study investigates the role of the adsorption mechanism of the L. hexandra Sw. biomass on the removal of chromium ions Cr(VI) and Cr(III) from an aqueous solution. The interaction between chromium ions and the L. hexandra Sw. biomass was characterized by using infrared spectroscopy. The results indicate that the binding process of the chromium ions involves the active participation of ligands present in the biomass, such as acylamide, carbonyl, amino, carboxyl, and hydroxyl groups, to immobilize the chromium ions. Equilibrium biosorption experiments were carried out to investigate the effects of pH values and contact time. Adsorption isotherms were modeled with the Langmuir and Freundlich equations and isotherm constants were calculated. Kinetic experiments showed the rapid process of biosorption and the pseudo-second-order model was successfully applied to predict the rate constant of biosorption. This study firstly discovered the kinetics equilibrium modelling of L. hexandra Sw. biomass on biosorption Cr(VI) and Cr(III). PMID:19251269

  11. KINETICS OF SLURRY PHASE FISCHER-TROPSCH SYNTHESIS

    SciTech Connect

    Dragomir B. Bukur; Gilbert F. Froment; Tomasz Olewski

    2006-09-29

    This report covers the fourth year of a research project conducted under the University Coal Research Program. The overall objective of this project is to develop a comprehensive kinetic model for slurry-phase Fischer-Tropsch synthesis (FTS) employing iron-based catalysts. This model will be validated with experimental data obtained in a stirred-tank slurry reactor (STSR) over a wide range of process conditions. The model will be able to predict molar flow rates and concentrations of all reactants and major product species (water, carbon dioxide, linear 1- and 2-olefins, and linear paraffins) as a function of reaction conditions in the STSR. During the fourth year of the project, an analysis of experimental data collected during the second year of this project was performed. Kinetic parameters were estimated utilizing product distributions from 27 mass balances. During the reporting period two kinetic models were employed: a comprehensive kinetic model of Dr. Li and co-workers (Yang et al., 2003) and a hydrocarbon selectivity model of Van der Laan and Beenackers (1998, 1999) The kinetic model of Yang et al. (2003) has 24 parameters (20 parameters for hydrocarbon formation, and 4 parameters for the water-gas-shift (WGS) reaction). Kinetic parameters for the WGS reaction and FTS synthesis were estimated first separately, and then simultaneously. The estimation of these kinetic parameters employed the Levenberg-Marquardt (LM) method and the trust-region reflective Newton large-scale (LS) method. A genetic algorithm (GA) was incorporated into estimation of parameters for FTS reaction to provide initial estimates of model parameters. All reaction rate constants and activation energies were found to be positive, but at the 95% confidence level the intervals were large. Agreement between predicted and experimental reaction rates has been fair to good. Light hydrocarbons are predicted fairly accurately, whereas the model underpredicts values of higher molecular weight

  12. Accurate monotone cubic interpolation

    NASA Technical Reports Server (NTRS)

    Huynh, Hung T.

    1991-01-01

    Monotone piecewise cubic interpolants are simple and effective. They are generally third-order accurate, except near strict local extrema where accuracy degenerates to second-order due to the monotonicity constraint. Algorithms for piecewise cubic interpolants, which preserve monotonicity as well as uniform third and fourth-order accuracy are presented. The gain of accuracy is obtained by relaxing the monotonicity constraint in a geometric framework in which the median function plays a crucial role.

  13. Accurate Finite Difference Algorithms

    NASA Technical Reports Server (NTRS)

    Goodrich, John W.

    1996-01-01

    Two families of finite difference algorithms for computational aeroacoustics are presented and compared. All of the algorithms are single step explicit methods, they have the same order of accuracy in both space and time, with examples up to eleventh order, and they have multidimensional extensions. One of the algorithm families has spectral like high resolution. Propagation with high order and high resolution algorithms can produce accurate results after O(10(exp 6)) periods of propagation with eight grid points per wavelength.

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

    PubMed Central

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

    2013-01-01

    This study explored the potential use of a sulfate radical (SO·−4)-based photochemical oxidation process to treat the commercial nonionic surfactant octylphenol polyethoxylate (OPPE) Triton™ X-45. For this purpose, the effect of initial S2O2−8 (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 S2O2−8 concentrations (≥2.5 mM). S2O2−8/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 S2O2−8. On the other hand, TOC removal efficiencies dropped down to only 40% under the same reaction conditions. S2O2−8/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 S2O2−8/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 SO·−4 and HO·, bimolecular reaction rate coefficients of OPPE with SO·−4 and HO· were determined by employing competition kinetics with aqueous phenol (47 μM) selected as the reference compound. The pseudo-first-order abatement rate coefficient obtained for OPPE during S2O2−8/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 pseudo-first-order abatement rate coefficients were obtained for both OPPE (0.087 min−1) and phenol (0.140 min−1). From the kinetic study, second-order reaction rate coefficients for OPPE with SO·−4 and HO· were determined as 9.8 × 108 M−1 s−1 and 4.1 × 109 M−1 s−1, respectively. The kinetic study also revealed

  15. Accurate stopping power measurements for (0.21-2.68) MeV/u 1H+ and 4He+ ions crossing thin Al foils; extraction of the (I, b) parameters

    NASA Astrophysics Data System (ADS)

    Moussa, D.; Damache, S.; Ouichaoui, S.

    2015-01-01

    The stopping powers of thin Al foils for H+ and 4He+ ions have been measured over the energy range E = (206.03- 2680.05) keV/amu with an overall relative uncertainty better than 1% using the transmission method. The derived S (E) experimental data are compared to previous ones from the literature, to values derived by the SRIM-2008 code or compiled in the ICRU-49 report, and to the predictions of Sigmund-Schinner binary collision stopping theory. Besides, the S (E) data for H+ ions together with those for He2+ ions reported by Andersen et al. (1977) have been analyzed over the energy interval E > 1.0 MeV using the modified Bethe-Bloch stopping theory. The following sets of values have been inferred for the mean excitation potential, I, and the Barkas-Andersen parameter, b, for H+ and He+ projectiles, respectively: { (I = 164 ± 3) eV, b = 1.40 } and { (I = 163 ± 2.5) eV, b = 1.38 } . As expected, the I parameter is found to be independent of the projectile electronic structure presumably indicating that the contribution of charge exchange effects becomes negligible as the projectile velocity increases. Therefore, the I parameter must be determined from precise stopping power measurements performed at high projectile energies where the Bethe stopping theory is fully valid.

  16. 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%.

  17. 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)

  18. 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)

  19. Estimation of the effective parameter of spinorbital interaction of electrons in intermetallic Er-In system compounds from the kinetic and magnetic properties

    NASA Astrophysics Data System (ADS)

    Kuvandikov, O. K.; Hamraev, N. S.; Razhabov, R. M.; Éshkulov, A. A.

    2012-05-01

    Normal, R 0 and anomalous, R S components of the Hall coefficient are determined from the results of experimental investigations of temperature dependences of the Hall coefficient, magnetic susceptibility, and specific electrical resistance for intermetallic Er2In, ErIn, and Er3In5 compounds. Effective parameters of spinorbital interaction λSO of intermetallic compounds are calculated from anomalous components RS of the Hall coefficient and specific electrical resistance. The results calculated for the band parameters and effective parameters of spin-orbital interaction λSO for Er-In system intermetallides coincide by orders of magnitude with the results obtained in [4,7,8] from the optical spectra of pure rare-earth metals.

  20. 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)

  1. Accurately Predicting Complex Reaction Kinetics from First Principles

    NASA Astrophysics Data System (ADS)

    Green, William

    Many important systems contain a multitude of reactive chemical species, some of which react on a timescale faster than collisional thermalization, i.e. they never achieve a Boltzmann energy distribution. Usually it is impossible to fully elucidate the processes by experiments alone. Here we report recent progress toward predicting the time-evolving composition of these systems a priori: how unexpected reactions can be discovered on the computer, how reaction rates are computed from first principles, and how the many individual reactions are efficiently combined into a predictive simulation for the whole system. Some experimental tests of the a priori predictions are also presented.

  2. 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

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

    PubMed

    Báez, María 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 μg(1-1/n)mL(1/n)g⁻¹. The relevance of humic acid and humin was deduced from isotherm and kinetics experiments. KOC values varied between 221 and 679 mLg⁻¹ 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

  4. Probing the Kinetic Parameters of Plutonium-Naturally Occurring Organic Matter Interactions in Freshwaters Using the Diffusive Gradients in Thin Films Technique.

    PubMed

    Cusnir, Ruslan; Jaccard, Maud; Bailat, Claude; Christl, Marcus; Steinmann, Philipp; Haldimann, Max; Bochud, François; Froidevaux, Pascal

    2016-05-17

    The interaction of trace metals with naturally occurring organic matter (NOM) is a key process of the speciation of trace elements in aquatic environments. The rate of dissociation of metal-NOM complexes will impact the amount of free metal available for biouptake. Assessing the bioavailability of plutonium (Pu) helps to predict its toxic effects on aquatic biota. However, the rate of dissociation of Pu-NOM complexes in natural freshwaters is currently unknown. Here, we used the technique of diffusive gradients in thin films (DGT) with several diffusive layer thicknesses to provide new insights into the dissociation kinetics of Pu-NOM complexes. Results show that Pu complexes with NOM (mainly fulvic acid) are somewhat labile (0.2 ≤ ξ ≤ 0.4), with kd = 7.5 × 10(-3) s(-1). DGT measurements of environmental Pu in organic-rich natural water confirm these findings. In addition, we determined the effective diffusion coefficients of Pu(V) in polyacrylamide (PAM) gel in the presence of humic acid using a diffusion cell (D = 1.70 ± 0.25 × 10(-6) cm(2) s(-1)). These results show that Pu(V) is a more mobile species than Pu(IV). PMID:27064997

  5. The influence of fibrin(ogen) fragments on the kinetic parameters of the tissue-type plasminogen-activator-mediated activation of different forms of plasminogen.

    PubMed

    Nieuwenhuizen, W; Voskuilen, M; Vermond, A; Hoegee-de Nobel, B; Traas, D W

    1988-05-16

    In the present work we have determined Km,app and kcat,app values for tissue-type plasminogen-activator-catalyzed activation of Glu-plasminogen, Lys-plasminogen and mini-plasminogen in the absence and in the presence of fibrinogen-derived fragments. These were CNBr fragment 2, the A alpha chain remnant of CNBr fragment 2 (A alpha 148-207) and plasmin-generated fragment D-EGTA. The time course of plasmin formation from the various types of plasminogen (plg) was measured spectrophotometrically in a coupled assay system where D-valyl-L-leucyl-L-lysine p-nitroanilide served as a plasmin substrate. The kinetic constants are summarized as follows. (Values in parentheses are concentrations at which the minimum Km,app and maximum kcat,app value is reached.) (Table: see text). In conclusion our results show that CNBr fragment 2, A alpha 148-207 and to some extent D-EGTA mimic the accelerating effect of fibrin. The first two of these fragments did not accelerate activation of mini-plasminogen, lacking the kringle structures I-IV. This suggests that the stimulating effects of these two fragments were dependent on the presence of kringles I-IV of the plasminogen molecule. PMID:3131143

  6. Accurate determination of optical bandgap and lattice parameters of Zn{sub 1-x}Mg{sub x}O epitaxial films (0{<=}x{<=}0.3) grown by plasma-assisted molecular beam epitaxy on a-plane sapphire

    SciTech Connect

    Laumer, Bernhard; Schuster, Fabian; Stutzmann, Martin; Bergmaier, Andreas; Dollinger, Guenther; Eickhoff, Martin

    2013-06-21

    Zn{sub 1-x}Mg{sub x}O epitaxial films with Mg concentrations 0{<=}x{<=}0.3 were grown by plasma-assisted molecular beam epitaxy on a-plane sapphire substrates. Precise determination of the Mg concentration x was performed by elastic recoil detection analysis. The bandgap energy was extracted from absorption measurements with high accuracy taking electron-hole interaction and exciton-phonon complexes into account. From these results a linear relationship between bandgap energy and Mg concentration is established for x{<=}0.3. Due to alloy disorder, the increase of the photoluminescence emission energy with Mg concentration is less pronounced. An analysis of the lattice parameters reveals that the epitaxial films grow biaxially strained on a-plane sapphire.

  7. Kinetic model of continuous-wave flow chemical lasers

    NASA Astrophysics Data System (ADS)

    Gao, Z.; X., E.

    1982-02-01

    A kinetic approach to modeling the gain in a chemical wave continuous laser when the lasing frequency is coincident with the center of the line shape is presented. Governing equations are defined for the relaxing behavior of an initially nonequilibrium distribution toward the local equilibrium Boltzmann-Maxwellian distribution. A new gain is introduced which is related to the thermal motion of the molecules and cold-reaction and premixed CW models are discussed. Coincidence of the lasing frequency with the line shape is demonstrated to result in a radiative intensity within the homogeneous broadening limit. The rate model predictions are compared with those of the kinetic model. It is found that when the broadening parameter is less than 0.2 the kinetic model more accurately describes the behavior of the CW chemical laser.

  8. Accurate measurement of time

    NASA Astrophysics Data System (ADS)

    Itano, Wayne M.; Ramsey, Norman F.

    1993-07-01

    The paper discusses current methods for accurate measurements of time by conventional atomic clocks, with particular attention given to the principles of operation of atomic-beam frequency standards, atomic hydrogen masers, and atomic fountain and to the potential use of strings of trapped mercury ions as a time device more stable than conventional atomic clocks. The areas of application of the ultraprecise and ultrastable time-measuring devices that tax the capacity of modern atomic clocks include radio astronomy and tests of relativity. The paper also discusses practical applications of ultraprecise clocks, such as navigation of space vehicles and pinpointing the exact position of ships and other objects on earth using the GPS.

  9. Accurate quantum chemical calculations

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.

    1989-01-01

    An important goal of quantum chemical calculations is to provide an understanding of chemical bonding and molecular electronic structure. A second goal, the prediction of energy differences to chemical accuracy, has been much harder to attain. First, the computational resources required to achieve such accuracy are very large, and second, it is not straightforward to demonstrate that an apparently accurate result, in terms of agreement with experiment, does not result from a cancellation of errors. Recent advances in electronic structure methodology, coupled with the power of vector supercomputers, have made it possible to solve a number of electronic structure problems exactly using the full configuration interaction (FCI) method within a subspace of the complete Hilbert space. These exact results can be used to benchmark approximate techniques that are applicable to a wider range of chemical and physical problems. The methodology of many-electron quantum chemistry is reviewed. Methods are considered in detail for performing FCI calculations. The application of FCI methods to several three-electron problems in molecular physics are discussed. A number of benchmark applications of FCI wave functions are described. Atomic basis sets and the development of improved methods for handling very large basis sets are discussed: these are then applied to a number of chemical and spectroscopic problems; to transition metals; and to problems involving potential energy surfaces. Although the experiences described give considerable grounds for optimism about the general ability to perform accurate calculations, there are several problems that have proved less tractable, at least with current computer resources, and these and possible solutions are discussed.

  10. 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

  11. Effects of particle size and coating on toxicologic parameters, fecal elimination kinetics and tissue distribution of acutely ingested silver nanoparticles in a mouse model.

    PubMed

    Bergin, Ingrid L; Wilding, Laura A; Morishita, Masako; Walacavage, Kim; Ault, Andrew P; Axson, Jessica L; Stark, Diana I; Hashway, Sara A; Capracotta, Sonja S; Leroueil, Pascale R; Maynard, Andrew D; Philbert, Martin A

    2016-01-01

    Consumer exposure to silver nanoparticles (AgNP) via ingestion can occur due to incorporation of AgNP into products such as food containers and dietary supplements. AgNP variations in size and coating may affect toxicity, elimination kinetics or tissue distribution. Here, we directly compared acute administration of AgNP of two differing coatings and sizes to mice, using doses of 0.1, 1 and 10 mg/kg body weight/day administered by oral gavage for 3 days. The maximal dose is equivalent to 2000× the EPA oral reference dose. Silver acetate at the same doses was used as ionic silver control. We found no toxicity and no significant tissue accumulation. Additionally, no toxicity was seen when AgNP were dosed concurrently with a broad-spectrum antibiotic. Between 70.5% and 98.6% of the administered silver dose was recovered in feces and particle size and coating differences did not significantly influence fecal silver. Peak fecal silver was detected between 6- and 9-h post-administration and <0.5% of the administered dose was cumulatively detected in liver, spleen, intestines or urine at 48 h. Although particle size and coating did not affect tissue accumulation, silver was detected in liver, spleen and kidney of mice administered ionic silver at marginally higher levels than those administered AgNP, suggesting that silver ion may be more bioavailable. Our results suggest that, irrespective of particle size and coating, acute oral exposure to AgNP at doses relevant to potential human exposure is associated with predominantly fecal elimination and is not associated with accumulation in tissue or toxicity. PMID:26305411

  12. 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

  13. Clinical application of a novel automatic algorithm for actigraphy-based activity and rest period identification to accurately determine awake and asleep ambulatory blood pressure parameters and cardiovascular risk.

    PubMed

    Crespo, Cristina; Fernández, José R; Aboy, Mateo; Mojón, Artemio

    2013-03-01

    This paper reports the results of a study designed to determine whether there are statistically significant differences between the values of ambulatory blood pressure monitoring (ABPM) parameters obtained using different methods-fixed schedule, diary, and automatic algorithm based on actigraphy-of defining the main activity and rest periods, and to determine the clinical relevance of such differences. We studied 233 patients (98 men/135 women), 61.29 ± .83 yrs of age (mean ± SD). Statistical methods were used to measure agreement in the diagnosis and classification of subjects within the context of ABPM and cardiovascular disease risk assessment. The results show that there are statistically significant differences both at the group and individual levels. Those at the individual level have clinically significant implications, as they can result in a different classification, and, therefore, different diagnosis and treatment for individual subjects. The use of an automatic algorithm based on actigraphy can lead to better individual treatment by correcting the accuracy problems associated with the fixed schedule on patients whose actual activity/rest routine differs from the fixed schedule assumed, and it also overcomes the limitations and reliability issues associated with the use of diaries. PMID:23130607

  14. Measurement of steady-state kinetic parameters for DNA unwinding by the bacteriophage T4 Dda helicase: use of peptide nucleic acids to trap single-stranded DNA products of helicase reactions

    PubMed Central

    Nanduri, Bindu; Eoff, Robert L.; Tackett, Alan J.; Raney, Kevin D.

    2001-01-01

    Measurement of steady-state rates of unwinding of double-stranded oligonucleotides by helicases is hampered due to rapid reannealing of the single-stranded DNA products. Including an oligonucleotide in the reaction mixture which can hybridize with one of the single strands can prevent reannealing. However, helicases bind to single-stranded DNA, therefore the additional oligonucleotide can sequester the enzyme, leading to slower observed rates for unwinding. To circumvent this problem, the oligonucleotide that serves as a trap was replaced with a strand of peptide nucleic acid (PNA). Fluorescence polarization was used to determine that a 15mer PNA strand does not bind to the bacteriophage T4 Dda helicase. Steady-state kinetic parameters of unwinding catalyzed by Dda were determined by using PNA as a trapping strand. The substrate consisted of a partial duplex with 15 nt of single-stranded DNA and 15 bp. In the presence of 250 nM substrate and 1 nM Dda, the rate of unwinding in the presence of the DNA trapping strand was 0.30 nM s–1 whereas the rate was 1.34 nM s–1 in the presence of the PNA trapping strand. PNA prevents reannealing of single-stranded DNA products, but does not sequester the helicase. This assay will prove useful in defining the complete kinetic mechanism for unwinding of oligonucleotide substrates by this helicase. PMID:11433029

  15. Kinetic isotope effect of the {sup 16}O + {sup 36}O{sub 2} and {sup 18}O + {sup 32}O{sub 2} isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study

    SciTech Connect

    Sun, Zhigang Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-07

    The O + O{sub 2} isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the {sup 18}O + {sup 32}O{sub 2} and {sup 16}O + {sup 36}O{sub 2} reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the “reef” structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients.

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

    PubMed

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

    2016-07-01

    This work proposes a novel and rigorous substrate characterisation methodology to be used with ADM1 to simulate the anaerobic digestion of solid organic waste. The proposed method uses data from both direct substrate analysis and the methane production from laboratory scale anaerobic digestion experiments and involves assessment of four substrate fractionation models. The models partition the organic matter into a mixture of particulate and soluble fractions with the decision on the most suitable model being made on quality of fit between experimental and simulated data and the uncertainty of the calibrated parameters. The method was tested using samples of domestic green and food waste and using experimental data from both short batch tests and longer semi-continuous trials. The results showed that in general an increased fractionation model complexity led to better fit but with increased uncertainty. When using batch test data the most suitable model for green waste included one particulate and one soluble fraction, whereas for food waste two particulate fractions were needed. With richer semi-continuous datasets, the parameter estimation resulted in less uncertainty therefore allowing the description of the substrate with a more complex model. The resulting substrate characterisations and fractionation models obtained from batch test data, for both waste samples, were used to validate the method using semi-continuous experimental data and showed good prediction of methane production, biogas composition, total and volatile solids, ammonia and alkalinity. PMID:27156366

  17. Application of adaptive kinetic modelling for bias propagation reduction in direct 4D image reconstruction

    NASA Astrophysics Data System (ADS)

    Kotasidis, F. A.; Matthews, J. C.; Reader, A. J.; Angelis, G. I.; Zaidi, H.

    2014-10-01

    Parametric imaging in thoracic and abdominal PET can provide additional parameters more relevant to the pathophysiology of the system under study. However, dynamic data in the body are noisy due to the limiting counting statistics leading to suboptimal kinetic parameter estimates. Direct 4D image reconstruction algorithms can potentially improve kinetic parameter precision and accuracy in dynamic PET body imaging. However, construction of a common kinetic model is not always feasible and in contrast to post-reconstruction kinetic analysis, errors in poorly modelled regions may spatially propagate to regions which are well modelled. To reduce error propagation from erroneous model fits, we implement and evaluate a new approach to direct parameter estimation by incorporating a recently proposed kinetic modelling strategy within a direct 4D image reconstruction framework. The algorithm uses a secondary more general model to allow a less constrained model fit in regions where the kinetic model does not accurately describe the underlying kinetics. A portion of the residuals then is adaptively included back into the image whilst preserving the primary model characteristics in other well modelled regions using a penalty term that trades off the models. Using fully 4D simulations based on dynamic [15O]H2O datasets, we demonstrate reduction in propagation-related bias for all kinetic parameters. Under noisy conditions, reductions in bias due to propagation are obtained at the cost of increased noise, which in turn results in increased bias and variance of the kinetic parameters. This trade-off reflects the challenge of separating the residuals arising from poor kinetic modelling fits from the residuals arising purely from noise. Nonetheless, the overall root mean square error is reduced in most regions and parameters. Using the adaptive 4D image reconstruction improved model fits can be obtained in poorly modelled regions, leading to reduced errors potentially propagating

  18. Application of adaptive kinetic modelling for bias propagation reduction in direct 4D image reconstruction.

    PubMed

    Kotasidis, F A; Matthews, J C; Reader, A J; Angelis, G I; Zaidi, H

    2014-10-21

    Parametric imaging in thoracic and abdominal PET can provide additional parameters more relevant to the pathophysiology of the system under study. However, dynamic data in the body are noisy due to the limiting counting statistics leading to suboptimal kinetic parameter estimates. Direct 4D image reconstruction algorithms can potentially improve kinetic parameter precision and accuracy in dynamic PET body imaging. However, construction of a common kinetic model is not always feasible and in contrast to post-reconstruction kinetic analysis, errors in poorly modelled regions may spatially propagate to regions which are well modelled. To reduce error propagation from erroneous model fits, we implement and evaluate a new approach to direct parameter estimation by incorporating a recently proposed kinetic modelling strategy within a direct 4D image reconstruction framework. The algorithm uses a secondary more general model to allow a less constrained model fit in regions where the kinetic model does not accurately describe the underlying kinetics. A portion of the residuals then is adaptively included back into the image whilst preserving the primary model characteristics in other well modelled regions using a penalty term that trades off the models. Using fully 4D simulations based on dynamic [(15)O]H2O datasets, we demonstrate reduction in propagation-related bias for all kinetic parameters. Under noisy conditions, reductions in bias due to propagation are obtained at the cost of increased noise, which in turn results in increased bias and variance of the kinetic parameters. This trade-off reflects the challenge of separating the residuals arising from poor kinetic modelling fits from the residuals arising purely from noise. Nonetheless, the overall root mean square error is reduced in most regions and parameters. Using the adaptive 4D image reconstruction improved model fits can be obtained in poorly modelled regions, leading to reduced errors potentially propagating

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

    PubMed Central

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

    2012-01-01

    Triplex forming oligonucleotides (TFOs) are the most commonly used approach for site-specific targeting of double stranded DNA (dsDNA). Important parameters describing triplex formation include equilibrium binding constants (Keq) and association/dissociation rate constants (kon and koff). The ‘fluorescent intercalator displacement replacement’ (FIDR) assay is introduced herein as an operationally simple approach toward determination of these parameters for triplexes involving TC-motif TFOs. Briefly described, relative rate constants are determined from fluorescence intensity changes upon: (i) TFO-mediated displacement of pre-intercalated and fluorescent ethidium from dsDNA targets (triplex association) and (ii) Watson–Crick complement-mediated displacement of the TFO and replacement with ethidium (triplex dissociation). The assay is used to characterize triplexes between purine-rich dsDNA targets and TC-motif TFOs modified with six different locked nucleic acid (LNA) monomers, i.e. conventional and C5-alkynyl-functionalized LNA and α-L-LNA pyrimidine monomers. All of the studied monomers increase triplex stability by decreasing the triplex dissociation rate. LNA-modified TFOs form more stable triplexes than α-L-LNA-modified counterparts owing to slower triplex dissociation. Triplexes modified with C5-(3-aminopropyn-1-yl)-LNA-U monomer Z are particularly stable. The study demonstrates that three affinity-enhancing features can be combined into one high-affinity TFO monomer: conformational restriction of the sugar ring, expansion of the pyrimidine π-stacking surface and introduction of an exocyclic amine. PMID:22855561

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

    PubMed

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

    2012-11-01

    Triplex forming oligonucleotides (TFOs) are the most commonly used approach for site-specific targeting of double stranded DNA (dsDNA). Important parameters describing triplex formation include equilibrium binding constants (K(eq)) and association/dissociation rate constants (k(on) and k(off)). The 'fluorescent intercalator displacement replacement' (FIDR) assay is introduced herein as an operationally simple approach toward determination of these parameters for triplexes involving TC-motif TFOs. Briefly described, relative rate constants are determined from fluorescence intensity changes upon: (i) TFO-mediated displacement of pre-intercalated and fluorescent ethidium from dsDNA targets (triplex association) and (ii) Watson-Crick complement-mediated displacement of the TFO and replacement with ethidium (triplex dissociation). The assay is used to characterize triplexes between purine-rich dsDNA targets and TC-motif TFOs modified with six different locked nucleic acid (LNA) monomers, i.e. conventional and C5-alkynyl-functionalized LNA and α-L-LNA pyrimidine monomers. All of the studied monomers increase triplex stability by decreasing the triplex dissociation rate. LNA-modified TFOs form more stable triplexes than α-L-LNA-modified counterparts owing to slower triplex dissociation. Triplexes modified with C5-(3-aminopropyn-1-yl)-LNA-U monomer Z are particularly stable. The study demonstrates that three affinity-enhancing features can be combined into one high-affinity TFO monomer: conformational restriction of the sugar ring, expansion of the pyrimidine π-stacking surface and introduction of an exocyclic amine. PMID:22855561

  1. Estimation of Temperature Dependent Parameters of a Batch Alcoholic Fermentation Process

    NASA Astrophysics Data System (ADS)

    de Andrade, Rafael Ramos; Rivera, Elmer Ccopa; Costa, Aline C.; Atala, Daniel I. P.; Filho, Francisco Maugeri; Filho, Rubens Maciel

    In this work, a procedure was established to develop a mathematical model considering the effect of temperature on reaction kinetics. Experiments were performed in batch mode in temperatures from 30 to 38°C. The microorganism used was Saccharomyces cerevisiae and the culture media, sugarcane molasses. The objective is to assess the difficulty in updating the kinetic parameters when there are changes in fermentation conditions. We conclude that, although the re-estimation is a time-consuming task, it is possible to accurately describe the process when there are changes in raw material composition if a re-estimation of parameters is performed.

  2. Processing parameters and kinetics of bromination and chlorination in the YBa sub 2 Cu sub 3 O sub 6+x system

    SciTech Connect

    Radousky, H.B.; Glass, R.S.; Back, D.; Chin, A.H.; Fluss, M.J. ); Liu, J.Z.; Mosly, W.D.; Klavins, P.; Shelton, R.N. . Dept. of Physics)

    1990-09-01

    The introduction of halogens such as Cl{sub 2}, Br{sub 2} can restore 90 K superconductivity to oxygen deficient YBa{sub 2}Cu{sub 3}O{sub 6+x}. This is potentially important for applications to thin film devices due to the low processing temperatures required relative to reprocessing with oxygen. Low temperature 260{degrees}C and short time (>5 minute) bromination has been shown to convert initially insulting YBa{sub 2}Cu{sub 3}O{sub 6.2} powder to a high temperature superconductor with properties similar to the standard O{sub 7} material. This process has now been extended to single crystals as well, but with somewhat different processing parameters. Thermal gravimetric analysis (TGA) coupled with mass spectrometry indicates that the Br becomes strongly bonded, with no release of Br observed in taking powder samples to 1000{degree}C in flowing forming gas (2%H{sub 2}/98%N{sub 2}). The reaction has also been found to be highly exothermic for both Br and Cl treatments, which is consistent with the strong bonding of the bromine discussed above.

  3. Developing Accurate Spatial Maps of Cotton Fiber Quality Parameters

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Awareness of the importance of cotton fiber quality (Gossypium, L. sps.) has increased as advances in spinning technology require better quality cotton fiber. Recent advances in geospatial information sciences allow an improved ability to study the extent and causes of spatial variability in fiber p...

  4. Inverse Kinetics

    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. Thermodynamics and mass transfer kinetics of phenol in reversed phase liquid chromatography

    SciTech Connect

    Kaczmarski, Krzysztof; Gritti, Fabrice; Guiochon, Georges A

    2006-05-01

    The thermodynamics and the mass transfer kinetics of the chromatographic system made of phenol, in a water-acetonitrile mobile phase, on a C18 RPLC column, were studied in the temperature range from 21 to 77 C and the interstitial velocity range of 0.021 to 1.27 cm/s. The equilibrium isotherm was accurately approximated by a multilayer model assuming lateral interactions between adsorbed molecules. The parameters of the kinetics of the phenol mass transfer in this column were measured by the method of moments. These data were analyzed using the available models and correlations. It was proven that the parameters of the mass transfer kinetics measured under linear conditions could be successfully used for the prediction of the concentration profiles obtained under overloaded conditions.

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

    NASA Astrophysics Data System (ADS)

    Widayatno, Tri

    2015-12-01

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

  7. 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.

  8. 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.

  9. Computer-Aided Construction of Chemical Kinetic Models

    SciTech Connect

    Green, William H.

    2014-12-31

    The combustion chemistry of even simple fuels can be extremely complex, involving hundreds or thousands of kinetically significant species. The most reasonable way to deal with this complexity is to use a computer not only to numerically solve the kinetic model, but also to construct the kinetic model in the first place. Because these large models contain so many numerical parameters (e.g. rate coefficients, thermochemistry) one never has sufficient data to uniquely determine them all experimentally. Instead one must work in “predictive” mode, using theoretical rather than experimental values for many of the numbers in the model, and as appropriate refining the most sensitive numbers through experiments. Predictive chemical kinetics is exactly what is needed for computer-aided design of combustion systems based on proposed alternative fuels, particularly for early assessment of the value and viability of proposed new fuels before those fuels are commercially available. This project was aimed at making accurate predictive chemical kinetics practical; this is a challenging goal which requires a range of science advances. The project spanned a wide range from quantum chemical calculations on individual molecules and elementary-step reactions, through the development of improved rate/thermo calculation procedures, the creation of algorithms and software for constructing and solving kinetic simulations, the invention of methods for model-reduction while maintaining error control, and finally comparisons with experiment. Many of the parameters in the models were derived from quantum chemistry calculations, and the models were compared with experimental data measured in our lab or in collaboration with others.

  10. Wild-type and mutant D-xylose isomerase from Actinoplanes missouriensis: metal-ion dissociation constants, kinetic parameters of deuterated and non-deuterated substrates and solvent-isotope effects.

    PubMed Central

    van Bastelaere, P B; Kersters-Hilderson, H L; Lambeir, A M

    1995-01-01

    The metal-ion dissociation constants (Mg2+, Mn2+) of wild-type and mutant D-xylose isomerases from Actinoplanes missouriensis have been determined by titrating the metal-ion-free enzymes with Mg2+ and Mn2+ respectively. Substitution of amino acids co-ordinated to metal-ion 1 (E181D, D245N) dramatically affects the dissociation constants, pH-activity profiles and apparent substrate binding. Mutagenesis of groups ligated to metal-ion 2 is less drastic except for that of Asp-255: a decrease in metal-ion affinity, a change in metal-ion preference and an improved apparent substrate binding (at pH values above the optimum), especially in the presence of Mn2+, are observed for the D255N enzyme. Similar effects, except for a slightly increased metal-ion affinity, are obtained by mutagenesis of the adjacent Glu-186 to Gln and the unconserved Ala-25 to Lys. Moreover, the striking acidic-pH shifts observed for the D255N and E186Q enzymes support the crucial role of the water molecule, Wa-690, Asp-255 and the adjacent Glu-186 in proton transfer from 2-OH to O-1 of the open and extended aldose substrate. Mutations of other important groups scarcely affect the metal-ion dissociation constants and pH-activity profiles, although pronounced effects on the kinetic parameters may be observed. PMID:7717967

  11. Multiple heating rate kinetic parameters, thermal, X-ray diffraction studies of newly synthesized octahedral copper complexes based on bromo-coumarins along with their antioxidant, anti-tubercular and antimicrobial activity evaluation

    NASA Astrophysics Data System (ADS)

    Patel, Ketan S.; Patel, Jiten C.; Dholariya, Hitesh R.; Patel, Kanuprasad D.

    2012-10-01

    Series of new Cu(II) complexes were synthesized by classical thermal technique. The biologically potent ligands (L) were prepared by refluxing 6-brom 3-acetyl coumarin with aldehydes in the presence of piperidine in ethanol. The Cu(II) complexes have been synthesized by mixing an aqueous solution of Cu(NO3)2 in 1:1 molar ratios with ethanolic bidentate ligands and Clioquinol. The structures of the ligands and their copper complexes were investigated and confirmed by the elemental analysis, FT-IR, 1H NMR, 13C NMR, mass spectral and powder X-ray diffraction studies respectively. Thermal behaviour of newly synthesized mixed ligand Cu(II) complexes were investigated by means of thermogravimetry, differential thermogravimetry, differential scanning calorimetry, electronic spectra and magnetic measurements. Dynamic scan of DSC experiments for Cu(II) complexes were taken at different heating rates (2.5-20 °C min-1). Kinetic parameters for second step degradation of all complexes obtained by Kissinger's and Ozawa's methods were in good agreement. On the basis of these studies it is clear that ligands coordinated to metal atom in a monobasic bidentate mode, by Osbnd O and Osbnd N donor system. Thus, suitable octahedral geometry for hexa-coordinated state has been suggested for the metal complexes. Both the ligands as well as its complexes have been screened for their in vitro antioxidant, anti-tubercular and antimicrobial activities. All were found to be significant potent compared to parent ligands employed for complexation.

  12. High Frequency QRS ECG Accurately Detects Cardiomyopathy

    NASA Technical Reports Server (NTRS)

    Schlegel, Todd T.; Arenare, Brian; Poulin, Gregory; Moser, Daniel R.; Delgado, Reynolds

    2005-01-01

    High frequency (HF, 150-250 Hz) analysis over the entire QRS interval of the ECG is more sensitive than conventional ECG for detecting myocardial ischemia. However, the accuracy of HF QRS ECG for detecting cardiomyopathy is unknown. We obtained simultaneous resting conventional and HF QRS 12-lead ECGs in 66 patients with cardiomyopathy (EF = 23.2 plus or minus 6.l%, mean plus or minus SD) and in 66 age- and gender-matched healthy controls using PC-based ECG software recently developed at NASA. The single most accurate ECG parameter for detecting cardiomyopathy was an HF QRS morphological score that takes into consideration the total number and severity of reduced amplitude zones (RAZs) present plus the clustering of RAZs together in contiguous leads. This RAZ score had an area under the receiver operator curve (ROC) of 0.91, and was 88% sensitive, 82% specific and 85% accurate for identifying cardiomyopathy at optimum score cut-off of 140 points. Although conventional ECG parameters such as the QRS and QTc intervals were also significantly longer in patients than controls (P less than 0.001, BBBs excluded), these conventional parameters were less accurate (area under the ROC = 0.77 and 0.77, respectively) than HF QRS morphological parameters for identifying underlying cardiomyopathy. The total amplitude of the HF QRS complexes, as measured by summed root mean square voltages (RMSVs), also differed between patients and controls (33.8 plus or minus 11.5 vs. 41.5 plus or minus 13.6 mV, respectively, P less than 0.003), but this parameter was even less accurate in distinguishing the two groups (area under ROC = 0.67) than the HF QRS morphologic and conventional ECG parameters. Diagnostic accuracy was optimal (86%) when the RAZ score from the HF QRS ECG and the QTc interval from the conventional ECG were used simultaneously with cut-offs of greater than or equal to 40 points and greater than or equal to 445 ms, respectively. In conclusion 12-lead HF QRS ECG employing

  13. Kinetic energy density dependent approximations to the exchange energy

    NASA Astrophysics Data System (ADS)

    Ernzerhof, Matthias; Scuseria, Gustavo E.

    1999-07-01

    Two nonempirical kinetic energy density dependent approximations are introduced. First, the local τ approximation (LTA) is proposed in which the exchange energy Ex depends only on a kinetic energy density τ. This LTA scheme appears to be complementary to the local spin density (LSD) approximation in the sense that its exchange contribution to the atomization energy ΔEx=Exatoms-Exmolecule is fairly accurate for systems where LSD fails. On the other hand, in cases where LSD works well LTA results for ΔEx are worse. Secondly, the τPBE approximation to Ex is developed which combines some of the advantages of LTA and of the Perdew-Burke-Ernzerhof (PBE) exchange functional. Like the PBE exchange functional, τPBE is free of empirical parameters. Furthermore, it yields improved atomization energies compared to the PBE approximation.

  14. Towards cleaner combustion engines through groundbreaking detailed chemical kinetic models

    PubMed Central

    Battin-Leclerc, Frédérique; Blurock, Edward; Bounaceur, Roda; Fournet, René; Glaude, Pierre-Alexandre; Herbinet, Olivier; Sirjean, Baptiste; Warth, V.

    2013-01-01

    In the context of limiting the environmental impact of transportation, this paper reviews new directions which are being followed in the development of more predictive and more accurate detailed chemical kinetic models for the combustion of fuels. In the first part, the performance of current models, especially in terms of the prediction of pollutant formation, is evaluated. In the next parts, recent methods and ways to improve these models are described. An emphasis is given on the development of detailed models based on elementary reactions, on the production of the related thermochemical and kinetic parameters, and on the experimental techniques available to produce the data necessary to evaluate model predictions under well defined conditions. PMID:21597604

  15. Kinetics of anaerobic purification of industrial wastewater

    SciTech Connect

    Bolle, W.L.; van Breugel, J.; van Eybergen, G.C.; Kossen, N.W.F.; van Gils, W.

    1986-04-01

    As part of the development of an integral mathematical model describing the up-flow anaerobic sludges blanket (UASB) reactor, the kinetics of the conversion of organic wastes has to be known. The Mondod model is compared with the model proposed by Andrews, et al. Together with the assumption that the substrate for the anaerobic bacteria is formed by nonionized, volatile fatty acids, the Andrews model is able to describe substrate inhibition and reactor failure due to pH changes. From four batch experiments, with different concentrations of microorganisms, it could be concluded with a reliability of over 95% that the Monod model was inadequate and Andrews' model was adequate to describe the measurements. Standard statistical techniques like the X2 and the F-test were used for this purpose. From a parameter sensitivity analysis for the Andrews model it followed that the maximum specific growth rate Mu(A) max of the bacteria and the inhibition constant K, are the parameters which influance the systems most. Thus, these parameters were determined experimentally and most accurately. The other parameters were taken from literature. From a calculation of the Thiele modulus for the particles it follows that transport limitation of the substrate in the flocs is not significant. The efficiency Eta is 0.85 in the worst case. 11 references.

  16. Blind estimation of compartmental model parameters.

    PubMed

    Di Bella, E V; Clackdoyle, R; Gullberg, G T

    1999-03-01

    Computation of physiologically relevant kinetic parameters from dynamic PET or SPECT imaging requires knowledge of the blood input function. This work is concerned with developing methods to accurately estimate these kinetic parameters blindly; that is, without use of a directly measured blood input function. Instead, only measurements of the output functions--the tissue time-activity curves--are used. The blind estimation method employed here minimizes a set of cross-relation equations, from which the blood term has been factored out, to determine compartmental model parameters. The method was tested with simulated data appropriate for dynamic SPECT cardiac perfusion imaging with 99mTc-teboroxime and for dynamic PET cerebral blood flow imaging with 15O water. The simulations did not model the tomographic process. Noise levels typical of the respective modalities were employed. From three to eight different regions were simulated, each with different time-activity curves. The time-activity curve (24 or 70 time points) for each region was simulated with a compartment model. The simulation used a biexponential blood input function and washin rates between 0.2 and 1.3 min(-1) and washout rates between 0.2 and 1.0 min(-1). The system of equations was solved numerically and included constraints to bound the range of possible solutions. From the cardiac simulations, washin was determined to within a scale factor of the true washin parameters with less than 6% bias and 12% variability. 99mTc-teboroxime washout results had less than 5% bias, but variability ranged from 14% to 43%. The cerebral blood flow washin parameters were determined with less than 5% bias and 4% variability. The washout parameters were determined with less than 4% bias, but had 15-30% variability. Since washin is often the parameter of most use in clinical studies, the blind estimation approach may eliminate the current necessity of measuring the input function when performing certain dynamic studies

  17. NNLOPS accurate associated HW production

    NASA Astrophysics Data System (ADS)

    Astill, William; Bizon, Wojciech; Re, Emanuele; Zanderighi, Giulia

    2016-06-01

    We present a next-to-next-to-leading order accurate description of associated HW production consistently matched to a parton shower. The method is based on reweighting events obtained with the HW plus one jet NLO accurate calculation implemented in POWHEG, extended with the MiNLO procedure, to reproduce NNLO accurate Born distributions. Since the Born kinematics is more complex than the cases treated before, we use a parametrization of the Collins-Soper angles to reduce the number of variables required for the reweighting. We present phenomenological results at 13 TeV, with cuts suggested by the Higgs Cross section Working Group.

  18. How to accurately bypass damage

    PubMed Central

    Broyde, Suse; Patel, Dinshaw J.

    2016-01-01

    Ultraviolet radiation can cause cancer through DNA damage — specifically, by linking adjacent thymine bases. Crystal structures show how the enzyme DNA polymerase η accurately bypasses such lesions, offering protection. PMID:20577203

  19. Accurate Evaluation of Quantum Integrals

    NASA Technical Reports Server (NTRS)

    Galant, David C.; Goorvitch, D.

    1994-01-01

    Combining an appropriate finite difference method with Richardson's extrapolation results in a simple, highly accurate numerical method for solving a Schr\\"{o}dinger's equation. Important results are that error estimates are provided, and that one can extrapolate expectation values rather than the wavefunctions to obtain highly accurate expectation values. We discuss the eigenvalues, the error growth in repeated Richardson's extrapolation, and show that the expectation values calculated on a crude mesh can be extrapolated to obtain expectation values of high accuracy.

  20. Activation of mouse macrophages causes no change in expression and function of phorbol diesters' receptors, but is accompanied by alterations in the activity and kinetic parameters of NADPH oxidase.

    PubMed Central

    Berton, G; Cassatella, M; Cabrini, G; Rossi, F

    1985-01-01

    Mouse peritoneal macrophages activated in vivo by the injection of Corynebacterium parvum release larger amounts of superoxide anion (O2-) than macrophages from control mice when stimulated with phorbol myristate acetate (PMA). The biochemical bases for this enhanced response of activated macrophages have been investigated by studying the expression and function of receptors for the stimulant, and the activity of the enzyme NADPH oxidase which is responsible for the production of O2- in leucocytes. Studies of binding of phorbol dibutyrate, an agent closely related to PMA, showed that the affinity constants (Kds) and the number of binding sites were the same in resident and activated peritoneal macrophages. The activity of the NADPH oxidase was, however, different in the two macrophage populations which differ in their capacity to release O2-. NADPH oxidase activity was studied in macrophage monolayers after lysis with deoxycholate. The main features of this activity were as follows: stimulation of macrophages with PMA or zymosan caused an increase in NADPH-dependent O2- production; NADPH oxidase activity in the lysates followed the same dose-response curve for different concentrations of PMA as O2- release by intact macrophages; O2- release by intact macrophages could be fully accounted for by NADPH-dependent O2- production by macrophage lysates; activity was strictly substrate-specific, in that NADH could not substitute for NADPH; after stimulation with PMA or zymosan, NADPH oxidase activity was higher in lysates of C. parvum-activated macrophages than in lysates of resident macrophages; NADPH oxidase activities of activated and resident macrophages differed markedly in their kinetic parameters. The NADPH oxidase of macrophages activated by C. parvum or trehalose dimycolate of mycobacterial origin displayed a five to seven times lower Km compared to the enzyme in resident macrophages. PMID:2981767

  1. Accurate wavelength calibration method for flat-field grating spectrometers.

    PubMed

    Du, Xuewei; Li, Chaoyang; Xu, Zhe; Wang, Qiuping

    2011-09-01

    A portable spectrometer prototype is built to study wavelength calibration for flat-field grating spectrometers. An accurate calibration method called parameter fitting is presented. Both optical and structural parameters of the spectrometer are included in the wavelength calibration model, which accurately describes the relationship between wavelength and pixel position. Along with higher calibration accuracy, the proposed calibration method can provide information about errors in the installation of the optical components, which will be helpful for spectrometer alignment. PMID:21929865

  2. Accurate Molecular Polarizabilities Based on Continuum Electrostatics

    PubMed Central

    Truchon, Jean-François; Nicholls, Anthony; Iftimie, Radu I.; Roux, Benoît; Bayly, Christopher I.

    2013-01-01

    A novel approach for representing the intramolecular polarizability as a continuum dielectric is introduced to account for molecular electronic polarization. It is shown, using a finite-difference solution to the Poisson equation, that the Electronic Polarization from Internal Continuum (EPIC) model yields accurate gas-phase molecular polarizability tensors for a test set of 98 challenging molecules composed of heteroaromatics, alkanes and diatomics. The electronic polarization originates from a high intramolecular dielectric that produces polarizabilities consistent with B3LYP/aug-cc-pVTZ and experimental values when surrounded by vacuum dielectric. In contrast to other approaches to model electronic polarization, this simple model avoids the polarizability catastrophe and accurately calculates molecular anisotropy with the use of very few fitted parameters and without resorting to auxiliary sites or anisotropic atomic centers. On average, the unsigned error in the average polarizability and anisotropy compared to B3LYP are 2% and 5%, respectively. The correlation between the polarizability components from B3LYP and this approach lead to a R2 of 0.990 and a slope of 0.999. Even the F2 anisotropy, shown to be a difficult case for existing polarizability models, can be reproduced within 2% error. In addition to providing new parameters for a rapid method directly applicable to the calculation of polarizabilities, this work extends the widely used Poisson equation to areas where accurate molecular polarizabilities matter. PMID:23646034

  3. Optimization of a direct spectrophotometric method to investigate the kinetics and inhibition of sialidases

    PubMed Central

    2012-01-01

    Backgrounds Streptococcus pneumoniae expresses three distinct sialidases, NanA, NanB, and NanC, that are believed to be key virulence factors and thus, potential important drug targets. We previously reported that the three enzymes release different products from sialosides, but could share a common catalytic mechanism before the final step of product formation. However, the kinetic investigations of the three sialidases have not been systematically done thus far, due to the lack of an easy and steady measurement of sialidase reaction rate. Results In this work, we present further kinetic characterization of pneumococcal sialidases by using a direct spectrophotometric method with the chromogenic substrate p-nitrophenyl-N-acetylneuraminic acid (p-NP-Neu5Ac). Using our assay, the measured kinetic parameters of the three purified pneumococcal sialidase, NanA, NanB and NanC, were obtained and were in perfect agreement with the previously published data. The major advantage of this alternative method resides in the direct measurement of the released product, allowing to readily determine of initial reaction rates and record complete hydrolysis time courses. Conclusion We developed an accurate, fast and sensitive spectrophotometric method to investigate the kinetics of sialidase-catalyzed reactions. This fast, sensitive, inexpensive and accurate method could benefit the study of the kinetics and inhibition of sialidases in general. PMID:23031230

  4. Accurate basis set truncation for wavefunction embedding

    NASA Astrophysics Data System (ADS)

    Barnes, Taylor A.; Goodpaster, Jason D.; Manby, Frederick R.; Miller, Thomas F.

    2013-07-01

    Density functional theory (DFT) provides a formally exact framework for performing embedded subsystem electronic structure calculations, including DFT-in-DFT and wavefunction theory-in-DFT descriptions. In the interest of efficiency, it is desirable to truncate the atomic orbital basis set in which the subsystem calculation is performed, thus avoiding high-order scaling with respect to the size of the MO virtual space. In this study, we extend a recently introduced projection-based embedding method [F. R. Manby, M. Stella, J. D. Goodpaster, and T. F. Miller III, J. Chem. Theory Comput. 8, 2564 (2012)], 10.1021/ct300544e to allow for the systematic and accurate truncation of the embedded subsystem basis set. The approach is applied to both covalently and non-covalently bound test cases, including water clusters and polypeptide chains, and it is demonstrated that errors associated with basis set truncation are controllable to well within chemical accuracy. Furthermore, we show that this approach allows for switching between accurate projection-based embedding and DFT embedding with approximate kinetic energy (KE) functionals; in this sense, the approach provides a means of systematically improving upon the use of approximate KE functionals in DFT embedding.

  5. Degradation Kinetics and Mechanism of a β-Lactam Antibiotic Intermediate, 6-Aminopenicillanic Acid, in a New Integrated Production Process.

    PubMed

    Su, Min; Sun, Hua; Zhao, Yingying; Lu, Aidang; Cao, Xiaohui; Wang, Jingkang

    2016-01-01

    In an effort to promote sustainability and to reduce manufacturing costs, the traditional production process for 6-aminopenicillanic acid (6-APA) has been modified to include less processing units. The objectives of this study are to investigate the degradation kinetics of 6-APA, to propose a reasonable degradation mechanism, and to optimize the manufacturing conditions within this new process. A series of degradation kinetic studies were conducted in the presence of impurities, as well as at various chemical and physical conditions. The concentrations of 6-APA were determined by high-performance liquid chromatography. An Arrhenius-type kinetic model was established to give a more accurate prediction on the degradation rates of 6-APA. A hydrolysis degradation mechanism is shown to be the major pathway for 6-APA. The degradation mechanisms and the kinetic models for 6-APA in the new system enable the design of a good manufacturing process with optimized parameters. PMID:26852849

  6. Removal of water and iodine by solid sorbents: adsorption isotherms and kinetics

    SciTech Connect

    Lin, R.; Tavlarides, L.L.

    2013-07-01

    Tritium and iodine-129 are two major radioactive elements that are present in off-gases from spent fuel reprocessing plants. Adsorption by solid sorbents is the state-of-the-art technique for removal of these species from off-gases. Modeling and simulating adsorption processes require accurate adsorption equilibrium and kinetic data to permit reasonable estimates of process parameters. We have developed a continuous flow single-pellet adsorption system to gather accurate adsorption equilibrium and kinetic data for adsorption of water by molecular sieve 3A and for adsorption of iodine by silver exchanged mordenite. In this paper, the design of the water and iodine adsorption experimental systems are briefly described and results of water adsorption experiments are presented and discussed. Water uptake curves are fitted with the linear-driving force (LDF) model and the shrinking-core model to determine kinetic parameters. It is shown that the kinetics of water adsorption on zeolite 3A under current experimental conditions is controlled by both the external film resistance and the macro-pore diffusion and can be predicted by both the LDF model and the shrinking-core model with the former one performing slightly better. Preliminary results from iodine adsorption experiments will be presented in the conference.

  7. Two highly accurate methods for pitch calibration

    NASA Astrophysics Data System (ADS)

    Kniel, K.; Härtig, F.; Osawa, S.; Sato, O.

    2009-11-01

    Among profiles, helix and tooth thickness pitch is one of the most important parameters of an involute gear measurement evaluation. In principle, coordinate measuring machines (CMM) and CNC-controlled gear measuring machines as a variant of a CMM are suited for these kinds of gear measurements. Now the Japan National Institute of Advanced Industrial Science and Technology (NMIJ/AIST) and the German national metrology institute the Physikalisch-Technische Bundesanstalt (PTB) have each developed independently highly accurate pitch calibration methods applicable to CMM or gear measuring machines. Both calibration methods are based on the so-called closure technique which allows the separation of the systematic errors of the measurement device and the errors of the gear. For the verification of both calibration methods, NMIJ/AIST and PTB performed measurements on a specially designed pitch artifact. The comparison of the results shows that both methods can be used for highly accurate calibrations of pitch standards.

  8. 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.

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

    PubMed

    Noé, Frank; Clementi, Cecilia

    2015-10-13

    Characterizing macromolecular kinetics from molecular dynamics (MD) simulations requires a distance metric that can distinguish slowly interconverting states. Here, we build upon diffusion map theory and define a kinetic distance metric for irreducible Markov processes that quantifies how slowly molecular conformations interconvert. The kinetic distance can be computed given a model that approximates the eigenvalues and eigenvectors (reaction coordinates) of the MD Markov operator. Here, we employ the time-lagged independent component analysis (TICA). The TICA components can be scaled to provide a kinetic map in which the Euclidean distance corresponds to the kinetic distance. As a result, the question of how many TICA dimensions should be kept in a dimensionality reduction approach becomes obsolete, and one parameter less needs to be specified in the kinetic model construction. We demonstrate the approach using TICA and Markov state model (MSM) analyses for illustrative models, protein conformation dynamics in bovine pancreatic trypsin inhibitor and protein-inhibitor association in trypsin and benzamidine. We find that the total kinetic variance (TKV) is an excellent indicator of model quality and can be used to rank different input feature sets. PMID:26574285

  10. Studies of Reaction Kinetics of Methane Hydrate Dissocation in Porous Media

    SciTech Connect

    Moridis, George J.; Seol, Yongkoo; Kneafsey, Timothy J.

    2005-03-10

    The objective of this study is the description of the kinetic dissociation of CH4-hydrates in porous media, and the determination of the corresponding kinetic parameters. Knowledge of the kinetic dissociation behavior of hydrates can play a critical role in the evaluation of gas production potential of gas hydrate accumulations in geologic media. We analyzed data from a sequence of tests of CH4-hydrate dissociation by means of thermal stimulation. These tests had been conducted on sand cores partially saturated with water, hydrate and CH4 gas, and contained in an x-ray-transparent aluminum pressure vessel. The pressure, volume of released gas, and temperature (at several locations within the cores) were measured. To avoid misinterpreting local changes as global processes, x-ray computed tomography scans provided accurate images of the location and movement of the reaction interface during the course of the experiments. Analysis of the data by means of inverse modeling (history matching ) provided estimates of the thermal properties and of the kinetic parameters of the hydration reaction in porous media. Comparison of the results from the hydrate-bearing porous media cores to those from pure CH4-hydrate samples provided a measure of the effect of the porous medium on the kinetic reaction. A tentative model of composite thermal conductivity of hydrate-bearing media was also developed.

  11. Busulfan kinetics.

    PubMed

    Ehrsson, H; Hassan, M; Ehrnebo, M; Beran, M

    1983-07-01

    Busulfan kinetics were studied in patients with chronic myelocytic leukemia after oral doses of 2, 4, and 6 mg. The plasma concentration-time data could be fitted to a zero-order absorption one-compartment open model. The elimination rate constant averaged 0.27 +/- 0.05 hr-1 (SD). The plasma AUC was linearly related to the dose. The lag time for the start of absorption, the time absorption ends, and the absorption rate constant showed some interindividual variations. About 1% of busulfan is excreted unchanged in urine over 24 hr. PMID:6574831

  12. Kinetics of Slurry Phase Fischer-Tropsch Synthesis

    SciTech Connect

    Dragomir B. Bukur; Gilbert F. Froment; Tomasz Olewski; Lech Nowicki; Madhav Nayapati

    2006-12-31

    be used only to fit product distribution of total olefins and n-paraffins. The kinetic model of Van der Laan and Beenackers was extended to account separately for formation of 1- and 2-olefins, as well as n-paraffins. A simplified form of the kinetic model of Lox and Froment (1993b) has only five parameters at isothermal conditions. Because of its relative simplicity, this model is well suited for initial studies where the main goal is to learn techniques for parameter estimation and statistical analysis of estimated values of model parameters. The same techniques and computer codes were used in the analysis of other kinetic models. The Levenberg-Marquardt (LM) method was employed for minimization of the objective function and kinetic parameter estimation. Predicted reaction rates of inorganic and hydrocarbon species were not in good agreement with experimental data. All reaction rate constants and activation energies (24 parameters) of the Yang et al. (2003) model were found to be positive, but the corresponding 95% confidence intervals were large. Agreement between predicted and experimental reaction rates has been fair to good. Light hydrocarbons were predicted fairly accurately, whereas the model predictions of higher molecular weight hydrocarbons values were lower than the experimental ones. The Van der Laan and Beenackers kinetic model (known as olefin readsorption product distribution model = ORPDM) provided a very good fit of the experimental data for hydrocarbons (total olefins and n-paraffins) up to about C{sub 20} (with the exception of experimental data that showed higher paraffin formation rates in C{sub 12}-C{sub 25} region, due to hydrocracking or other secondary reactions). Estimated values of all model parameters (true and pseudo-kinetic parameters) had high statistical significance after combining parameters related to olefin termination and readsorption into one (total of 7 model parameters). The original ORPDM was extended to account separately

  13. Tolrestat kinetics

    SciTech Connect

    Hicks, D.R.; Kraml, M.; Cayen, M.N.; Dubuc, J.; Ryder, S.; Dvornik, D.

    1984-10-01

    The kinetics of tolrestat, a potent inhibitor of aldose reductase, were examined. Serum concentrations of tolrestat and of total /sup 14/C were measured after dosing normal subjects and subjects with diabetes with /sup 14/C-labeled tolrestat. In normal subjects, tolrestat was rapidly absorbed and disappearance from serum was biphasic. Distribution and elimination t 1/2s were approximately 2 and 10 to 12 hr, respectively, after single and multiple doses. Unchanged tolrestat accounted for the major portion of /sup 14/C in serum. Radioactivity was rapidly and completely excreted in urine and feces in an approximate ratio of 2:1. Findings were much the same in subjects with diabetes. In normal subjects, the kinetics of oral tolrestat were independent of dose in the 10 to 800 mg range. Repetitive dosing did not result in unexpected cumulation. Tolrestat was more than 99% bound to serum protein; it did not compete with warfarin for binding sites but was displaced to some extent by high concentrations of tolbutamide or salicylate.

  14. 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.

  15. Accurate single-molecule FRET studies using multiparameter fluorescence detection.

    PubMed

    Sisamakis, Evangelos; Valeri, Alessandro; Kalinin, Stanislav; Rothwell, Paul J; Seidel, Claus A M

    2010-01-01

    In the recent decade, single-molecule (sm) spectroscopy has come of age and is providing important insight into how biological molecules function. So far our view of protein function is formed, to a significant extent, by traditional structure determination showing many beautiful static protein structures. Recent experiments by single-molecule and other techniques have questioned the idea that proteins and other biomolecules are static structures. In particular, Förster resonance energy transfer (FRET) studies of single molecules have shown that biomolecules may adopt many conformations as they perform their function. Despite the success of sm-studies, interpretation of smFRET data are challenging since they can be complicated due to many artifacts arising from the complex photophysical behavior of fluorophores, dynamics, and motion of fluorophores, as well as from small amounts of contaminants. We demonstrate that the simultaneous acquisition of a maximum of fluorescence parameters by multiparameter fluorescence detection (MFD) allows for a robust assessment of all possible artifacts arising from smFRET and offers unsurpassed capabilities regarding the identification and analysis of individual species present in a population of molecules. After a short introduction, the data analysis procedure is described in detail together with some experimental considerations. The merits of MFD are highlighted further with the presentation of some applications to proteins and nucleic acids, including accurate structure determination based on FRET. A toolbox is introduced in order to demonstrate how complications originating from orientation, mobility, and position of fluorophores have to be taken into account when determining FRET-related distances with high accuracy. Furthermore, the broad time resolution (picoseconds to hours) of MFD allows for kinetic studies that resolve interconversion events between various subpopulations as a biomolecule of interest explores its

  16. Enhanced von Weizsäcker Wang-Govind-Carter kinetic energy density functional for semiconductors

    SciTech Connect

    Shin, Ilgyou; Carter, Emily A.

    2014-05-14

    We propose a new form of orbital-free (OF) kinetic energy density functional (KEDF) for semiconductors that is based on the Wang-Govind-Carter (WGC99) nonlocal KEDF. We enhance within the latter the semi-local von Weizsäcker KEDF term, which is exact for a single orbital. The enhancement factor we introduce is related to the extent to which the electron density is localized. The accuracy of the new KEDF is benchmarked against Kohn-Sham density functional theory (KSDFT) by comparing predicted energy differences between phases, equilibrium volumes, and bulk moduli for various semiconductors, along with metal-insulator phase transition pressures. We also compare point defect and (100) surface energies in silicon for a broad test of its applicability. This new KEDF accurately reproduces the exact non-interacting kinetic energy of KSDFT with only one additional adjustable parameter beyond the three parameters in the WGC99 KEDF; it exhibits good transferability between semiconducting to metallic silicon phases and between various III-V semiconductors without parameter adjustment. Overall, this KEDF is more accurate than previously proposed OF KEDFs (e.g., the Huang-Carter (HC) KEDF) for semiconductors, while the computational efficiency remains at the level of the WGC99 KEDF (several hundred times faster than the HC KEDF). This accurate, fast, and transferable new KEDF holds considerable promise for large-scale OFDFT simulations of metallic through semiconducting materials.

  17. Enhanced von Weizsäcker Wang-Govind-Carter kinetic energy density functional for semiconductors

    NASA Astrophysics Data System (ADS)

    Shin, Ilgyou; Carter, Emily A.

    2014-05-01

    We propose a new form of orbital-free (OF) kinetic energy density functional (KEDF) for semiconductors that is based on the Wang-Govind-Carter (WGC99) nonlocal KEDF. We enhance within the latter the semi-local von Weizsäcker KEDF term, which is exact for a single orbital. The enhancement factor we introduce is related to the extent to which the electron density is localized. The accuracy of the new KEDF is benchmarked against Kohn-Sham density functional theory (KSDFT) by comparing predicted energy differences between phases, equilibrium volumes, and bulk moduli for various semiconductors, along with metal-insulator phase transition pressures. We also compare point defect and (100) surface energies in silicon for a broad test of its applicability. This new KEDF accurately reproduces the exact non-interacting kinetic energy of KSDFT with only one additional adjustable parameter beyond the three parameters in the WGC99 KEDF; it exhibits good transferability between semiconducting to metallic silicon phases and between various III-V semiconductors without parameter adjustment. Overall, this KEDF is more accurate than previously proposed OF KEDFs (e.g., the Huang-Carter (HC) KEDF) for semiconductors, while the computational efficiency remains at the level of the WGC99 KEDF (several hundred times faster than the HC KEDF). This accurate, fast, and transferable new KEDF holds considerable promise for large-scale OFDFT simulations of metallic through semiconducting materials.

  18. 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.

  19. Kinetic study on biomass gasification

    SciTech Connect

    Bingyan, X.; Chuangzhi, W.; Zhengfen, L.; Guang, Z.X. )

    1992-09-01

    An experimental apparatus, with the features of fast heating rate and continuous record of reaction parameters, was developed to study kinetics of fast pyrolysis. The temperature effects, at a range of 400 C to 900 C, on pyrolysis rate, products profile, gas quality and quantity, and so on, were studied and the results are listed and analyzed. The effect of secondary reaction of gas phase at 700 C was tested and the regression result is expressed in an experimental formula. Based on the experimental results, the three-stage-reaction mechanism module is suggested. The kinetic expression to calculate gas formation rate is concluded as: d{alpha}/dt = A exp({minus}E/RT)(1 {minus} {alpha}){sup n}. The kinetic parameters of A, E, and n at different temperatures are given in the paper.

  20. Droplet Growth Kinetics in Various Environments

    NASA Astrophysics Data System (ADS)

    Raatikainen, T. E.; Lathem, T. L.; Moore, R.; Lin, J. J.; Cerully, K. M.; Padro, L.; Lance, S.; Cozic, J.; Anderson, B. E.; Nenes, A.

    2012-12-01

    The largest uncertainties in the effects of atmospherics aerosols on the global radiation budget are related to their indirect effects on cloud properties (IPCC, the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, 2007). Cloud formation is a kinetic process where the resulting cloud properties depend on aerosol properties and meteorological parameters such as updraft velocity (e.g. McFiggans et al., Atmos. Chem. Phys., 6, 2593-2649, 2006). Droplet growth rates are limited by the water vapor diffusion, but additional kinetic limitations, e.g., due to organic surface films, slow solute dissociation or highly viscous or glassy aerosol states have been hypothesized. Significant additional kinetic limitations can lead to increased cloud droplet number concentration, thus the effect is similar to those of increased aerosol number concentration or changes in vertical velocity (e.g. Nenes et al., Geophys. Res. Lett., 29, 1848, 2002). There are a few studies where slow droplet growth has been observed (e.g. Ruehl et al., Geophys. Res. Lett., 36, L15814, 2009), however, little is currently known about their global occurrence and magnitude. Cloud micro-physics models often describe kinetic limitations by an effective water vapor uptake coefficient or similar parameter. Typically, determining aerosol water vapor uptake coefficients requires experimental observations of droplet growth which are interpreted by a numerical droplet growth model where the uptake coefficient is an adjustable parameter (e.g. Kolb et al., Atmos. Chem. Phys., 10, 10561-10605, 2010). Such methods have not been practical for high time-resolution or long term field measurements, until a model was recently developed for analyzing Droplet Measurement Technologies (DMT) cloud condensation nuclei (CCN) counter data (Raatikainen et al., Atmos. Chem. Phys., 12, 4227-4243, 2012). Model verification experiments showed that the calibration aerosol droplet size can be predicted accurately

  1. Kinetic modeling of pH-dependent antimony (V) sorption and transport in iron oxide-coated sand.

    PubMed

    Cai, Yongbing; Li, Lulu; Zhang, Hua

    2015-11-01

    Understanding the mechanisms and kinetics controlling the retention and transport of antimony (Sb) is prerequisite for evaluating the risk of groundwater contamination by the toxic element. In this study, kinetic batch and saturated miscible displacement experiments were performed to investigate effects of protonation-deprotonation reactions on sorption-desorption and transport of Sb(V) in iron oxide-coated sand (IOCS). Results clearly demonstrated that Sb(V) sorption was highly nonlinear and time dependent, where both sorption capacity and kinetic rates decreased with increasing solution pH. Breakthrough curves (BTCs) obtained at different solution pH exhibited that mobility of Sb(V) were higher under neutral to alkaline condition than under acidic condition. Because of the nonlinear and non-equilibrium nature of Sb(V) retention and transport, multi-reaction models (MRM) with equilibrium and kinetic sorption expressions were utilized successfully to simulate the experiment data. Equilibrium distribution coefficient (Ke) and reversible kinetic retention parameters (k1 and k2) of both kinetic sorption and transport experiment showed marked decrease as pH increased from 4.0 to 7.5. Surface complexation is suggested as the dominant mechanism for the observed pH-dependent phenomena, which need to be incorporated into the kinetic models to accurately simulate the reactive transport of Sb(V) in vadose zone and aquifers. PMID:26291756

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

    NASA Astrophysics Data System (ADS)

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

    2007-02-01

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

  3. 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…

  4. Comparative kinetic analysis of two fungal β-glucosidases

    PubMed Central

    2010-01-01

    . Conclusions This article provides a useful comparison between the activity of β-glucosidases from two different fungi, and shows the importance of fully characterizing both enzymes. A Michaelis-Menten model was developed, including glucose inhibition and kinetic parameters, which were accurately determined and compared. This model can be further integrated into a cellulose hydrolysis model dissociating β-glucosidase activity from that of other cellulases. It can also help to define the optimal enzymatic cocktails for new β-glucosidase activities. PMID:20181208

  5. Kinetics of HMX and Phase Transitions: Effects of Grain Size at Elevated Temperature

    SciTech Connect

    Saw, C K

    2002-06-13

    To date a global kinetic rate law has not been written to accurately describe solid-solid phase transformations of HMX and TATB where contributions from grain size effects, binder contents, and impurity levels are explicitly defined. Our recent work presented at the 2001 SCCM topical APS meeting, Atlanta, GA, demonstrated one can not confidently use the second harmonic generation (SHG) diagnostic to study energetic material phase transitions where non-uniform grain size distributions are present. For example, in HMX, the early arrival of SHG before the XRD in the SHG/XRD simultaneous high temperature experiment clearly indicates the partial molecular conversion from centrosymmetric to non-centrosymmetric without any structural changes as exhibit by the XRD pattern. This conversion is attributed to the changes of the surface molecules due to the differences in potential between the surface and the bulk. The present paper reports on accurate XRD measurements following changes of {beta}-HMX to {delta}-HMX at elevated temperature. The results are compared for sample with 2 different grain sizes for HMX. We report accurate temperature dependent lattice parameters and hence volume and linear thermal expansion coefficients along each crystallographic axis. We have also conducted kinetic studies of the behavior of 2 grain-sizes of HMX and concluded that their kinetics, are drastically different.

  6. Global parameter estimation methods for stochastic biochemical systems

    PubMed Central

    2010-01-01

    described in this work have provided an effective and practical approach in the estimation of kinetic parameters of stochastic systems from either sparse or dense cell population data. Nevertheless, similar to kinetic parameter estimation in other modelling frameworks, not all parameters can be estimated accurately, which is a common problem arising from the lack of complete parameter identifiability from the available data. PMID:20691037

  7. Modeling of hydrogen production methods: Single particle model and kinetics assessment

    SciTech Connect

    Miller, R.S.; Bellan, J.

    1996-10-01

    The investigation carried out by the Jet Propulsion Laboratory (JPL) is devoted to the modeling of biomass pyrolysis reactors producing an oil vapor (tar) which is a precursor to hydrogen. This is an informal collaboration with NREL whereby JPL uses the experimentally-generated NREL data both as initial and boundary conditions for the calculations, and as a benchmark for model validation. The goal of this investigation is to find drivers of biomass fast-pyrolysis in the low temperature regime. The rationale is that experimental observations produce sparse discrete conditions for model validation, and that numerical simulations produced with a validated model are an economic way to find control parameters and an optimal operation regime, thereby circumventing costly changes in hardware and tests. During this first year of the investigation, a detailed mathematical model has been formulated for the temporal and spatial accurate modeling of solid-fluid reactions in biomass particles. These are porous particles for which volumetric reaction rate data is known a priori and both the porosity and the permeability of the particle are large enough to allow for continuous gas phase flow. The methodology has been applied to the pyrolysis of spherically symmetric biomass particles by considering previously published kinetics schemes for both cellulose and wood. The results show that models which neglect the thermal and species boundary layers exterior to the particle will generally over predict both the pyrolysis rates and experimentally obtainable tar yields. An evaluation of the simulation results through comparisons with experimental data indicates that while the cellulose kinetics is reasonably accurate, the wood pyrolysis kinetics is not accurate; particularly at high reactor temperatures. Current effort in collaboration with NREL is aimed at finding accurate wood kinetics.

  8. Compartmental model of leucine kinetics in humans.

    PubMed

    Cobelli, C; Saccomani, M P; Tessari, P; Biolo, G; Luzi, L; Matthews, D E

    1991-10-01

    The complexity of amino acid and protein metabolism has limited the development of comprehensive, accurate whole body kinetic models. For leucine, simplified approaches are in use to measure in vivo leucine fluxes, but their domain of validity is uncertain. We propose here a comprehensive compartmental model of the kinetics of leucine and alpha-ketoisocaproate (KIC) in humans. Data from a multiple-tracer administration were generated with a two-stage (I and II) experiment. Six normal subjects were studied. In experiment I, labeled leucine and KIC were simultaneously injected into plasma. Four plasma leucine and KIC tracer concentration curves and label in the expired CO2 were measured. In experiment II, labeled bicarbonate was injected into plasma, and labeled CO2 in the expired air was measured. Radioactive (L-[1-14C]leucine, [4,5-3H]KIC, [14C]bicarbonate) and stable isotope (L-[1-13C]leucine, [5,5,5-2H3]KIC, [13C]bicarbonate) tracers were employed. The input format was a bolus (impulse) dose in the radioactive case and a constant infusion in the stable isotope case. A number of physiologically based, linear time-invariant compartmental models were proposed and tested against the data. The model finally chosen for leucine-KIC kinetics has 10 compartments: 4 for leucine, 3 for KIC, and 3 for bicarbonate. The model is a priori uniquely identifiable, and its parameters were estimated with precision from the five curves of experiment I. The separate assessment of bicarbonate kinetics (experiment II) was shown to be unnecessary. The model defines masses and fluxes of leucine in the organism, in particular its intracellular appearance from protein breakdown, its oxidation, and its incorporation into proteins. An important feature of the model is its ability to estimate leucine oxidation by resolving the bicarbonate model in each individual subject. Finally, the model allows the assessment of the domain of validity of the simpler commonly used models. PMID:1928344

  9. Toward Accurate and Quantitative Comparative Metagenomics.

    PubMed

    Nayfach, Stephen; Pollard, Katherine S

    2016-08-25

    Shotgun metagenomics and computational analysis are used to compare the taxonomic and functional profiles of microbial communities. Leveraging this approach to understand roles of microbes in human biology and other environments requires quantitative data summaries whose values are comparable across samples and studies. Comparability is currently hampered by the use of abundance statistics that do not estimate a meaningful parameter of the microbial community and biases introduced by experimental protocols and data-cleaning approaches. Addressing these challenges, along with improving study design, data access, metadata standardization, and analysis tools, will enable accurate comparative metagenomics. We envision a future in which microbiome studies are replicable and new metagenomes are easily and rapidly integrated with existing data. Only then can the potential of metagenomics for predictive ecological modeling, well-powered association studies, and effective microbiome medicine be fully realized. PMID:27565341

  10. How Accurately can we Calculate Thermal Systems?

    SciTech Connect

    Cullen, D; Blomquist, R N; Dean, C; Heinrichs, D; Kalugin, M A; Lee, M; Lee, Y; MacFarlan, R; Nagaya, Y; Trkov, A

    2004-04-20

    I would like to determine how accurately a variety of neutron transport code packages (code and cross section libraries) can calculate simple integral parameters, such as K{sub eff}, for systems that are sensitive to thermal neutron scattering. Since we will only consider theoretical systems, we cannot really determine absolute accuracy compared to any real system. Therefore rather than accuracy, it would be more precise to say that I would like to determine the spread in answers that we obtain from a variety of code packages. This spread should serve as an excellent indicator of how accurately we can really model and calculate such systems today. Hopefully, eventually this will lead to improvements in both our codes and the thermal scattering models that they use in the future. In order to accomplish this I propose a number of extremely simple systems that involve thermal neutron scattering that can be easily modeled and calculated by a variety of neutron transport codes. These are theoretical systems designed to emphasize the effects of thermal scattering, since that is what we are interested in studying. I have attempted to keep these systems very simple, and yet at the same time they include most, if not all, of the important thermal scattering effects encountered in a large, water-moderated, uranium fueled thermal system, i.e., our typical thermal reactors.

  11. Predict amine solution properties accurately

    SciTech Connect

    Cheng, S.; Meisen, A.; Chakma, A.

    1996-02-01

    Improved process design begins with using accurate physical property data. Especially in the preliminary design stage, physical property data such as density viscosity, thermal conductivity and specific heat can affect the overall performance of absorbers, heat exchangers, reboilers and pump. These properties can also influence temperature profiles in heat transfer equipment and thus control or affect the rate of amine breakdown. Aqueous-amine solution physical property data are available in graphical form. However, it is not convenient to use with computer-based calculations. Developed equations allow improved correlations of derived physical property estimates with published data. Expressions are given which can be used to estimate physical properties of methyldiethanolamine (MDEA), monoethanolamine (MEA) and diglycolamine (DGA) solutions.

  12. Detecting Cancer Quickly and Accurately

    NASA Astrophysics Data System (ADS)

    Gourley, Paul; McDonald, Anthony; Hendricks, Judy; Copeland, Guild; Hunter, John; Akhil, Ohmar; Capps, Heather; Curry, Marc; Skirboll, Steve

    2000-03-01

    We present a new technique for high throughput screening of tumor cells in a sensitive nanodevice that has the potential to quickly identify a cell population that has begun the rapid protein synthesis and mitosis characteristic of cancer cell proliferation. Currently, pathologists rely on microscopic examination of cell morphology using century-old staining methods that are labor-intensive, time-consuming and frequently in error. New micro-analytical methods for automated, real time screening without chemical modification are critically needed to advance pathology and improve diagnoses. We have teamed scientists with physicians to create a microlaser biochip (based upon our R&D award winning bio-laser concept)1 which evaluates tumor cells by quantifying their growth kinetics. The key new discovery was demonstrating that the lasing spectra are sensitive to the biomolecular mass in the cell, which changes the speed of light in the laser microcavity. Initial results with normal and cancerous human brain cells show that only a few hundred cells -- the equivalent of a billionth of a liter -- are required to detect abnormal growth. The ability to detect cancer in such a minute tissue sample is crucial for resecting a tumor margin or grading highly localized tumor malignancy. 1. P. L. Gourley, NanoLasers, Scientific American, March 1998, pp. 56-61. This work supported under DOE contract DE-AC04-94AL85000 and the Office of Basic Energy Sciences.

  13. Detecting cancer quickly and accurately

    NASA Astrophysics Data System (ADS)

    Gourley, Paul L.; McDonald, Anthony E.; Hendricks, Judy K.; Copeland, G. C.; Hunter, John A.; Akhil, O.; Cheung, D.; Cox, Jimmy D.; Capps, H.; Curry, Mark S.; Skirboll, Steven K.

    2000-03-01

    We present a new technique for high throughput screening of tumor cells in a sensitive nanodevice that has the potential to quickly identify a cell population that has begun the rapid protein synthesis and mitosis characteristic of cancer cell proliferation. Currently, pathologists rely on microscopic examination of cell morphology using century-old staining methods that are labor-intensive, time-consuming and frequently in error. New micro-analytical methods for automated, real time screening without chemical modification are critically needed to advance pathology and improve diagnoses. We have teamed scientists with physicians to create a microlaser biochip (based upon our R&D award winning bio- laser concept) which evaluates tumor cells by quantifying their growth kinetics. The key new discovery was demonstrating that the lasing spectra are sensitive to the biomolecular mass in the cell, which changes the speed of light in the laser microcavity. Initial results with normal and cancerous human brain cells show that only a few hundred cells -- the equivalent of a billionth of a liter -- are required to detect abnormal growth. The ability to detect cancer in such a minute tissue sample is crucial for resecting a tumor margin or grading highly localized tumor malignancy.

  14. Accurate thickness measurement of graphene

    NASA Astrophysics Data System (ADS)

    Shearer, Cameron J.; Slattery, Ashley D.; Stapleton, Andrew J.; Shapter, Joseph G.; Gibson, Christopher T.

    2016-03-01

    Graphene has emerged as a material with a vast variety of applications. The electronic, optical and mechanical properties of graphene are strongly influenced by the number of layers present in a sample. As a result, the dimensional characterization of graphene films is crucial, especially with the continued development of new synthesis methods and applications. A number of techniques exist to determine the thickness of graphene films including optical contrast, Raman scattering and scanning probe microscopy techniques. Atomic force microscopy (AFM), in particular, is used extensively since it provides three-dimensional images that enable the measurement of the lateral dimensions of graphene films as well as the thickness, and by extension the number of layers present. However, in the literature AFM has proven to be inaccurate with a wide range of measured values for single layer graphene thickness reported (between 0.4 and 1.7 nm). This discrepancy has been attributed to tip-surface interactions, image feedback settings and surface chemistry. In this work, we use standard and carbon nanotube modified AFM probes and a relatively new AFM imaging mode known as PeakForce tapping mode to establish a protocol that will allow users to accurately determine the thickness of graphene films. In particular, the error in measuring the first layer is reduced from 0.1-1.3 nm to 0.1-0.3 nm. Furthermore, in the process we establish that the graphene-substrate adsorbate layer and imaging force, in particular the pressure the tip exerts on the surface, are crucial components in the accurate measurement of graphene using AFM. These findings can be applied to other 2D materials.

  15. Kinetics of Reactive Wetting

    SciTech Connect

    YOST, FREDERICK G.

    1999-09-09

    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. The wide diversity of processes, such as diffusion, chemical reaction, and fluxing, and their possible combinations suggest that various rate laws should be expected for wetting kinetics depending on the controlling processes. These rate laws are expected to differ crucially from the standard fluid controlled wetting models found in the literature. Voitovitch et al. and Mortensen et al. have shown data that suggests diffusion control for some systems and reaction control for others. They also presented a model of wetting kinetics controlled by the diffusion of a constituent contained by the wetting fluid. 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

  16. Dynamic Positron Emission Tomography Image Restoration via a Kinetics-Induced Bilateral Filter

    PubMed Central

    Bian, Zhaoying; Huang, Jing; Ma, Jianhua; Lu, Lijun; Niu, Shanzhou; Zeng, Dong; Feng, Qianjin; Chen, Wufan

    2014-01-01

    Dynamic positron emission tomography (PET) imaging is a powerful tool that provides useful quantitative information on physiological and biochemical processes. However, low signal-to-noise ratio in short dynamic frames makes accurate kinetic parameter estimation from noisy voxel-wise time activity curves (TAC) a challenging task. To address this problem, several spatial filters have been investigated to reduce the noise of each frame with noticeable gains. These filters include the Gaussian filter, bilateral filter, and wavelet-based filter. These filters usually consider only the local properties of each frame without exploring potential kinetic information from entire frames. Thus, in this work, to improve PET parametric imaging accuracy, we present a kinetics-induced bilateral filter (KIBF) to reduce the noise of dynamic image frames by incorporating the similarity between the voxel-wise TACs using the framework of bilateral filter. The aim of the proposed KIBF algorithm is to reduce the noise in homogeneous areas while preserving the distinct kinetics of regions of interest. Experimental results on digital brain phantom and in vivo rat study with typical 18F-FDG kinetics have shown that the present KIBF algorithm can achieve notable gains over other existing algorithms in terms of quantitative accuracy measures and visual inspection. PMID:24586657

  17. Accurate ab Initio Spin Densities

    PubMed Central

    2012-01-01

    We present an approach for the calculation of spin density distributions for molecules that require very large active spaces for a qualitatively correct description of their electronic structure. Our approach is based on the density-matrix renormalization group (DMRG) algorithm to calculate the spin density matrix elements as a basic quantity for the spatially resolved spin density distribution. The spin density matrix elements are directly determined from the second-quantized elementary operators optimized by the DMRG algorithm. As an analytic convergence criterion for the spin density distribution, we employ our recently developed sampling-reconstruction scheme [J. Chem. Phys.2011, 134, 224101] to build an accurate complete-active-space configuration-interaction (CASCI) wave function from the optimized matrix product states. The spin density matrix elements can then also be determined as an expectation value employing the reconstructed wave function expansion. Furthermore, the explicit reconstruction of a CASCI-type wave function provides insight into chemically interesting features of the molecule under study such as the distribution of α and β electrons in terms of Slater determinants, CI coefficients, and natural orbitals. The methodology is applied to an iron nitrosyl complex which we have identified as a challenging system for standard approaches [J. Chem. Theory Comput.2011, 7, 2740]. PMID:22707921

  18. 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.

  19. Enzymolysis kinetics, thermodynamics and model of porcine cerebral protein with single-frequency countercurrent and pulsed ultrasound-assisted processing.

    PubMed

    Zou, Ye; Ding, Yangyang; Feng, Weiwei; Wang, Wei; Li, Qian; Chen, Yao; Wu, Huiyu; Wang, Xintong; Yang, Liuqing; Wu, Xiangyang

    2016-01-01

    The present work investigated the enzymolysis kinetics, thermodynamics and model of porcine cerebral protein (PCP) which was pretreated by single-frequency countercurrent and pulsed ultrasound. The kinetic constants for ultrasonic pretreated and traditional enzymolysis have been determined. Results showed that the value of KM in ultrasonic PCP (UPCP) enzymolysis decreased by 9% over that in the traditional enzymolysis. The values of reaction rate constant (k) for UPCP enzymolysis increased by 207%, 121%, 62%, and 45% at 293, 303, 313 and 323 K, respectively. For the thermodynamic parameters, ultrasound decreased activation energy (Ea), change in enthalpy (ΔH) and entropy (ΔS) by 76%, 82% and 31% in PCP, respectively. However, ultrasound had little change in Gibbs free energy (ΔG) value in the temperature range of 293-323 K. Therefore, a general kinetic equation for the enzymolysis model of UPCP by a simple empirical equation was suggested. The experimental values fits with the enzymolysis kinetic model with a low average relative error (4%) confirmed that the kinetic model was accurate to reflect the enzymolysis process. The positive effect of single-frequency countercurrent and pulsed ultrasound in this study and application of the kinetic model may be useful for the release of bioactive peptides from meat processing by-products. PMID:26384911

  20. Kinetics of aggregation in non-Brownian magnetic particle dispersions in the presence of perturbations

    NASA Astrophysics Data System (ADS)

    Donado, F.; Sandoval, U.; Carrillo, J. L.

    2009-01-01

    An experimental and theoretical study on the kinetics of the aggregation process of magnetic particles dispersed in mineral oils is presented. A static magnetic field and an oscillating magnetic perturbation are applied on the dispersion. In the low-particle concentrations, the effects on the aggregation of the frequency, the concentration of particles and the viscosity of the liquid are analyzed. It was found that the behavior of the cluster length as a function of the main control parameters can be accurately characterized by scaling relations. The physical characteristics of the aggregates are discussed in relation to measurements of viscosity as a function of time.

  1. Kinetic MHD simulation of large 'circ; tearing mode

    NASA Astrophysics Data System (ADS)

    Cheng, Jianhua; Chen, Yang; Parker, Scott; Uzdensky, Dmitri

    2012-03-01

    We have developed a second-order accurate semi-implicit δ method for kinetic MHD simulation with Lorentz force ions and fluid electrons. The model has been used to study the resistive tearing mode instability, which involves multiple spatial scales. In small 'circ; cases, the linear growth rate and eigenmode structure are consistent with resistive MHD analysis. The Rutherford stage and saturation are demonstrated, but the simulation exhibits different saturation island widths compared with previous MHD simulations. In large 'circ; cases, nonlinear simulations show multiple islands forming, followed by the islands coalescing at later times. The competition between these two processes strongly influences the reconnection rates and eventually leads to a steady state reconnection. We will present various parameter studies and show that our hybrid results agree with fluid analysis in certain limits (e.g., relatively large resisitivities).

  2. A kinetic model of municipal sludge degradation during non-catalytic wet oxidation.

    PubMed

    Prince-Pike, Arrian; Wilson, David I; Baroutian, Saeid; Andrews, John; Gapes, Daniel J

    2015-12-15

    Wet oxidation is a successful process for the treatment of municipal sludge. In addition, the resulting effluent from wet oxidation is a useful carbon source for subsequent biological nutrient removal processes in wastewater treatment. Owing to limitations with current kinetic models, this study produced a kinetic model which predicts the concentrations of key intermediate components during wet oxidation. The model was regressed from lab-scale experiments and then subsequently validated using data from a wet oxidation pilot plant. The model was shown to be accurate in predicting the concentrations of each component, and produced good results when applied to a plant 500 times larger in size. A statistical study was undertaken to investigate the validity of the regressed model parameters. Finally the usefulness of the model was demonstrated by suggesting optimum operating conditions such that volatile fatty acids were maximised. PMID:26426294

  3. Kinetics of phenol degradation in an anaerobic fixed-biofilm process

    SciTech Connect

    Lin, Y.H.; Lee, K.K.

    2006-06-15

    A mathematical model was developed to describe phenol degradation in an anaerobic fixed-biofilm process. The model incorporates the mechanisms of diffusive mass transport and Monod kinetics. The model was solved using a combination of the orthogonal collocation method and Gear's method. A pilot-scale column reactor was used to verify the model. Batch kinetic tests were conducted independently to determine the biokinetic parameters used in the model, while shear loss and initial thickness of biofilm were assumed so that the model simulated the substrate concentration results well. The removal efficiency for phenol was approximately 98.5% at a steady-state condition. The model accurately described the effluent substrate concentrations and the sequence of biodegradation in the reactor. The model simulations are in agreement with the experimental results. The approaches presented in this paper could be used to design full-scale anaerobic fixed-biofilm reactor systems for the biodegradation of phenolic substrates.

  4. α-Phase transformation kinetics of U - 8 wt% Mo established by in situ neutron diffraction

    NASA Astrophysics Data System (ADS)

    Steiner, M. A.; Calhoun, C. A.; Klein, R. W.; An, K.; Garlea, E.; Agnew, S. R.

    2016-08-01

    The α-phase transformation kinetics of as-cast U - 8 wt% Mo below the eutectoid temperature have been established by in situ neutron diffraction. α-phase weight fraction data acquired through Rietveld refinement at five different isothermal hold temperatures can be modeled accurately utilizing a simple Johnson-Mehl-Avrami-Kolmogorov impingement-based theory, and the results are validated by a corresponding evolution in the γ-phase lattice parameter during transformation that follows Vegard's law. Neutron diffraction data is used to produce a detailed Time-Temperature-Transformation diagram that improves upon inconsistencies in the current literature, exhibiting a minimum transformation start time of 40 min at temperatures between 500 °C and 510 °C. The transformation kinetics of U - 8 wt% Mo can vary significantly from as-cast conditions after extensive heat treatments, due to homogenization of the typical dendritic microstructure which possesses non-negligible solute segregation.

  5. A Kinetic and Mass Transfer Model for Glycerol Hydrogenolysis in a Trickle-Bed Reactor

    SciTech Connect

    Xi, Yaoyan; Holladay, Johnathan E.; Frye, John G.; Oberg, Aaron A.; Jackson, James E.; Miller, Dennis J.

    2010-11-15

    A detailed model of glycerol hydrogenolysis in a trickle-bed reactor is presented that includes a mechanistically based kinetic rate expression, energy transport, mass transport across the gas-liquid and liquid-solid interfaces, intraparticle catalyst mass transfer, and partial wetting of the bed. Optimal kinetic parameters for the glycerol hydrogenolysis rate expression were determined via nonlinear regression analysis on the basis of experiments conducted in a laboratory-scale trickle-bed reactor over a broad range of operating conditions. Model predictions agree well with experimental data and accurately predict trends in reactor performance with liquid flow rate, temperature, hydrogen pressure, and base promoter concentration. The model is thus a useful tool for predicting laboratory reactor performance and for design of commercial-scale trickle-bed systems.

  6. 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 = 77–300 K and magnetic fields H = 0.5–5 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.

  7. Towards an accurate bioimpedance identification

    NASA Astrophysics Data System (ADS)

    Sanchez, B.; Louarroudi, E.; Bragos, R.; Pintelon, R.

    2013-04-01

    This paper describes the local polynomial method (LPM) for estimating the time-invariant bioimpedance frequency response function (FRF) considering both the output-error (OE) and the errors-in-variables (EIV) identification framework and compare it with the traditional cross— and autocorrelation spectral analysis techniques. The bioimpedance FRF is measured with the multisine electrical impedance spectroscopy (EIS) technique. To show the overwhelming accuracy of the LPM approach, both the LPM and the classical cross— and autocorrelation spectral analysis technique are evaluated through the same experimental data coming from a nonsteady-state measurement of time-varying in vivo myocardial tissue. The estimated error sources at the measurement frequencies due to noise, σnZ, and the stochastic nonlinear distortions, σZNL, have been converted to Ω and plotted over the bioimpedance spectrum for each framework. Ultimately, the impedance spectra have been fitted to a Cole impedance model using both an unweighted and a weighted complex nonlinear least square (CNLS) algorithm. A table is provided with the relative standard errors on the estimated parameters to reveal the importance of which system identification frameworks should be used.

  8. Determining anaerobic degradation kinetics from batch tests.

    PubMed

    Moreda, Iván López

    2016-01-01

    Data obtained from a biomethane potential (BMP) test were used in order to obtain the parameters of a kinetic model of solid wastes anaerobic degradation. The proposed model considers a hydrolysis step with a first order kinetic, a Monod kinetic for the soluble organic substrate degradation and a first order decay of microorganisms. The instantaneous release of methane was assumed. The parameters of the model are determined following a direct search optimization procedure. A 'multiple-shooting' technique was used as a first step of the optimization process. The confidence interval of the parameters was determined by using Monte Carlo simulations. Also, the distribution functions of the parameters were determined. Only the hydrolysis first order constant shows a normal distribution. PMID:27191569

  9. A general moment expansion method for stochastic kinetic models

    NASA Astrophysics Data System (ADS)

    Ale, Angelique; Kirk, Paul; Stumpf, Michael P. H.

    2013-05-01

    Moment approximation methods are gaining increasing attention for their use in the approximation of the stochastic kinetics of chemical reaction systems. In this paper we derive a general moment expansion method for any type of propensities and which allows expansion up to any number of moments. For some chemical reaction systems, more than two moments are necessary to describe the dynamic properties of the system, which the linear noise approximation is unable to provide. Moreover, also for systems for which the mean does not have a strong dependence on higher order moments, moment approximation methods give information about higher order moments of the underlying probability distribution. We demonstrate the method using a dimerisation reaction, Michaelis-Menten kinetics and a model of an oscillating p53 system. We show that for the dimerisation reaction and Michaelis-Menten enzyme kinetics system higher order moments have limited influence on the estimation of the mean, while for the p53 system, the solution for the mean can require several moments to converge to the average obtained from many stochastic simulations. We also find that agreement between lower order moments does not guarantee that higher moments will agree. Compared to stochastic simulations, our approach is numerically highly efficient at capturing the behaviour of stochastic systems in terms of the average and higher moments, and we provide expressions for the computational cost for different system sizes and orders of approximation. We show how the moment expansion method can be employed to efficiently quantify parameter sensitivity. Finally we investigate the effects of using too few moments on parameter estimation, and provide guidance on how to estimate if the distribution can be accurately approximated using only a few moments.

  10. Kinetic evidence for protein clustering at a surface

    SciTech Connect

    Ramsden, J.J. ); Bachmanova, G.I.; Archakov, A.I. )

    1994-12-01

    The molecules designated 1A2 and 2B4 belong to the cytochrome P450 protein superfamily. They can interact specifically with lipid bilayers via the penetration of part of their amino acid chains into the bilayer. The kinetics of their irreversible adsorption from solution to phospholipid bilayers, accurately measured in the low to intermediate coverage range using an integrated optics reflectance technique, differ significantly: at intermediate bulk solution concentrations, 2B4 shows typical random sequential adsorption (RSA) kinetics, whereas 1A2 shows Langmuir kinetics. At higher bulk concentration the behavior of 1[ital A]2 switches to RSA kinetics, and at very low concentrations 2[ital B]4 switches to Langmuir kinetics. The Langmuir kinetics provides strong evidence for clustering of the molecules at the bilayer surface, and the observed concentration dependence of the kinetics is consistent with the clusters arising through lateral diffusion of the proteins on the surface.

  11. 38 CFR 4.46 - Accurate measurement.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 38 Pensions, Bonuses, and Veterans' Relief 1 2013-07-01 2013-07-01 false Accurate measurement. 4... RATING DISABILITIES Disability Ratings The Musculoskeletal System § 4.46 Accurate measurement. Accurate measurement of the length of stumps, excursion of joints, dimensions and location of scars with respect...

  12. 38 CFR 4.46 - Accurate measurement.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 38 Pensions, Bonuses, and Veterans' Relief 1 2010-07-01 2010-07-01 false Accurate measurement. 4... RATING DISABILITIES Disability Ratings The Musculoskeletal System § 4.46 Accurate measurement. Accurate measurement of the length of stumps, excursion of joints, dimensions and location of scars with respect...

  13. 38 CFR 4.46 - Accurate measurement.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 38 Pensions, Bonuses, and Veterans' Relief 1 2011-07-01 2011-07-01 false Accurate measurement. 4... RATING DISABILITIES Disability Ratings The Musculoskeletal System § 4.46 Accurate measurement. Accurate measurement of the length of stumps, excursion of joints, dimensions and location of scars with respect...

  14. 38 CFR 4.46 - Accurate measurement.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 38 Pensions, Bonuses, and Veterans' Relief 1 2014-07-01 2014-07-01 false Accurate measurement. 4... RATING DISABILITIES Disability Ratings The Musculoskeletal System § 4.46 Accurate measurement. Accurate measurement of the length of stumps, excursion of joints, dimensions and location of scars with respect...

  15. 38 CFR 4.46 - Accurate measurement.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 38 Pensions, Bonuses, and Veterans' Relief 1 2012-07-01 2012-07-01 false Accurate measurement. 4... RATING DISABILITIES Disability Ratings The Musculoskeletal System § 4.46 Accurate measurement. Accurate measurement of the length of stumps, excursion of joints, dimensions and location of scars with respect...

  16. 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.

  17. Modulated inflation from the kinetic term

    SciTech Connect

    Matsuda, Tomohiro

    2008-05-15

    We study modulated inflation from the kinetic term. Using the Mukhanov-Sasaki variable, it is possible to determine how mixing induced by the kinetic term feeds the curvature perturbation with the isocurvature perturbation. We show explicitly that the analytic result obtained from the evolution of the Mukhanov-Sasaki variable is consistent with the {delta}N-formula. From our results, we find analytic conditions for the modulated fluctuation and the non-Gaussianity parameter.

  18. Parameter estimation for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Santhanagopalan, Shriram

    With an increase in the demand for lithium based batteries at the rate of about 7% per year, the amount of effort put into improving the performance of these batteries from both experimental and theoretical perspectives is increasing. There exist a number of mathematical models ranging from simple empirical models to complicated physics-based models to describe the processes leading to failure of these cells. The literature is also rife with experimental studies that characterize the various properties of the system in an attempt to improve the performance of lithium ion cells. However, very little has been done to quantify the experimental observations and relate these results to the existing mathematical models. In fact, the best of the physics based models in the literature show as much as 20% discrepancy when compared to experimental data. The reasons for such a big difference include, but are not limited to, numerical complexities involved in extracting parameters from experimental data and inconsistencies in interpreting directly measured values for the parameters. In this work, an attempt has been made to implement simplified models to extract parameter values that accurately characterize the performance of lithium ion cells. The validity of these models under a variety of experimental conditions is verified using a model discrimination procedure. Transport and kinetic properties are estimated using a non-linear estimation procedure. The initial state of charge inside each electrode is also maintained as an unknown parameter, since this value plays a significant role in accurately matching experimental charge/discharge curves with model predictions and is not readily known from experimental data. The second part of the dissertation focuses on parameters that change rapidly with time. For example, in the case of lithium ion batteries used in Hybrid Electric Vehicle (HEV) applications, the prediction of the State of Charge (SOC) of the cell under a variety of

  19. Kinetic modeling of dissolution and crystallization of slurries with attenuated total reflectance UV-visible absorbance and near-infrared reflectance measurements.

    PubMed

    Hsieh, Chun H; Billeter, Julien; McNally, Mary Ellen P; Hoffman, Ronald M; Gemperline, Paul J

    2013-06-01

    Slurries are often used in chemical and pharmaceutical manufacturing processes but present challenging online measurement and monitoring problems. In this paper, a novel multivariate kinetic modeling application is described that provides calibration-free estimates of time-resolved profiles of the solid and dissolved fractions of a substance in a model slurry system. The kinetic model of this system achieved data fusion of time-resolved spectroscopic measurements from two different kinds of fiber-optic probes. Attenuated total reflectance UV-vis (ATR UV-vis) and diffuse reflectance near-infrared (NIR) spectra were measured simultaneously in a small-scale semibatch reactor. A simplified comprehensive kinetic model was then fitted to the time-resolved spectroscopic data to determine the kinetics of crystallization and the kinetics of dissolution for online monitoring and quality control purposes. The parameters estimated in the model included dissolution and crystal growth rate constants, as well as the dissolution rate order. The model accurately estimated the degree of supersaturation as a function of time during conditions when crystallization took place and accurately estimated the degree of undersaturation during conditions when dissolution took place. PMID:23565977

  20. Accurate projector calibration method by using an optical coaxial camera.

    PubMed

    Huang, Shujun; Xie, Lili; Wang, Zhangying; Zhang, Zonghua; Gao, Feng; Jiang, Xiangqian

    2015-02-01

    Digital light processing (DLP) projectors have been widely utilized to project digital structured-light patterns in 3D imaging systems. In order to obtain accurate 3D shape data, it is important to calibrate DLP projectors to obtain the internal parameters. The existing projector calibration methods have complicated procedures or low accuracy of the obtained parameters. This paper presents a novel method to accurately calibrate a DLP projector by using an optical coaxial camera. The optical coaxial geometry is realized by a plate beam splitter, so the DLP projector can be treated as a true inverse camera. A plate having discrete markers on the surface is used to calibrate the projector. The corresponding projector pixel coordinate of each marker on the plate is determined by projecting vertical and horizontal sinusoidal fringe patterns on the plate surface and calculating the absolute phase. The internal parameters of the DLP projector are obtained by the corresponding point pair between the projector pixel coordinate and the world coordinate of discrete markers. Experimental results show that the proposed method can accurately calibrate the internal parameters of a DLP projector. PMID:25967789

  1. Raman mapping for kinetic analysis of crystallization of amorphous drug based on distributional images.

    PubMed

    Ueda, Hiroshi; Ida, Yasuo; Kadota, Kazunori; Tozuka, Yuichi

    2014-02-28

    The feasibility of Raman mapping for understanding the crystallization mechanism of an amorphous drug was investigated using described images. The crystallization tendency of amorphous indomethacin under dry condition at 30 °C was kinetically evaluated by means of Raman mapping and X-ray powder diffraction (XRPD) with change in the calculated crystallinities. Raman images directly revealed the occurrence of particle size-dependent non-uniform crystallization; slow crystallization of large particles, but fast crystallization of small particles. Kinetic analysis by fitting to the Kolmogorov-Johnson-Mehl-Avrami equation was performed for the crystallization profiles of both Raman mapping and XRPD data. For the Raman mapping data, the distribution of large particles was characterized and examined. The kinetic parameters calculated from the whole Raman image area agreed well with those of XRPD, suggesting accurate prediction of both techniques for the entire crystallization. Raman images revealed the change in the crystallization mechanism for the focused area; the large particles showed a reduced crystallization rate constant and an increase in the dimensional crystal growth exponent. Raman mapping is an attractive tool for quantitative and kinetic investigation of the crystallization mechanism with distributional images. PMID:24368105

  2. Kinetics of hydrogen consumption by rumen fluid, anaerobic digestor sludge, and sediment.

    PubMed

    Robinson, J A; Tiedje, J M

    1982-12-01

    Michaelis-Menten kinetic parameters for H(2) consumption by three methanogenic habitats were determined from progress curve and initial velocity experiments. The influences of mass transfer resistance, endogenous H(2) production, and growth on apparent parameter estimates were also investigated. Kinetic parameters could not be determined for undiluted rumen fluid and some digestor sludge from gas-phase measurements of H(2), since mass transfer of H(2) across the gas-liquid interface was rate limiting. However, accurate values were obtained once the samples were diluted. H(2) consumption by digestor sludge with a long retention time and by hypereutrophic lake sediment was not phase transfer limited. The K(m) values for H(2) uptake by these habitats were similar, with means of 5.8, 6.0, and 7.1 muM for rumen fluid, digestor sludge, and sediment, respectively. V(max) estimates suggested a ratio of activity of approximately 100 (rumen fluid):10 (sludge):1 (sediment); their ranges were as follows: rumen fluid, 14 to 28 mM h; Holt sludge, 0.7 to 4.3 mM h; and Wintergreen sediment, 0.13 to 0.49 mM h. The principles of phase transfer limitation, studied here for H(2), are the same for all gaseous substrates and products. The limitations and errors associated with gas phase determination of kinetic parameters were evaluated with a mathematical model that combined mass transport and Michaelis-Menten kinetics. Three criteria are described which can be used to evaluate the possibility that a phase transfer limitation exists. If it does not exist, (i) substrate consumption curves are Michaelis-Menten and not first order, (ii) the K(m) is independent of initial substrate concentration, and (iii) the K(m) is independent of biomass (V(max)) and remains constant with dilution of sample. Errors in the Michaelis-Menten kinetic parameters are caused by endogenously produced H(2), but they were <15% for rumen fluid and 10% for lake sediment and digestor sludge. Increases in V

  3. Extracting kinetic information from literature with KineticRE.

    PubMed

    Freitas, Ana Alão; Costa, Hugo; Rocha, Miguel; Rocha, Isabel

    2015-01-01

    To better understand the dynamic behavior of metabolic networks in a wide variety of conditions, the field of Systems Biology has increased its interest in the use of kinetic models. The different databases, available these days, do not contain enough data regarding this topic. Given that a significant part of the relevant information for the development of such models is still wide spread in the literature, it becomes essential to develop specific and powerful text mining tools to collect these data. In this context, this work has as main objective the development of a text mining tool to extract, from scientific literature, kinetic parameters, their respective values and their relations with enzymes and metabolites. The approach proposed integrates the development of a novel plug-in over the text mining framework @Note2. In the end, the pipeline developed was validated with a case study on Kluyveromyces lactis, spanning the analysis and results of 20 full text documents. PMID:26673933

  4. 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.

  5. 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.

  6. Effect of kinetics on residue curve maps for reactive distillation

    SciTech Connect

    Venimadhavan, G.; Buzad, G.; Doherty, M.F.; Malone, M.F. . Dept. of Chemical Engineering)

    1994-11-01

    A class of models is derived for studying the effects of chemical kinetics on residue curve maps for reactive distillation. Activity-based rate and phase equilibrium expressions provide an accurate and thermodynamically consistent description of composition changes in nonideal, reacting vapor-liquid mixtures. For certain strategies of operation, which dictate the rate of product removal, the model equations are nonautonomous, leading to unusual dynamic behavior. However, for a certain special product removal policy, the effects of kinetics can be described by a single parameter, the Damkoehler number, which measures the rate of reaction relative to product removal. For small values of the Damkoehler number, the nonreactive simple distillation residue curve map is recovered and the singular points are the pure components and azeotropes in the nonreactive mixture. A bifurcation analysis shows the deformation and, in some cases, the disappearance of these singular points as the Damkoehler number is increased until the equilibrium reactive residue curve map is recovered at large values. A model problem for the reactive distillation of methyl tert-butyl ether from isobutene and methanol is solved.

  7. Modeling Ignition of a Heptane Isomer: Improved Thermodynamics, Reaction Pathways, Kinetics, and Rate Rule Optimizations for 2-Methylhexane.

    PubMed

    Mohamed, Samah Y; Cai, Liming; Khaled, Fethi; Banyon, Colin; Wang, Zhandong; Al Rashidi, Mariam J; Pitsch, Heinz; Curran, Henry J; Farooq, Aamir; Sarathy, S Mani

    2016-04-14

    Accurate chemical kinetic combustion models of lightly branched alkanes (e.g., 2-methylalkanes) are important to investigate the combustion behavior of real fuels. Improving the fidelity of existing kinetic models is a necessity, as new experiments and advanced theories show inaccuracies in certain portions of the models. This study focuses on updating thermodynamic data and the kinetic reaction mechanism for a gasoline surrogate component, 2-methylhexane, based on recently published thermodynamic group values and rate rules derived from quantum calculations and experiments. Alternative pathways for the isomerization of peroxy-alkylhydroperoxide (OOQOOH) radicals are also investigated. The effects of these updates are compared against new high-pressure shock tube and rapid compression machine ignition delay measurements. It is shown that rate constant modifications are required to improve agreement between kinetic modeling simulations and experimental data. We further demonstrate the ability to optimize the kinetic model using both manual and automated techniques for rate parameter tunings to improve agreement with the measured ignition delay time data. Finally, additional low temperature chain branching reaction pathways are shown to improve the model's performance. The present approach to model development provides better performance across extended operating conditions while also strengthening the fundamental basis of the model. PMID:26998618

  8. Multiple-Bond Kinetics from Single-Molecule Pulling Experiments: Evidence for Multiple NCAM Bonds

    PubMed Central

    Hukkanen, E. J.; Wieland, J. A.; Gewirth, A.; Leckband, D. E.; Braatz, R. D.

    2005-01-01

    The kinetic parameters of single bonds between neural cell adhesion molecules were determined from atomic force microscope measurements of the forced dissociation of the homophilic protein-protein bonds. The analytical approach described provides a systematic procedure for obtaining rupture kinetics for single protein bonds from bond breakage frequency distributions obtained from single-molecule pulling experiments. For these studies, we used the neural cell adhesion molecule (NCAM), which was recently shown to form two independent protein bonds. The analysis of the bond rupture data at different loading rates, using the single-bond full microscopic model, indicates that the breakage frequency distribution is most sensitive to the distance to the transition state and least sensitive to the molecular spring constant. The analysis of bond failure data, however, motivates the use of a double-bond microscopic model that requires an additional kinetic parameter. This double-bond microscopic model assumes two independent NCAM-NCAM bonds, and more accurately describes the breakage frequency distribution, particularly at high loading rates. This finding agrees with recent surface-force measurements, which showed that NCAM forms two spatially distinct bonds between opposed proteins. PMID:16100278

  9. Poster — Thur Eve — 44: Linearization of Compartmental Models for More Robust Estimates of Regional Hemodynamic, Metabolic and Functional Parameters using DCE-CT/PET Imaging

    SciTech Connect

    Blais, AR; Dekaban, M; Lee, T-Y

    2014-08-15

    Quantitative analysis of dynamic positron emission tomography (PET) data usually involves minimizing a cost function with nonlinear regression, wherein the choice of starting parameter values and the presence of local minima affect the bias and variability of the estimated kinetic parameters. These nonlinear methods can also require lengthy computation time, making them unsuitable for use in clinical settings. Kinetic modeling of PET aims to estimate the rate parameter k{sub 3}, which is the binding affinity of the tracer to a biological process of interest and is highly susceptible to noise inherent in PET image acquisition. We have developed linearized kinetic models for kinetic analysis of dynamic contrast enhanced computed tomography (DCE-CT)/PET imaging, including a 2-compartment model for DCE-CT and a 3-compartment model for PET. Use of kinetic parameters estimated from DCE-CT can stabilize the kinetic analysis of dynamic PET data, allowing for more robust estimation of k{sub 3}. Furthermore, these linearized models are solved with a non-negative least squares algorithm and together they provide other advantages including: 1) only one possible solution and they do not require a choice of starting parameter values, 2) parameter estimates are comparable in accuracy to those from nonlinear models, 3) significantly reduced computational time. Our simulated data show that when blood volume and permeability are estimated with DCE-CT, the bias of k{sub 3} estimation with our linearized model is 1.97 ± 38.5% for 1,000 runs with a signal-to-noise ratio of 10. In summary, we have developed a computationally efficient technique for accurate estimation of k{sub 3} from noisy dynamic PET data.

  10. LSENS - GENERAL CHEMICAL KINETICS AND SENSITIVITY ANALYSIS CODE

    NASA Technical Reports Server (NTRS)

    Bittker, D. A.

    1994-01-01

    LSENS has been developed for solving complex, homogeneous, gas-phase, chemical kinetics problems. The motivation for the development of this program is the continuing interest in developing detailed chemical reaction mechanisms for complex reactions such as the combustion of fuels and pollutant formation and destruction. A reaction mechanism is the set of all elementary chemical reactions that are required to describe the process of interest. Mathematical descriptions of chemical kinetics problems constitute sets of coupled, nonlinear, first-order ordinary differential equations (ODEs). The number of ODEs can be very large because of the numerous chemical species involved in the reaction mechanism. Further complicating the situation are the many simultaneous reactions needed to describe the chemical kinetics of practical fuels. For example, the mechanism describing the oxidation of the simplest hydrocarbon fuel, methane, involves over 25 species participating in nearly 100 elementary reaction steps. Validating a chemical reaction mechanism requires repetitive solutions of the governing ODEs for a variety of reaction conditions. Analytical solutions to the systems of ODEs describing chemistry are not possible, except for the simplest cases, which are of little or no practical value. Consequently, there is a need for fast and reliable numerical solution techniques for chemical kinetics problems. In addition to solving the ODEs describing chemical kinetics, it is often necessary to know what effects variations in either initial condition values or chemical reaction mechanism parameters have on the solution. Such a need arises in the development of reaction mechanisms from experimental data. The rate coefficients are often not known with great precision and in general, the experimental data are not sufficiently detailed to accurately estimate the rate coefficient parameters. The development of a reaction mechanism is facilitated by a systematic sensitivity analysis

  11. On fast reactor kinetics studies

    SciTech Connect

    Seleznev, E. F.; Belov, A. A.; Matveenko, I. P.; Zhukov, A. M.; Raskach, K. F.

    2012-07-01

    The results and the program of fast reactor core time and space kinetics experiments performed and planned to be performed at the IPPE critical facility is presented. The TIMER code was taken as computation support of the experimental work, which allows transient equations to be solved in 3-D geometry with multi-group diffusion approximation. The number of delayed neutron groups varies from 6 to 8. The code implements the solution of both transient neutron transfer problems: a direct one, where neutron flux density and its derivatives, such as reactor power, etc, are determined at each time step, and an inverse one for the point kinetics equation form, where such a parameter as reactivity is determined with a well-known reactor power time variation function. (authors)

  12. Accurate method of modeling cluster scaling relations in modified gravity

    NASA Astrophysics Data System (ADS)

    He, Jian-hua; Li, Baojiu

    2016-06-01

    We propose a new method to model cluster scaling relations in modified gravity. Using a suite of nonradiative hydrodynamical simulations, we show that the scaling relations of accumulated gas quantities, such as the Sunyaev-Zel'dovich effect (Compton-y parameter) and the x-ray Compton-y parameter, can be accurately predicted using the known results in the Λ CDM model with a precision of ˜3 % . This method provides a reliable way to analyze the gas physics in modified gravity using the less demanding and much more efficient pure cold dark matter simulations. Our results therefore have important theoretical and practical implications in constraining gravity using cluster surveys.

  13. Communication: An accurate global potential energy surface for the ground electronic state of ozone

    SciTech Connect

    Dawes, Richard E-mail: hguo@unm.edu; Lolur, Phalgun; Li, Anyang; Jiang, Bin; Guo, Hua E-mail: hguo@unm.edu

    2013-11-28

    We report a new full-dimensional and global potential energy surface (PES) for the O + O{sub 2} → O{sub 3} ozone forming reaction based on explicitly correlated multireference configuration interaction (MRCI-F12) data. It extends our previous [R. Dawes, P. Lolur, J. Ma, and H. Guo, J. Chem. Phys. 135, 081102 (2011)] dynamically weighted multistate MRCI calculations of the asymptotic region which showed the widely found submerged reef along the minimum energy path to be the spurious result of an avoided crossing with an excited state. A spin-orbit correction was added and the PES tends asymptotically to the recently developed long-range electrostatic model of Lepers et al. [J. Chem. Phys. 137, 234305 (2012)]. This PES features: (1) excellent equilibrium structural parameters, (2) good agreement with experimental vibrational levels, (3) accurate dissociation energy, and (4) most-notably, a transition region without a spurious reef. The new PES is expected to allow insight into the still unresolved issues surrounding the kinetics, dynamics, and isotope signature of ozone.

  14. Theory of bi-molecular association dynamics in 2D for accurate model and experimental parameterization of binding rates

    NASA Astrophysics Data System (ADS)

    Yogurtcu, Osman N.; Johnson, Margaret E.

    2015-08-01

    The dynamics of association between diffusing and reacting molecular species are routinely quantified using simple rate-equation kinetics that assume both well-mixed concentrations of species and a single rate constant for parameterizing the binding rate. In two-dimensions (2D), however, even when systems are well-mixed, the assumption of a single characteristic rate constant for describing association is not generally accurate, due to the properties of diffusional searching in dimensions d ≤ 2. Establishing rigorous bounds for discriminating between 2D reactive systems that will be accurately described by rate equations with a single rate constant, and those that will not, is critical for both modeling and experimentally parameterizing binding reactions restricted to surfaces such as cellular membranes. We show here that in regimes of intrinsic reaction rate (ka) and diffusion (D) parameters ka/D > 0.05, a single rate constant cannot be fit to the dynamics of concentrations of associating species independently of the initial conditions. Instead, a more sophisticated multi-parametric description than rate-equations is necessary to robustly characterize bimolecular reactions from experiment. Our quantitative bounds derive from our new analysis of 2D rate-behavior predicted from Smoluchowski theory. Using a recently developed single particle reaction-diffusion algorithm we extend here to 2D, we are able to test and validate the predictions of Smoluchowski theory and several other theories of reversible reaction dynamics in 2D for the first time. Finally, our results also mean that simulations of reactive systems in 2D using rate equations must be undertaken with caution when reactions have ka/D > 0.05, regardless of the simulation volume. We introduce here a simple formula for an adaptive concentration dependent rate constant for these chemical kinetics simulations which improves on existing formulas to better capture non-equilibrium reaction dynamics from dilute

  15. An investigation into the crystallization tendency/kinetics of amorphous active pharmaceutical ingredients: A case study with dipyridamole and cinnarizine.

    PubMed

    Baghel, Shrawan; Cathcart, Helen; Redington, Wynette; O'Reilly, Niall J

    2016-07-01

    Amorphous drug formulations have great potential to enhance solubility and thus bioavailability of BCS class II drugs. However, the higher free energy and molecular mobility of the amorphous form drive them towards the crystalline state which makes them unstable. Accurate determination of the crystallization tendency/kinetics is the key to the successful design and development of such systems. In this study, dipyridamole (DPM) and cinnarizine (CNZ) have been selected as model compounds. Thermodynamic fragility (mT) was measured from the heat capacity change at the glass transition temperature (Tg) whereas dynamic fragility (mD) was evaluated using methods based on extrapolation of configurational entropy to zero [Formula: see text] , and heating rate dependence of Tg [Formula: see text] . The mean relaxation time of amorphous drugs was calculated from the Vogel-Tammann-Fulcher (VTF) equation. Furthermore, the correlation between fragility and glass forming ability (GFA) of the model drugs has been established and the relevance of these parameters to crystallization of amorphous drugs is also assessed. Moreover, the crystallization kinetics of model drugs under isothermal conditions has been studied using Johnson-Mehl-Avrami (JMA) approach to determine the Avrami constant 'n' which provides an insight into the mechanism of crystallization. To further probe into the crystallization mechanism, the non-isothermal crystallization kinetics of model systems were also analysed by statistically fitting the crystallization data to 15 different kinetic models and the relevance of model-free kinetic approach has been established. The crystallization mechanism for DPM and CNZ at each extent of transformation has been predicted. The calculated fragility, glass forming ability (GFA) and crystallization kinetics are found to be in good correlation with the stability prediction of amorphous solid dispersions. Thus, this research work involves a multidisciplinary approach to

  16. Kinetics of C-14 Translocation in Soybean

    PubMed Central

    Fisher, Donald B.

    1970-01-01

    The kinetics of 14C-assimilates in the soybean leaf were studied in pulse labeling and steady state labeling experiments. 14C-Sucrose apparently served as the ultimate source, at least, of translocated 14C-sucrose. However, since the specific activity of leaf sucrose reached a maximum within 5 minutes after pulse labeling, whereas that of exported sucrose did not reach a maximum until at least 20 minutes, it appeared that there were two sucrose compartments in the leaf. A possible physical basis for the two compartments may be the mesophyll (a photosynthetic compartment) and a specialized “paraveinal mesophyll” (a nonphotosynthetic compartment), through which photosynthate must pass on its way to the veins. The 14C kinetics of sterol glucoside, and probably esterified sterol glucoside, were similar to those for 14C-sucrose export. Sterol glucoside was labeled only in its glucose moiety and was the only stem lipid which became strongly labeled during 14C-sucrose translocation. These sterol derivatives may act as membrane carriers of sucrose between the translocation stream and surrounding cells. The kinetics of 14C-sucrose and its movement to the veins are discussed with reference to compartmentation within the leaf and metabolic exchange with other compounds, particularly with starch. Although a simple compartmental model gave a fairly accurate description of 14C-sucrose kinetics, an entirely accurate model could not be provided, primarily because of loss of 14C from sucrose, at an unknown rate, to starch. PMID:16657287

  17. Nucleation and growth transformation kinetics

    NASA Astrophysics Data System (ADS)

    Erukhimovitch, V.; Baram, J.

    1995-03-01

    As a result of the reassessment of the Kolmogorov-Johnson-Mehl-Avrami (KJMA) theory for the kinetics of nucleation and growth transformations, an integral-equation formulation has been developed instead of the well-known and widely used Avrami equation. The presented formulation considers interfacial and diffusional growths, in one, two, and three dimensions, with both time-dependent and time-invariant nucleation and growth rates. The integral-equation model corrects reported inadequacies of the KJMA theory when applied in numerous experiments and various solid-state transformations. It is shown that in the example cases examined in this paper, crystallization from the amorphous state in melt-spun ribbons, isothermal aging of CuAlZn, pearlitic transition in an eutectoid steel, and crystallization in a PEKK polymer, the thermodynamic and kinetic interpretation and parameters extracted from best fits of the Avrami equations to the experimental data are erroneous. The KJMA formulation is a simplification of the real physical conditions. The main limitation of the new model is that almost all the integral equations representing the kinetics of solid-state transformations have no analytical solutions.

  18. Length dependent folding kinetics of phenylacetylene oligomers: Structural characterization of a kinetic trap

    NASA Astrophysics Data System (ADS)

    Elmer, Sidney P.; Pande, Vijay S.

    2005-03-01

    Using simulation to study the folding kinetics of 20-mer poly-phenylacetylene (pPA) oligomers, we find a long time scale trapped kinetic phase in the cumulative folding time distribution. This is demonstrated using molecular dynamics to simulate an ensemble of over 100 folding trajectories. The simulation data are fit to a four-state kinetic model which includes the typical folded and unfolded states, along with an intermediate state, and most surprisingly, a kinetically trapped state. Topologically diverse conformations reminiscent of α helices, β turns, and sheets in proteins are observed, along with unique structures in the form of knots. The nonhelical conformations are implicated, on the basis of structural correlations to kinetic parameters, to contribute to the trapped kinetic behavior. The strong solvophobic forces which mediate the folding process and produce a stable helical folded state also serve to overstabilize the nonhelical conformations, ultimately trapping them. From our simulations, the folding time is predicted to be on the order of 2.5-12.5 μs in the presence of the trapped kinetic phase. The folding mechanism for these 20-mer chains is compared with the previously reported folding mechanism for the pPA 12-mer chains. A linear scaling relationship between the chain length and the mean first passage time is predicted in the absence of the trapped kinetic phase. We discuss the major implications of this discovery in the design of self-assembling nanostructures.

  19. Mill profiler machines soft materials accurately

    NASA Technical Reports Server (NTRS)

    Rauschl, J. A.

    1966-01-01

    Mill profiler machines bevels, slots, and grooves in soft materials, such as styrofoam phenolic-filled cores, to any desired thickness. A single operator can accurately control cutting depths in contour or straight line work.

  20. Remote balance weighs accurately amid high radiation

    NASA Technical Reports Server (NTRS)

    Eggenberger, D. N.; Shuck, A. B.

    1969-01-01

    Commercial beam-type balance, modified and outfitted with electronic controls and digital readout, can be remotely controlled for use in high radiation environments. This allows accurate weighing of breeder-reactor fuel pieces when they are radioactively hot.

  1. Understanding the Code: keeping accurate records.

    PubMed

    Griffith, Richard

    2015-10-01

    In his continuing series looking at the legal and professional implications of the Nursing and Midwifery Council's revised Code of Conduct, Richard Griffith discusses the elements of accurate record keeping under Standard 10 of the Code. This article considers the importance of accurate record keeping for the safety of patients and protection of district nurses. The legal implications of records are explained along with how district nurses should write records to ensure these legal requirements are met. PMID:26418404

  2. Thermodynamic and kinetic study of phenol degradation by a non-catalytic wet air oxidation process.

    PubMed

    Lefèvre, Sébastien; Boutin, Olivier; Ferrasse, Jean-Henry; Malleret, Laure; Faucherand, Rémy; Viand, Alain

    2011-08-01

    This work is dedicated to an accurate evaluation of thermodynamic and kinetics aspects of phenol degradation using wet air oxidation process. Phenol is a well known polluting molecule and therefore it is important having data of its behaviour during this process. A view cell is used for the experimental study, with an internal volume of 150 mL, able to reach pressures up to 30 MPa and temperatures up to 350°C. Concerning the thermodynamic phase equilibria, experimental and modelling results are obtained for different binary systems (water/nitrogen, water/air) and ternary system (water/nitrogen/phenol). The best model is the Predictive Soave Redlich Kwong one. This information is necessary to predict the composition of the gas phase during the process. It is also important for an implementation in a process simulation. The second part is dedicated to kinetics evaluation of the degradation of phenol. Different compounds have been detected using GC coupled with a MS. A kinetic scheme is deduced, taking into account the evolution of phenol, hydroquinones, catechol, resorcinol and acetic acid. The kinetic parameters are calculated for this scheme. These data are important to evaluate the evolution of the concentration of the different polluting molecules during the process. A simplified kinetic scheme, which can be easily implemented in a process simulation, is also determined for the direct degradation of phenol into H(2)O and CO(2). The Arrhenius law data obtained for the phenol disappearance are the following: k=1.8×10(6)±3.9×10(5)M(-1)s(-1) (pre-exponential factor) and E(a)=77±8 kJ mol(-1) (activation energy). PMID:21700312

  3. Simplification of the unified gas kinetic scheme.

    PubMed

    Chen, Songze; Guo, Zhaoli; Xu, Kun

    2016-08-01

    The unified gas kinetic scheme (UGKS) is an asymptotic preserving (AP) scheme for kinetic equations. It is superior for transition flow simulation and has been validated in the past years. However, compared to the well-known discrete ordinate method (DOM), which is a classical numerical method solving the kinetic equations, the UGKS needs more computational resources. In this study, we propose a simplification of the unified gas kinetic scheme. It allows almost identical numerical cost as the DOM, but predicts numerical results as accurate as the UGKS. In the simplified scheme, the numerical flux for the velocity distribution function and the numerical flux for the macroscopic conservative quantities are evaluated separately. The equilibrium part of the UGKS flux is calculated by analytical solution instead of the numerical quadrature in velocity space. The simplification is equivalent to a flux hybridization of the gas kinetic scheme for the Navier-Stokes (NS) equations and the conventional discrete ordinate method. Several simplification strategies are tested, through which we can identify the key ingredient of the Navier-Stokes asymptotic preserving property. Numerical tests show that, as long as the collision effect is built into the macroscopic numerical flux, the numerical scheme is Navier-Stokes asymptotic preserving, regardless the accuracy of the microscopic numerical flux for the velocity distribution function. PMID:27627418

  4. A study of the kinetic, dielectric, and rheological properties of thermosetting resins used in pultruded polymer composites

    NASA Astrophysics Data System (ADS)

    Shanku, Reshma

    A comprehensive analysis has been conducted of the curing behavior of AOC VIBRINRTM E-606-6 (medium reactivity isophthalic), E-964 (high reactivity isophthalic), and P-341 (highest reactivity) polyester resins, and Shell EPON 9310 resin/EPON 9360 curing agent/EPON 537 accelerator resin system using calorimetric, dielectric, and rheological methods. The unsaturated polyester resins were cured with two different catalysts at three levels of concentration. Calorimetry and dielectrometry were employed to obtain polyester resin curing properties for the resin formulations studied. Rheological characterization of selected polyester resin formulations and the EPON 9310 resin system were also conducted. Kinetic parameters for all resin formulations were determined using a differential scanning calorimeter (DSC) by dynamic and isothermal methods. The dynamic and isothermal kinetic parameters obtained were used to generate heat flow values which were compared to the experimental DSC heat flow recorded; kinetic parameters that accurately modeled the pultrusion process were selected. The kinetic parameters were used in a numerical model to predict temperatures and degrees of cure under pultrusion processing conditions. The results obtained from the in-situ dielectric tests conducted on the pultruder in the Composites Material Laboratory at the University of Mississippi were compared to the degree of cure predictions from the numerical model and the experimental degree of cure from calorimetric analysis. Prior to the in-situ pultrusion studies, small quantities of resin formulations were tested for their dielectric cure properties when heated in an oven simulating pultrusion processing temperatures and rate of heating. This technique allowed small quantities of resins to be tested for degrees of cure. It was determined that such screening tests can be effectively conducted and can aid in pultrusion process planning. Complex viscosity profiles until gelation were generated for

  5. Part I. Evaluation of thermodynamic and kinetic parameters for electron transfer and following chemical reaction from a global analysis of current-potential-time data. Part II. Electro-catalytic detection in high-performance liquid chromatography of vitamin B[sub 12] and other molecules of biological and environmental interest

    SciTech Connect

    Kumar, V.T.

    1992-01-01

    Simultaneous evaluation of electron transfer rate constant, k[sup 0], following chemical reaction rate constant, k[sub f], electron transfer coefficient, [alpha] and standard potential, E[sup 0][prime] for an electrochemical reaction following the EC mechanism is described. A mathematical model for the current response to a potential step is developed, starting with the Butler-Volmer equation for electrode kinetics and concentration expressions for the redox couple. The resulting integral equations are solved numerically via the Step Function method. Current-potential and current-time curves are simulated and tested under limiting conditions. The four parameters of the system are evaluated by fitting simulated current-voltage-time (i-E-t) surface to the theoretical equation. The method is applied to study an important biological molecule, viz., methyl cobalamin, in DMSO. Included in the discussion part is the use of kinetic zone diagrams to depict chronoamperometric current response as a function of dimensionless rate constants for the EC reaction scheme. This compact display of the influence of the two rate constants on current in all time windows can be used to select the best data for analysis. Theoretical limits of measurable rate constants can be estimated from the zone diagram. The development of a dropping mercury electrode detector for High Performance Liquid Chromatography (HPLC) and its application to analysis of B[sub 12] and other vitamins is described. This EC detector is able to achieve high levels of sensitivity by exploiting the catalytic hydrogen evolution undergone by many nitrogenous organic molecules. Vitamin B[sub 12], thiamine, riboflavin and niacinamide were analyzed individually and in mixtures on reverse phase C18 column. Preliminary results from the analysis of commercial multivitamin preparations are also discussed.

  6. Oxidation kinetics of aluminum diboride

    SciTech Connect

    Whittaker, Michael L.; Sohn, H.Y.; Cutler, Raymond A.

    2013-11-15

    The oxidation characteristics of aluminum diboride (AlB{sub 2}) and a physical mixture of its constituent elements (Al+2B) were studied in dry air and pure oxygen using thermal gravimetric analysis to obtain non-mechanistic kinetic parameters. Heating in air at a constant linear heating rate of 10 °C/min showed a marked difference between Al+2B and AlB{sub 2} in the onset of oxidation and final conversion fraction, with AlB{sub 2} beginning to oxidize at higher temperatures but reaching nearly complete conversion by 1500 °C. Kinetic parameters were obtained in both air and oxygen using a model-free isothermal method at temperatures between 500 and 1000 °C. Activation energies were found to decrease, in general, with increasing conversion for AlB{sub 2} and Al+2B in both air and oxygen. AlB{sub 2} exhibited O{sub 2}-pressure-independent oxidation behavior at low conversions, while the activation energies of Al+2B were higher in O{sub 2} than in air. Differences in the composition and morphology between oxidized Al+2B and AlB{sub 2} suggested that Al{sub 2}O{sub 3}–B{sub 2}O{sub 3} interactions slowed Al+2B oxidation by converting Al{sub 2}O{sub 3} on aluminum particles into a Al{sub 4}B{sub 2}O{sub 9} shell, while the same Al{sub 4}B{sub 2}O{sub 9} developed a needle-like morphology in AlB{sub 2} that reduced oxygen diffusion distances and increased conversion. The model-free kinetic analysis was critical for interpreting the complex, multistep oxidation behavior for which a single mechanism could not be assigned. At low temperatures, moisture increased the oxidation rate of Al+2B and AlB{sub 2}, but both appear to be resistant to oxidation in cool, dry environments. - Graphical abstract: Isothermal kinetic data for AlB{sub 2} in air, showing a constantly decreasing activation energy with increasing conversion. Model-free analysis allowed for the calculation of global kinetic parameters despite many simultaneous mechanisms occurring concurrently. (a) Time

  7. The thermodynamics and kinetics of a nucleotide base pair.

    PubMed

    Wang, Yujie; Gong, Sha; Wang, Zhen; Zhang, Wenbing

    2016-03-21

    The thermodynamic and kinetic parameters of an RNA base pair were obtained through a long-time molecular dynamics simulation of the opening-closing switch process of the base pair near its melting temperature. The thermodynamic parameters were in good agreement with the nearest-neighbor model. The opening rates showed strong temperature dependence, however, the closing rates showed only weak temperature dependence. The transition path time was weakly temperature dependent and was insensitive to the energy barrier. The diffusion constant exhibited super-Arrhenius behavior. The free energy barrier of breaking a single base stack results from the enthalpy increase, ΔH, caused by the disruption of hydrogen bonding and base-stacking interactions. The free energy barrier of base pair closing comes from the unfavorable entropy loss, ΔS, caused by the restriction of torsional angles. These results suggest that a one-dimensional free energy surface is sufficient to accurately describe the dynamics of base pair opening and closing, and the dynamics are Brownian. PMID:27004898

  8. The thermodynamics and kinetics of a nucleotide base pair

    NASA Astrophysics Data System (ADS)

    Wang, Yujie; Gong, Sha; Wang, Zhen; Zhang, Wenbing

    2016-03-01

    The thermodynamic and kinetic parameters of an RNA base pair were obtained through a long-time molecular dynamics simulation of the opening-closing switch process of the base pair near its melting temperature. The thermodynamic parameters were in good agreement with the nearest-neighbor model. The opening rates showed strong temperature dependence, however, the closing rates showed only weak temperature dependence. The transition path time was weakly temperature dependent and was insensitive to the energy barrier. The diffusion constant exhibited super-Arrhenius behavior. The free energy barrier of breaking a single base stack results from the enthalpy increase, ΔH, caused by the disruption of hydrogen bonding and base-stacking interactions. The free energy barrier of base pair closing comes from the unfavorable entropy loss, ΔS, caused by the restriction of torsional angles. These results suggest that a one-dimensional free energy surface is sufficient to accurately describe the dynamics of base pair opening and closing, and the dynamics are Brownian.

  9. Kinetics of vortex formation in superconductors with d pairing

    NASA Astrophysics Data System (ADS)

    Filippov, A. E.; Radievsky, A. V.; Zeltser, A. S.

    1996-08-01

    We study the kinetics of vortex formation in superconductors with d pairing. We find order-parameter peculiarities and associated magnetic field maxima at intermediate stages of the evolution from the disordered to the ordered state.

  10. Determining the Desorption Kinetics of U(VI) from Contaminated Sediments Under Complex and Changing Solution Conditions

    NASA Astrophysics Data System (ADS)

    Hay, M. B.; Curtis, G. P.; Johnson, K. J.; Greskowiak, J.; Davis, J. A.

    2009-12-01

    Uranium(VI) transport in contaminated sediments is strongly controlled by the thermodynamics and kinetics of adsorption on mineral surfaces. Many studies on natural sediments and synthetic mineral phases have demonstrated the dependence of U(VI) sorption equilibrium on aqueous chemical conditions, with alkalinity, pH, ionic strength, and Ca concentration of particular importance in many natural systems. Desorption of U(VI) from contaminated sediments from DOE sites in Hanford, WA, Rifle, CO, and Naturita, CO also exhibits a significant kinetic limitation, with timescales of several weeks to months required to reach desorption equilibrium in some cases. This kinetic limitation is believed to be due to diffusion in intragranular pore space, which includes small fractures within grains and pores within clay aggregates and grain coatings. Development of appropriate reactive transport models that can be applied to predict the fate and transport of U(VI) in contaminated aquifers relies on accurately quantifying sorption equilibrium and kinetics at the grain scale, which vary from site to site based on sediment characteristics. This analysis typically involves laboratory batch- and column-scale adsorption/desorption experiments performed under a variety of chemical conditions to fully constrain surface complexation and kinetic models, requiring a constant set of chemical conditions over the duration of the experiment. In practice, however, this can be difficult in experiments aiming to quantify long-term kinetics (weeks to months time scale), due to slow ion exchange, mineral dissolution/precipitation, and redox processes. Long-term changes in solution conditions affect U(VI) sorption equilibrium, making it necessary to determine model parameters for U(VI) surface complexation, diffusion kinetics, and chemical weathering/ion exchange processes simultaneously from a given data set. We will present kinetic surface complexation model results obtained for size

  11. Parameter Estimation and Model Selection in Computational Biology

    PubMed Central

    Lillacci, Gabriele; Khammash, Mustafa

    2010-01-01

    A central challenge in computational modeling of biological systems is the determination of the model parameters. Typically, only a fraction of the parameters (such as kinetic rate constants) are experimentally measured, while the rest are often fitted. The fitting process is usually based on experimental time course measurements of observables, which are used to assign parameter values that minimize some measure of the error between these measurements and the corresponding model prediction. The measurements, which can come from immunoblotting assays, fluorescent markers, etc., tend to be very noisy and taken at a limited number of time points. In this work we present a new approach to the problem of parameter selection of biological models. We show how one can use a dynamic recursive estimator, known as extended Kalman filter, to arrive at estimates of the model parameters. The proposed method follows. First, we use a variation of the Kalman filter that is particularly well suited to biological applications to obtain a first guess for the unknown parameters. Secondly, we employ an a posteriori identifiability test to check the reliability of the estimates. Finally, we solve an optimization problem to refine the first guess in case it should not be accurate enough. The final estimates are guaranteed to be statistically consistent with the measurements. Furthermore, we show how the same tools can be used to discriminate among alternate models of the same biological process. We demonstrate these ideas by applying our methods to two examples, namely a model of the heat shock response in E. coli, and a model of a synthetic gene regulation system. The methods presented are quite general and may be applied to a wide class of biological systems where noisy measurements are used for parameter estimation or model selection. PMID:20221262

  12. Oxidation kinetics of aluminum diboride

    NASA Astrophysics Data System (ADS)

    Whittaker, Michael L.; Sohn, H. Y.; Cutler, Raymond A.

    2013-11-01

    The oxidation characteristics of aluminum diboride (AlB2) and a physical mixture of its constituent elements (Al+2B) were studied in dry air and pure oxygen using thermal gravimetric analysis to obtain non-mechanistic kinetic parameters. Heating in air at a constant linear heating rate of 10 °C/min showed a marked difference between Al+2B and AlB2 in the onset of oxidation and final conversion fraction, with AlB2 beginning to oxidize at higher temperatures but reaching nearly complete conversion by 1500 °C. Kinetic parameters were obtained in both air and oxygen using a model-free isothermal method at temperatures between 500 and 1000 °C. Activation energies were found to decrease, in general, with increasing conversion for AlB2 and Al+2B in both air and oxygen. AlB2 exhibited O2-pressure-independent oxidation behavior at low conversions, while the activation energies of Al+2B were higher in O2 than in air. Differences in the composition and morphology between oxidized Al+2B and AlB2 suggested that Al2O3-B2O3 interactions slowed Al+2B oxidation by converting Al2O3 on aluminum particles into a Al4B2O9 shell, while the same Al4B2O9 developed a needle-like morphology in AlB2 that reduced oxygen diffusion distances and increased conversion. The model-free kinetic analysis was critical for interpreting the complex, multistep oxidation behavior for which a single mechanism could not be assigned. At low temperatures, moisture increased the oxidation rate of Al+2B and AlB2, but both appear to be resistant to oxidation in cool, dry environments.

  13. Kinetics of Propargyl Radical Dissociation.

    PubMed

    Klippenstein, Stephen J; Miller, James A; Jasper, Ahren W

    2015-07-16

    Due to the prominent role of the propargyl radical for hydrocarbon growth within combustion environments, it is important to understand the kinetics of its formation and loss. The ab initio transition state theory-based master equation method is used to obtain theoretical kinetic predictions for the temperature and pressure dependence of the thermal decomposition of propargyl, which may be its primary loss channel under some conditions. The potential energy surface for the decomposition of propargyl is first mapped at a high level of theory with a combination of coupled cluster and multireference perturbation calculations. Variational transition state theory is then used to predict the microcanonical rate coefficients, which are subsequently implemented within the multiple-well multiple-channel master equation. A variety of energy transfer parameters are considered, and the sensitivity of the thermal rate predictions to these parameters is explored. The predictions for the thermal decomposition rate coefficient are found to be in good agreement with the limited experimental data. Modified Arrhenius representations of the rate constants are reported for utility in combustion modeling. PMID:25871530

  14. Modelling Heart Rate Kinetics

    PubMed Central

    Zakynthinaki, Maria S.

    2015-01-01

    The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual’s cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women). PMID:25876164

  15. Modelling heart rate kinetics.

    PubMed

    Zakynthinaki, Maria S

    2015-01-01

    The objective of the present study was to formulate a simple and at the same time effective mathematical model of heart rate kinetics in response to movement (exercise). Based on an existing model, a system of two coupled differential equations which give the rate of change of heart rate and the rate of change of exercise intensity is used. The modifications introduced to the existing model are justified and discussed in detail, while models of blood lactate accumulation in respect to time and exercise intensity are also presented. The main modification is that the proposed model has now only one parameter which reflects the overall cardiovascular condition of the individual. The time elapsed after the beginning of the exercise, the intensity of the exercise, as well as blood lactate are also taken into account. Application of the model provides information regarding the individual's cardiovascular condition and is able to detect possible changes in it, across the data recording periods. To demonstrate examples of successful numerical fit of the model, constant intensity experimental heart rate data sets of two individuals have been selected and numerical optimization was implemented. In addition, numerical simulations provided predictions for various exercise intensities and various cardiovascular condition levels. The proposed model can serve as a powerful tool for a complete means of heart rate analysis, not only in exercise physiology (for efficiently designing training sessions for healthy subjects) but also in the areas of cardiovascular health and rehabilitation (including application in population groups for which direct heart rate recordings at intense exercises are not possible or not allowed, such as elderly or pregnant women). PMID:25876164

  16. More-Accurate Model of Flows in Rocket Injectors

    NASA Technical Reports Server (NTRS)

    Hosangadi, Ashvin; Chenoweth, James; Brinckman, Kevin; Dash, Sanford

    2011-01-01

    An improved computational model for simulating flows in liquid-propellant injectors in rocket engines has been developed. Models like this one are needed for predicting fluxes of heat in, and performances of, the engines. An important part of predicting performance is predicting fluctuations of temperature, fluctuations of concentrations of chemical species, and effects of turbulence on diffusion of heat and chemical species. Customarily, diffusion effects are represented by parameters known in the art as the Prandtl and Schmidt numbers. Prior formulations include ad hoc assumptions of constant values of these parameters, but these assumptions and, hence, the formulations, are inaccurate for complex flows. In the improved model, these parameters are neither constant nor specified in advance: instead, they are variables obtained as part of the solution. Consequently, this model represents the effects of turbulence on diffusion of heat and chemical species more accurately than prior formulations do, and may enable more-accurate prediction of mixing and flows of heat in rocket-engine combustion chambers. The model has been implemented within CRUNCH CFD, a proprietary computational fluid dynamics (CFD) computer program, and has been tested within that program. The model could also be implemented within other CFD programs.

  17. Accurate camera calibration method specialized for virtual studios

    NASA Astrophysics Data System (ADS)

    Okubo, Hidehiko; Yamanouchi, Yuko; Mitsumine, Hideki; Fukaya, Takashi; Inoue, Seiki

    2008-02-01

    Virtual studio is a popular technology for TV programs, that makes possible to synchronize computer graphics (CG) to realshot image in camera motion. Normally, the geometrical matching accuracy between CG and realshot image is not expected so much on real-time system, we sometimes compromise on directions, not to come out the problem. So we developed the hybrid camera calibration method and CG generating system to achieve the accurate geometrical matching of CG and realshot on virtual studio. Our calibration method is intended for the camera system on platform and tripod with rotary encoder, that can measure pan/tilt angles. To solve the camera model and initial pose, we enhanced the bundle adjustment algorithm to fit the camera model, using pan/tilt data as known parameters, and optimizing all other parameters invariant against pan/tilt value. This initialization yields high accurate camera position and orientation consistent with any pan/tilt values. Also we created CG generator implemented the lens distortion function with GPU programming. By applying the lens distortion parameters obtained by camera calibration process, we could get fair compositing results.

  18. Robust ODF smoothing for accurate estimation of fiber orientation.

    PubMed

    Beladi, Somaieh; Pathirana, Pubudu N; Brotchie, Peter

    2010-01-01

    Q-ball imaging was presented as a model free, linear and multimodal diffusion sensitive approach to reconstruct diffusion orientation distribution function (ODF) using diffusion weighted MRI data. The ODFs are widely used to estimate the fiber orientations. However, the smoothness constraint was proposed to achieve a balance between the angular resolution and noise stability for ODF constructs. Different regularization methods were proposed for this purpose. However, these methods are not robust and quite sensitive to the global regularization parameter. Although, numerical methods such as L-curve test are used to define a globally appropriate regularization parameter, it cannot serve as a universal value suitable for all regions of interest. This may result in over smoothing and potentially end up in neglecting an existing fiber population. In this paper, we propose to include an interpolation step prior to the spherical harmonic decomposition. This interpolation based approach is based on Delaunay triangulation provides a reliable, robust and accurate smoothing approach. This method is easy to implement and does not require other numerical methods to define the required parameters. Also, the fiber orientations estimated using this approach are more accurate compared to other common approaches. PMID:21096202

  19. Mammalian Cell Culture Process for Monoclonal Antibody Production: Nonlinear Modelling and Parameter Estimation

    PubMed Central

    Selişteanu, Dan; Șendrescu, Dorin; Georgeanu, Vlad

    2015-01-01

    Monoclonal antibodies (mAbs) are at present one of the fastest growing products of pharmaceutical industry, with widespread applications in biochemistry, biology, and medicine. The operation of mAbs production processes is predominantly based on empirical knowledge, the improvements being achieved by using trial-and-error experiments and precedent practices. The nonlinearity of these processes and the absence of suitable instrumentation require an enhanced modelling effort and modern kinetic parameter estimation strategies. The present work is dedicated to nonlinear dynamic modelling and parameter estimation for a mammalian cell culture process used for mAb production. By using a dynamical model of such kind of processes, an optimization-based technique for estimation of kinetic parameters in the model of mammalian cell culture process is developed. The estimation is achieved as a result of minimizing an error function by a particle swarm optimization (PSO) algorithm. The proposed estimation approach is analyzed in this work by using a particular model of mammalian cell culture, as a case study, but is generic for this class of bioprocesses. The presented case study shows that the proposed parameter estimation technique provides a more accurate simulation of the experimentally observed process behaviour than reported in previous studies. PMID:25685797

  20. Mammalian cell culture process for monoclonal antibody production: nonlinear modelling and parameter estimation.

    PubMed

    Selişteanu, Dan; Șendrescu, Dorin; Georgeanu, Vlad; Roman, Monica

    2015-01-01

    Monoclonal antibodies (mAbs) are at present one of the fastest growing products of pharmaceutical industry, with widespread applications in biochemistry, biology, and medicine. The operation of mAbs production processes is predominantly based on empirical knowledge, the improvements being achieved by using trial-and-error experiments and precedent practices. The nonlinearity of these processes and the absence of suitable instrumentation require an enhanced modelling effort and modern kinetic parameter estimation strategies. The present work is dedicated to nonlinear dynamic modelling and parameter estimation for a mammalian cell culture process used for mAb production. By using a dynamical model of such kind of processes, an optimization-based technique for estimation of kinetic parameters in the model of mammalian cell culture process is developed. The estimation is achieved as a result of minimizing an error function by a particle swarm optimization (PSO) algorithm. The proposed estimation approach is analyzed in this work by using a particular model of mammalian cell culture, as a case study, but is generic for this class of bioprocesses. The presented case study shows that the proposed parameter estimation technique provides a more accurate simulation of the experimentally observed process behaviour than reported in previous studies. PMID:25685797

  1. Parameter Identification of Robot Manipulators: A Heuristic Particle Swarm Search Approach

    PubMed Central

    Yan, Danping; Lu, Yongzhong; Levy, David

    2015-01-01

    Parameter identification of robot manipulators is an indispensable pivotal process of achieving accurate dynamic robot models. Since these kinetic models are highly nonlinear, it is not easy to tackle the matter of identifying their parameters. To solve the difficulty effectively, we herewith present an intelligent approach, namely, a heuristic particle swarm optimization (PSO) algorithm, which we call the elitist learning strategy (ELS) and proportional integral derivative (PID) controller hybridized PSO approach (ELPIDSO). A specified PID controller is designed to improve particles’ local and global positions information together with ELS. Parameter identification of robot manipulators is conducted for performance evaluation of our proposed approach. Experimental results clearly indicate the following findings: Compared with standard PSO (SPSO) algorithm, ELPIDSO has improved a lot. It not only enhances the diversity of the swarm, but also features better search effectiveness and efficiency in solving practical optimization problems. Accordingly, ELPIDSO is superior to least squares (LS) method, genetic algorithm (GA), and SPSO algorithm in estimating the parameters of the kinetic models of robot manipulators. PMID:26039090

  2. Parameter identification of robot manipulators: a heuristic particle swarm search approach.

    PubMed

    Yan, Danping; Lu, Yongzhong; Levy, David

    2015-01-01

    Parameter identification of robot manipulators is an indispensable pivotal process of achieving accurate dynamic robot models. Since these kinetic models are highly nonlinear, it is not easy to tackle the matter of identifying their parameters. To solve the difficulty effectively, we herewith present an intelligent approach, namely, a heuristic particle swarm optimization (PSO) algorithm, which we call the elitist learning strategy (ELS) and proportional integral derivative (PID) controller hybridized PSO approach (ELPIDSO). A specified PID controller is designed to improve particles' local and global positions information together with ELS. Parameter identification of robot manipulators is conducted for performance evaluation of our proposed approach. Experimental results clearly indicate the following findings: Compared with standard PSO (SPSO) algorithm, ELPIDSO has improved a lot. It not only enhances the diversity of the swarm, but also features better search effectiveness and efficiency in solving practical optimization problems. Accordingly, ELPIDSO is superior to least squares (LS) method, genetic algorithm (GA), and SPSO algorithm in estimating the parameters of the kinetic models of robot manipulators. PMID:26039090

  3. Molecular Dynamics Simulations and Kinetic Measurements to Estimate and Predict Protein-Ligand Residence Times.

    PubMed

    Mollica, Luca; Theret, Isabelle; Antoine, Mathias; Perron-Sierra, Françoise; Charton, Yves; Fourquez, Jean-Marie; Wierzbicki, Michel; Boutin, Jean A; Ferry, Gilles; Decherchi, Sergio; Bottegoni, Giovanni; Ducrot, Pierre; Cavalli, Andrea

    2016-08-11

    Ligand-target residence time is emerging as a key drug discovery parameter because it can reliably predict drug efficacy in vivo. Experimental approaches to binding and unbinding kinetics are nowadays available, but we still lack reliable computational tools for predicting kinetics and residence time. Most attempts have been based on brute-force molecular dynamics (MD) simulations, which are CPU-demanding and not yet particularly accurate. We recently reported a new scaled-MD-based protocol, which showed potential for residence time prediction in drug discovery. Here, we further challenged our procedure's predictive ability by applying our methodology to a series of glucokinase activators that could be useful for treating type 2 diabetes mellitus. We combined scaled MD with experimental kinetics measurements and X-ray crystallography, promptly checking the protocol's reliability by directly comparing computational predictions and experimental measures. The good agreement highlights the potential of our scaled-MD-based approach as an innovative method for computationally estimating and predicting drug residence times. PMID:27391254

  4. Significance of Xenobiotic Metabolism for Bioaccumulation Kinetics of Organic Chemicals in Gammarus pulex

    PubMed Central

    2012-01-01

    Bioaccumulation and biotransformation are key toxicokinetic processes that modify toxicity of chemicals and sensitivity of organisms. Bioaccumulation kinetics vary greatly among organisms and chemicals; thus, we investigated the influence of biotransformation kinetics on bioaccumulation in a model aquatic invertebrate using fifteen 14C-labeled organic xenobiotics from diverse chemical classes and physicochemical properties (1,2,3-trichlorobenzene, imidacloprid, 4,6-dinitro-o-cresol, ethylacrylate, malathion, chlorpyrifos, aldicarb, carbofuran, carbaryl, 2,4-dichlorophenol, 2,4,5-trichlorophenol, pentachlorophenol, 4-nitrobenzyl-chloride, 2,4-dichloroaniline, and sea-nine (4,5-dichloro-2-octyl-3-isothiazolone)). We detected and identified metabolites using HPLC with UV and radio-detection as well as high resolution mass spectrometry (LTQ-Orbitrap). Kinetics of uptake, biotransformation, and elimination of parent compounds and metabolites were modeled with a first-order one-compartment model. Bioaccumulation factors were calculated for parent compounds and metabolite enrichment factors for metabolites. Out of 19 detected metabolites, we identified seven by standards or accurate mass measurements and two via pathway analysis and analogies to other compounds. 1,2,3-Trichlorobenzene, imidacloprid, and 4,6-dinitro-o-cresol were not biotransformed. Dietary uptake contributed little to overall uptake. Differentiation between parent and metabolites increased accuracy of bioaccumulation parameters compared to total 14C measurements. Biotransformation dominated toxicokinetics and strongly affected internal concentrations of parent compounds and metabolites. Many metabolites reached higher internal concentrations than their parents, characterized by large metabolite enrichment factors. PMID:22321051

  5. Kinetic and mechanistic studies of free-radical reactions in combustion

    SciTech Connect

    Tully, F.P.

    1993-12-01

    Combustion is driven by energy-releasing chemical reactions. Free radicals that participate in chain reactions carry the combustion process from reactants to products. Research in chemical kinetics enables us to understand the microscopic mechanisms involved in individual chemical reactions as well as to determine the rates at which they proceed. Both types of information are required for an understanding of how flames burn, why engines knock, how to minimize the production of pollutants, and many other important questions in combustion. In this program the authors emphasize accurate measurements over wide temperature ranges of the rates at which ubiquitous free radicals react with stable molecules. The authors investigate a variety of OH, CN, and CH + stable molecule reactions important to fuel conversion, emphasizing application of the extraordinarily precise technique of laser photolysis/continuous-wave laser-induced fluorescence (LP/cwLIF). This precision enables kinetic measurements to serve as mechanistic probes. Since considerable effort is required to study each individual reaction, prudent selection is critical. Two factors encourage selection of a specific reaction: (1) the rates and mechanisms of the subject reaction are required input to a combustion model; and (2) the reaction is a chemical prototype which, upon characterization, will provide fundamental insight into chemical reactivity, facilitate estimation of kinetic parameters for similar reactions, and constrain and test the computational limits of reaction-rate theory. Most studies performed in this project satisfy both conditions.

  6. LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 3: Illustrative test problems

    NASA Technical Reports Server (NTRS)

    Bittker, David A.; Radhakrishnan, Krishnan

    1994-01-01

    LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 3 of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part 3 explains the kinetics and kinetics-plus-sensitivity analysis problems supplied with LSENS and presents sample results. These problems illustrate the various capabilities of, and reaction models that can be solved by, the code and may provide a convenient starting point for the user to construct the problem data file required to execute LSENS. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

  7. Fast and accurate estimation for astrophysical problems in large databases

    NASA Astrophysics Data System (ADS)

    Richards, Joseph W.

    2010-10-01

    A recent flood of astronomical data has created much demand for sophisticated statistical and machine learning tools that can rapidly draw accurate inferences from large databases of high-dimensional data. In this Ph.D. thesis, methods for statistical inference in such databases will be proposed, studied, and applied to real data. I use methods for low-dimensional parametrization of complex, high-dimensional data that are based on the notion of preserving the connectivity of data points in the context of a Markov random walk over the data set. I show how this simple parameterization of data can be exploited to: define appropriate prototypes for use in complex mixture models, determine data-driven eigenfunctions for accurate nonparametric regression, and find a set of suitable features to use in a statistical classifier. In this thesis, methods for each of these tasks are built up from simple principles, compared to existing methods in the literature, and applied to data from astronomical all-sky surveys. I examine several important problems in astrophysics, such as estimation of star formation history parameters for galaxies, prediction of redshifts of galaxies using photometric data, and classification of different types of supernovae based on their photometric light curves. Fast methods for high-dimensional data analysis are crucial in each of these problems because they all involve the analysis of complicated high-dimensional data in large, all-sky surveys. Specifically, I estimate the star formation history parameters for the nearly 800,000 galaxies in the Sloan Digital Sky Survey (SDSS) Data Release 7 spectroscopic catalog, determine redshifts for over 300,000 galaxies in the SDSS photometric catalog, and estimate the types of 20,000 supernovae as part of the Supernova Photometric Classification Challenge. Accurate predictions and classifications are imperative in each of these examples because these estimates are utilized in broader inference problems

  8. Leveraging Two Kinect Sensors for Accurate Full-Body Motion Capture

    PubMed Central

    Gao, Zhiquan; Yu, Yao; Zhou, Yu; Du, Sidan

    2015-01-01

    Accurate motion capture plays an important role in sports analysis, the medical field and virtual reality. Current methods for motion capture often suffer from occlusions, which limits the accuracy of their pose estimation. In this paper, we propose a complete system to measure the pose parameters of the human body accurately. Different from previous monocular depth camera systems, we leverage two Kinect sensors to acquire more information about human movements, which ensures that we can still get an accurate estimation even when significant occlusion occurs. Because human motion is temporally constant, we adopt a learning analysis to mine the temporal information across the posture variations. Using this information, we estimate human pose parameters accurately, regardless of rapid movement. Our experimental results show that our system can perform an accurate pose estimation of the human body with the constraint of information from the temporal domain. PMID:26402681

  9. Leveraging Two Kinect Sensors for Accurate Full-Body Motion Capture.

    PubMed

    Gao, Zhiquan; Yu, Yao; Zhou, Yu; Du, Sidan

    2015-01-01

    Accurate motion capture plays an important role in sports analysis, the medical field and virtual reality. Current methods for motion capture often suffer from occlusions, which limits the accuracy of their pose estimation. In this paper, we propose a complete system to measure the pose parameters of the human body accurately. Different from previous monocular depth camera systems, we leverage two Kinect sensors to acquire more information about human movements, which ensures that we can still get an accurate estimation even when significant occlusion occurs. Because human motion is temporally constant, we adopt a learning analysis to mine the temporal information across the posture variations. Using this information, we estimate human pose parameters accurately, regardless of rapid movement. Our experimental results show that our system can perform an accurate pose estimation of the human body with the constraint of information from the temporal domain. PMID:26402681

  10. Large-scale reactive molecular dynamics simulation and kinetic modeling of high-temperature pyrolysis of the Gloeocapsomorphaprisca microfossils.

    PubMed

    Zou, Chenyu; Raman, Sumathy; van Duin, Adri C T

    2014-06-12

    The ability to predict accurately the thermal conversion of complex carbonaceous materials is of value in both petroleum exploration and refining operations. Modeling the thermal cracking of kerogen under basinal heating conditions improves the predrill prediction of oil and gas yields and quality, thereby ultimately lowering the exploration risk. Modeling the chemical structure and reactivity of asphaltene from petroleum vacuum residues enables prediction of coke formation and properties in refinery processes, thereby lowering operating cost. The chemical structure-chemical yield modeling (CS-CYM) developed by Freund et al. is more rigorous, time-consuming, and requires a great deal of chemical insight into reaction network and reaction kinetics. The present work explores the applicability of a more fundamental atomistic simulation using the quantum mechanically based reactive force field to predict the product yield and overall kinetics of decomposition of two biopolymers, namely, the Kukersite and Gutternberg. Reactive molecular dynamics (RMD) simulations were performed on systems consisting of 10(4) to 10(5) atoms at different densities and temperatures to derive the overall kinetic parameters and a lumped kinetic model for pyrolysis. The kinetic parameters derived from the simulated pyrolysis of an individual component and the mixture of all four components in Guttenberg reveal the role of cross-talk between the fragments and enhanced reactivity of component A by radicals from other components. The Arrhenius extrapolation of the model yields reasonable prediction for the overall barrier for cracking. Because simulations were run at very high temperature (T > 1500 K) to study cracking within the simulation time of up to 1 ns, it, however, led to the entropically favored ethylene formation as a dominant decomposition route. Future work will focus on evaluating the applicability of accelerated reactive MD approaches to study cracking. PMID:24821589

  11. A highly accurate interatomic potential for argon

    NASA Astrophysics Data System (ADS)

    Aziz, Ronald A.

    1993-09-01

    A modified potential based on the individually damped model of Douketis, Scoles, Marchetti, Zen, and Thakkar [J. Chem. Phys. 76, 3057 (1982)] is presented which fits, within experimental error, the accurate ultraviolet (UV) vibration-rotation spectrum of argon determined by UV laser absorption spectroscopy by Herman, LaRocque, and Stoicheff [J. Chem. Phys. 89, 4535 (1988)]. Other literature potentials fail to do so. The potential also is shown to predict a large number of other properties and is probably the most accurate characterization of the argon interaction constructed to date.

  12. Oxidation and hydrolysis kinetic studies on UN

    NASA Astrophysics Data System (ADS)

    Rao, G. A. Rama; Mukerjee, S. K.; Vaidya, V. N.; Venugopal, V.; Sood, D. D.

    1991-11-01

    The reaction of oxygen and water vapour with UN microspheres containing 0.78 and 10.9 mol% UO 2 as impurity was studied under non-isothermal heating conditions in a thermobalance under different partial pressures of oxygen, a fixed pressure of water vapour in argon, and in air. Uranium mononitride was ultimately converted to U 3O 8, with the formation of UO 2 and U 2N 3 as intermediates. The end product of pyrohydrolysis was UO 2. The kinetic parameters were evaluated and the mechanism of the reaction was suggested. Different kinetic models were used to explain the oxidation behaviour of UN.

  13. Accurate analysis of EBSD data for phase identification

    NASA Astrophysics Data System (ADS)

    Palizdar, Y.; Cochrane, R. C.; Brydson, R.; Leary, R.; Scott, A. J.

    2010-07-01

    This paper aims to investigate the reliability of software default settings in the analysis of EBSD results. To study the effect of software settings on the EBSD results, the presence of different phases in high Al steel has been investigated by EBSD. The results show the importance of appropriate automated analysis parameters for valid and reliable phase discrimination. Specifically, the importance of the minimum number of indexed bands and the maximum solution error have been investigated with values of 7-9 and 1.0-1.5° respectively, found to be needed for accurate analysis.

  14. Cluster kinetics model for mixtures of glassformers.

    PubMed

    Brenskelle, Lisa A; McCoy, Benjamin J

    2007-10-14

    For glassformers we propose a binary mixture relation for parameters in a cluster kinetics model previously shown to represent pure compound data for viscosity and dielectric relaxation as functions of either temperature or pressure. The model parameters are based on activation energies and activation volumes for cluster association-dissociation processes. With the mixture parameters, we calculated dielectric relaxation times and compared the results to experimental values for binary mixtures. Mixtures of sorbitol and glycerol (seven compositions), sorbitol and xylitol (three compositions), and polychloroepihydrin and polyvinylmethylether (three compositions) were studied. PMID:17935407

  15. Cluster kinetics model for mixtures of glassformers

    NASA Astrophysics Data System (ADS)

    Brenskelle, Lisa A.; McCoy, Benjamin J.

    2007-10-01

    For glassformers we propose a binary mixture relation for parameters in a cluster kinetics model previously shown to represent pure compound data for viscosity and dielectric relaxation as functions of either temperature or pressure. The model parameters are based on activation energies and activation volumes for cluster association-dissociation processes. With the mixture parameters, we calculated dielectric relaxation times and compared the results to experimental values for binary mixtures. Mixtures of sorbitol and glycerol (seven compositions), sorbitol and xylitol (three compositions), and polychloroepihydrin and polyvinylmethylether (three compositions) were studied.

  16. Chemical Kinetics Database

    National Institute of Standards and Technology Data Gateway

    SRD 17 NIST Chemical Kinetics Database (Web, free access)   The NIST Chemical Kinetics Database includes essentially all reported kinetics results for thermal gas-phase chemical reactions. The database is designed to be searched for kinetics data based on the specific reactants involved, for reactions resulting in specified products, for all the reactions of a particular species, or for various combinations of these. In addition, the bibliography can be searched by author name or combination of names. The database contains in excess of 38,000 separate reaction records for over 11,700 distinct reactant pairs. These data have been abstracted from over 12,000 papers with literature coverage through early 2000.

  17. A "Stationery" Kinetics Experiment.

    ERIC Educational Resources Information Center

    Hall, L.; Goberdhansingh, A.

    1988-01-01

    Describes a simple redox reaction that occurs between potassium permanganate and oxalic acid that can be used to prepare an interesting disappearing ink for demonstrating kinetics for introductory chemistry. Discusses laboratory procedures and factors that influence disappearance times. (CW)

  18. Enzyme Kinetics in Microgravity

    NASA Astrophysics Data System (ADS)

    Liu, C. C.; Licata, V. J.

    2010-04-01

    The kinetics of some enzymes have been found to be enhanced by the microgravity environment. This is a relatively small effect, but is sufficient to have physiological effects and to impact pharmaceutical therapy in microgravity.

  19. Using temperature-programmed reaction for kinetic analysis of reactions in dilute aqueous solutions at high pressure

    SciTech Connect

    Brown, L.F.; Robinson, B.A.

    1986-01-01

    The technique of temperature-programmed reaction (TPR) is shown to be a practical experimental method for determining reaction-rate expressions and kinetics parameters for reactions in dilute aqueous solutions under high ambient pressure. By sampling and measuring the extent of reaction during a rise in temperature, information normally obtained from a series of isothermal batch kinetics experiments can be found in a single TPR test. The use of nonlinear least-squares regression eliminates the need to achieve a constant rate of temperature rise, simplifies the experimental requirements for TPR results, and gives more accurate answers than does a linear analysis of TPR results. Numerical simulations of TPR tests in the presence of random concentration-measurement error is used to assess the accuracy of the technique and to identify the best values of crucial operating parameters. The results of two TPR experiments measuring the alkaline hydrolysis of ethyl acetate demonstrate the applicability of the technique to reactions in dilute aqueous solutions at high pressure. These preliminary experimental results, along with numerical simulations, allow us to chart a course for future TPR kinetics experiments on a large number of similar reactions. 16 refs., 6 figs., 8 tabs.

  20. FIRST ORDER KINETIC GAS GENERATION MODEL PARAMETERS FOR WET LANDFILLS

    EPA Science Inventory

    Landfill gas is produced as a result of a sequence of physical, chemical, and biological processes occurring within an anaerobic landfill. Landfill operators, energy recovery project owners, regulators, and energy users need to be able to project the volume of gas produced and re...

  1. Accurate pointing of tungsten welding electrodes

    NASA Technical Reports Server (NTRS)

    Ziegelmeier, P.

    1971-01-01

    Thoriated-tungsten is pointed accurately and quickly by using sodium nitrite. Point produced is smooth and no effort is necessary to hold the tungsten rod concentric. The chemically produced point can be used several times longer than ground points. This method reduces time and cost of preparing tungsten electrodes.

  2. Parameter estimation in food science.

    PubMed

    Dolan, Kirk D; Mishra, Dharmendra K

    2013-01-01

    Modeling includes two distinct parts, the forward problem and the inverse problem. The forward problem-computing y(t) given known parameters-has received much attention, especially with the explosion of commercial simulation software. What is rarely made clear is that the forward results can be no better than the accuracy of the parameters. Therefore, the inverse problem-estimation of parameters given measured y(t)-is at least as important as the forward problem. However, in the food science literature there has been little attention paid to the accuracy of parameters. The purpose of this article is to summarize the state of the art of parameter estimation in food science, to review some of the common food science models used for parameter estimation (for microbial inactivation and growth, thermal properties, and kinetics), and to suggest a generic method to standardize parameter estimation, thereby making research results more useful. Scaled sensitivity coefficients are introduced and shown to be important in parameter identifiability. Sequential estimation and optimal experimental design are also reviewed as powerful parameter estimation methods that are beginning to be used in the food science literature. PMID:23297775

  3. A new generalized correlation for accurate vapor pressure prediction

    NASA Astrophysics Data System (ADS)

    An, Hui; Yang, Wenming

    2012-08-01

    An accurate knowledge of the vapor pressure of organic liquids is very important for the oil and gas processing operations. In combustion modeling, the accuracy of numerical predictions is also highly dependent on the fuel properties such as vapor pressure. In this Letter, a new generalized correlation is proposed based on the Lee-Kesler's method where a fuel dependent parameter 'A' is introduced. The proposed method only requires the input parameters of critical temperature, normal boiling temperature and the acentric factor of the fluid. With this method, vapor pressures have been calculated and compared with the data reported in data compilation for 42 organic liquids over 1366 data points, and the overall average absolute percentage deviation is only 1.95%.

  4. 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

  5. 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

  6. Scallops skeletons as tools for accurate proxy calibration

    NASA Astrophysics Data System (ADS)

    Lorrain, A.; Paulet, Y.-M.; Chauvaud, L.; Dunbar, R.; Mucciarone, D.; Pécheyran, C.; Amouroux, D.; Fontugne, M.

    2003-04-01

    Bivalves skeletons are able to produce great geochemical proxies. But general calibration of those proxies are based on approximate time basis because of misunderstanding of growth rhythm. In this context, the Great scallop, Pecten maximus, appears to be a powerful tool as a daily growth deposit has been clearly identified for this species (Chauvaud et al, 1998; Lorrain et al, 2000), allowing accurate environmental calibration. Indeed, using this species, a date can be affiliated to each growth increment, and as a consequence environmental parameters can be closely compared (at a daily scale) to observed chemical and structural shell variations. This daily record provides an unequivocal basis to calibrate proxies. Isotopic (Delta-13C and Delta-15N) and trace element analysis (LA-ICP-MS) have been performed on several individuals and different years depending on the analysed parameter. Seawater parameters measured one meter above the sea-bottom were compared to chemical variations in the calcitic shell. Their confrontation showed that even with a daily basis for data interpretation, calibration is still a challenge. Inter-individual variations are found and correlations are not always reproducible from one year to the others. The first explanation could be an inaccurate appreciation of the proximate environment of the animal, notably the water-sediment interface could best represent Pecten maximus environment. Secondly, physiological parameters could be inferred for those discrepancies. In particular, calcification takes places in the extrapallial fluid, which composition might be very different from external environment. Accurate calibration of chemical proxies should consider biological aspects to gain better insights into the processes controlling the incorporation of those chemical elements. The characterisation of isotopic and trace element composition of the extrapallial fluid and hemolymph could greatly help our understanding of chemical shell variations.

  7. TH-E-BRF-06: Kinetic Modeling of Tumor Response to Fractionated Radiotherapy

    SciTech Connect

    Zhong, H; Gordon, J; Chetty, I

    2014-06-15

    Purpose: Accurate calibration of radiobiological parameters is crucial to predicting radiation treatment response. Modeling differences may have a significant impact on calibrated parameters. In this study, we have integrated two existing models with kinetic differential equations to formulate a new tumor regression model for calibrating radiobiological parameters for individual patients. Methods: A system of differential equations that characterizes the birth-and-death process of tumor cells in radiation treatment was analytically solved. The solution of this system was used to construct an iterative model (Z-model). The model consists of three parameters: tumor doubling time Td, half-life of dying cells Tr and cell survival fraction SFD under dose D. The Jacobian determinant of this model was proposed as a constraint to optimize the three parameters for six head and neck cancer patients. The derived parameters were compared with those generated from the two existing models, Chvetsov model (C-model) and Lim model (L-model). The C-model and L-model were optimized with the parameter Td fixed. Results: With the Jacobian-constrained Z-model, the mean of the optimized cell survival fractions is 0.43±0.08, and the half-life of dying cells averaged over the six patients is 17.5±3.2 days. The parameters Tr and SFD optimized with the Z-model differ by 1.2% and 20.3% from those optimized with the Td-fixed C-model, and by 32.1% and 112.3% from those optimized with the Td-fixed L-model, respectively. Conclusion: The Z-model was analytically constructed from the cellpopulation differential equations to describe changes in the number of different tumor cells during the course of fractionated radiation treatment. The Jacobian constraints were proposed to optimize the three radiobiological parameters. The developed modeling and optimization methods may help develop high-quality treatment regimens for individual patients.

  8. Accurate and occlusion-robust multi-view stereo

    NASA Astrophysics Data System (ADS)

    Zhu, Zhaokun; Stamatopoulos, Christos; Fraser, Clive S.

    2015-11-01

    This paper proposes an accurate multi-view stereo method for image-based 3D reconstruction that features robustness in the presence of occlusions. The new method offers improvements in dealing with two fundamental image matching problems. The first concerns the selection of the support window model, while the second centers upon accurate visibility estimation for each pixel. The support window model is based on an approximate 3D support plane described by a depth and two per-pixel depth offsets. For the visibility estimation, the multi-view constraint is initially relaxed by generating separate support plane maps for each support image using a modified PatchMatch algorithm. Then the most likely visible support image, which represents the minimum visibility of each pixel, is extracted via a discrete Markov Random Field model and it is further augmented by parameter clustering. Once the visibility is estimated, multi-view optimization taking into account all redundant observations is conducted to achieve optimal accuracy in the 3D surface generation for both depth and surface normal estimates. Finally, multi-view consistency is utilized to eliminate any remaining observational outliers. The proposed method is experimentally evaluated using well-known Middlebury datasets, and results obtained demonstrate that it is amongst the most accurate of the methods thus far reported via the Middlebury MVS website. Moreover, the new method exhibits a high completeness rate.

  9. Method and apparatus for accurately manipulating an object during microelectrophoresis

    DOEpatents

    Parvin, Bahram A.; Maestre, Marcos F.; Fish, Richard H.; Johnston, William E.

    1997-01-01

    An apparatus using electrophoresis provides accurate manipulation of an object on a microscope stage for further manipulations add reactions. The present invention also provides an inexpensive and easily accessible means to move an object without damage to the object. A plurality of electrodes are coupled to the stage in an array whereby the electrode array allows for distinct manipulations of the electric field for accurate manipulations of the object. There is an electrode array control coupled to the plurality of electrodes for manipulating the electric field. In an alternative embodiment, a chamber is provided on the stage to hold the object. The plurality of electrodes are positioned in the chamber, and the chamber is filled with fluid. The system can be automated using visual servoing, which manipulates the control parameters, i.e., x, y stage, applying the field, etc., after extracting the significant features directly from image data. Visual servoing includes an imaging device and computer system to determine the location of the object. A second stage having a plurality of tubes positioned on top of the second stage, can be accurately positioned by visual servoing so that one end of one of the plurality of tubes surrounds at least part of the object on the first stage.

  10. Method and apparatus for accurately manipulating an object during microelectrophoresis

    DOEpatents

    Parvin, B.A.; Maestre, M.F.; Fish, R.H.; Johnston, W.E.

    1997-09-23

    An apparatus using electrophoresis provides accurate manipulation of an object on a microscope stage for further manipulations and reactions. The present invention also provides an inexpensive and easily accessible means to move an object without damage to the object. A plurality of electrodes are coupled to the stage in an array whereby the electrode array allows for distinct manipulations of the electric field for accurate manipulations of the object. There is an electrode array control coupled to the plurality of electrodes for manipulating the electric field. In an alternative embodiment, a chamber is provided on the stage to hold the object. The plurality of electrodes are positioned in the chamber, and the chamber is filled with fluid. The system can be automated using visual servoing, which manipulates the control parameters, i.e., x, y stage, applying the field, etc., after extracting the significant features directly from image data. Visual servoing includes an imaging device and computer system to determine the location of the object. A second stage having a plurality of tubes positioned on top of the second stage, can be accurately positioned by visual servoing so that one end of one of the plurality of tubes surrounds at least part of the object on the first stage. 11 figs.

  11. Kinetic Approaches to Measuring Peroxiredoxin Reactivity

    PubMed Central

    Winterbourn, Christine C.; Peskin, Alexander V.

    2016-01-01

    Peroxiredoxins are ubiquitous thiol proteins that catalyse the breakdown of peroxides and regulate redox activity in the cell. Kinetic analysis of their reactions is required in order to identify substrate preferences, to understand how molecular structure affects activity and to establish their physiological functions. Various approaches can be taken, including the measurement of rates of individual steps in the reaction pathway by stopped flow or competitive kinetics, classical enzymatic analysis and measurement of peroxidase activity. Each methodology has its strengths and they can often give complementary information. However, it is important to understand the experimental conditions of the assay so as to interpret correctly what parameter is being measured. This brief review discusses different kinetic approaches and the information that can be obtained from them. PMID:26813658

  12. An algorithm for the kinetics of tire pyrolysis under different heating rates.

    PubMed

    Quek, Augustine; Balasubramanian, Rajashekhar

    2009-07-15

    Tires exhibit different kinetic behaviors when pyrolyzed under different heating rates. A new algorithm has been developed to investigate pyrolysis behavior of scrap tires. The algorithm includes heat and mass transfer equations to account for the different extents of thermal lag as the tire is heated at different heating rates. The algorithm uses an iterative approach to fit model equations to experimental data to obtain quantitative values of kinetic parameters. These parameters describe the pyrolysis process well, with good agreement (r(2)>0.96) between the model and experimental data when the model is applied to three different brands of automobile tires heated under five different heating rates in a pure nitrogen atmosphere. The model agrees with other researchers' results that frequencies factors increased and time constants decreased with increasing heating rates. The model also shows the change in the behavior of individual tire components when the heating rates are increased above 30 K min(-1). This result indicates that heating rates, rather than temperature, can significantly affect pyrolysis reactions. This algorithm is simple in structure and yet accurate in describing tire pyrolysis under a wide range of heating rates (10-50 K min(-1)). It improves our understanding of the tire pyrolysis process by showing the relationship between the heating rate and the many components in a tire that depolymerize as parallel reactions. PMID:19111984

  13. Supergranular Parameters

    NASA Astrophysics Data System (ADS)

    Udayashankar, Paniveni

    2016-07-01

    I study the complexity of supergranular cells using intensity patterns from Kodaikanal solar observatory. The chaotic and turbulent aspect of the solar supergranulation can be studied by examining the interrelationships amongst the parameters characterizing supergranular cells namely size, horizontal flow field, lifetime and physical dimensions of the cells and the fractal dimension deduced from the size data. The findings are supportive of Kolmogorov's theory of turbulence. The Data consists of visually identified supergranular cells, from which a fractal dimension 'D' for supergranulation is obtained according to the relation P α AD/2 where 'A' is the area and 'P' is the perimeter of the supergranular cells. I find a fractal dimension close to about 1.3 which is consistent with that for isobars and suggests a possible turbulent origin. The cell circularity shows a dependence on the perimeter with a peak around (1.1-1.2) x 105 m. The findings are supportive of Kolmogorov's theory of turbulence.

  14. Feedback about More Accurate versus Less Accurate Trials: Differential Effects on Self-Confidence and Activation

    ERIC Educational Resources Information Center

    Badami, Rokhsareh; VaezMousavi, Mohammad; Wulf, Gabriele; Namazizadeh, Mahdi

    2012-01-01

    One purpose of the present study was to examine whether self-confidence or anxiety would be differentially affected by feedback from more accurate rather than less accurate trials. The second purpose was to determine whether arousal variations (activation) would predict performance. On Day 1, participants performed a golf putting task under one of…

  15. The initial value problem in Lagrangian drift kinetic theory

    NASA Astrophysics Data System (ADS)

    Burby, J. W.

    2016-06-01

    > Existing high-order variational drift kinetic theories contain unphysical rapidly varying modes that are not seen at low orders. These unphysical modes, which may be rapidly oscillating, damped or growing, are ushered in by a failure of conventional high-order drift kinetic theory to preserve the structure of its parent model's initial value problem. In short, the (infinite dimensional) system phase space is unphysically enlarged in conventional high-order variational drift kinetic theory. I present an alternative, `renormalized' variational approach to drift kinetic theory that manifestly respects the parent model's initial value problem. The basic philosophy underlying this alternate approach is that high-order drift kinetic theory ought to be derived by truncating the all-orders system phase-space Lagrangian instead of the usual `field particle' Lagrangian. For the sake of clarity, this story is told first through the lens of a finite-dimensional toy model of high-order variational drift kinetics; the analogous full-on drift kinetic story is discussed subsequently. The renormalized drift kinetic system, while variational and just as formally accurate as conventional formulations, does not support the troublesome rapidly varying modes.

  16. The initial value problem in Lagrangian drift kinetic theory

    NASA Astrophysics Data System (ADS)

    Burby, J. W.

    2016-06-01

    Existing high-order variational drift kinetic theories contain unphysical rapidly varying modes that are not seen at low orders. These unphysical modes, which may be rapidly oscillating, damped or growing, are ushered in by a failure of conventional high-order drift kinetic theory to preserve the structure of its parent model's initial value problem. In short, the (infinite dimensional) system phase space is unphysically enlarged in conventional high-order variational drift kinetic theory. I present an alternative, `renormalized' variational approach to drift kinetic theory that manifestly respects the parent model's initial value problem. The basic philosophy underlying this alternate approach is that high-order drift kinetic theory ought to be derived by truncating the all-orders system phase-space Lagrangian instead of the usual `field particle' Lagrangian. For the sake of clarity, this story is told first through the lens of a finite-dimensional toy model of high-order variational drift kinetics; the analogous full-on drift kinetic story is discussed subsequently. The renormalized drift kinetic system, while variational and just as formally accurate as conventional formulations, does not support the troublesome rapidly varying modes.

  17. Kinetics of photoacclimation in corals.

    PubMed

    Anthony, Kenneth R N; Hoegh-Guldberg, Ove

    2003-01-01

    Traditional models describing the relationship between photosynthesis (P) and irradiance (I) do not account for photoacclimation to short-term variation in irradiance. Here we develop and test a model that predicts the rate of photosynthesis under fluctuating irradiances at the scale of days to weeks. Using oxygen respirometry, we measured the rates of change in the P-I model parameters P(max) (maximum rate of gross photosynthesis) and I(k) (sub-saturation irradiance) of the photo-symbiotic coral Turbinaria mesenterina (Lamarck) following large and small increases and decreases in growth irradiance. We analyse the behaviour of the dynamic P-I model in turbid-water conditions using a dataset of 3-month continuous irradiance as the input variable. In response to upward or downward changes in experimental growth irradiance, I(k) values decreased or increased exponentially, reaching new and stable levels within 5-10 days. I(k) responded 4 times stronger than P(max) to changes in growth irradiance. The kinetics of I(k) did not show hysteresis, and changed in similar ways when irradiance was increased or decreased in small or large amounts. This suggests that mechanisms associated with photo-protection during increases in irradiance, and the maximisation of photosynthetic efficiency during decreases in irradiance, are equally potent. On the scale of months, the dynamic P-I model did not predict higher rates of photosynthesis than the static P-I model, but buffered the variation in photosynthesis during periods of reduced irradiance. Fourier analysis indicated that the kinetics of I(k) closely matches the main periodicities in daily irradiance (1-2 weeks). The recorded kinetics of photoacclimation in the Turbinaria-zooxanthella symbiosis is comparable to that of free-living phytoplankton and faster than that of higher plants. PMID:12647175

  18. Isomerism of Cyanomethanimine: Accurate Structural, Energetic, and Spectroscopic Characterization.

    PubMed

    Puzzarini, Cristina

    2015-11-25

    The structures, relative stabilities, and rotational and vibrational parameters of the Z-C-, E-C-, and N-cyanomethanimine isomers have been evaluated using state-of-the-art quantum-chemical approaches. Equilibrium geometries have been calculated by means of a composite scheme based on coupled-cluster calculations that accounts for the extrapolation to the complete basis set limit and core-correlation effects. The latter approach is proved to provide molecular structures with an accuracy of 0.001-0.002 Å and 0.05-0.1° for bond lengths and angles, respectively. Systematically extrapolated ab initio energies, accounting for electron correlation through coupled-cluster theory, including up to single, double, triple, and quadruple excitations, and corrected for core-electron correlation and anharmonic zero-point vibrational energy, have been used to accurately determine relative energi