Frequency-dependent selection predicts patterns of radiations and biodiversity.

PubMed

Melián, Carlos J; Alonso, David; Vázquez, Diego P; Regetz, James; Allesina, Stefano

2010-08-26

Most empirical studies support a decline in speciation rates through time, although evidence for constant speciation rates also exists. Declining rates have been explained by invoking pre-existing niches, whereas constant rates have been attributed to non-adaptive processes such as sexual selection and mutation. Trends in speciation rate and the processes underlying it remain unclear, representing a critical information gap in understanding patterns of global diversity. Here we show that the temporal trend in the speciation rate can also be explained by frequency-dependent selection. We construct a frequency-dependent and DNA sequence-based model of speciation. We compare our model to empirical diversity patterns observed for cichlid fish and Darwin's finches, two classic systems for which speciation rates and richness data exist. Negative frequency-dependent selection predicts well both the declining speciation rate found in cichlid fish and explains their species richness. For groups like the Darwin's finches, in which speciation rates are constant and diversity is lower, speciation rate is better explained by a model without frequency-dependent selection. Our analysis shows that differences in diversity may be driven by incipient species abundance with frequency-dependent selection. Our results demonstrate that genetic-distance-based speciation and frequency-dependent selection are sufficient to explain the high diversity observed in natural systems and, importantly, predict decay through time in speciation rate in the absence of pre-existing niches.

Assessing the effect of different treatments on decomposition rate of dairy manure.

PubMed

Khalil, Tariq M; Higgins, Stewart S; Ndegwa, Pius M; Frear, Craig S; Stöckle, Claudio O

2016-11-01

Confined animal feeding operations (CAFOs) contribute to greenhouse gas emission, but the magnitude of these emissions as a function of operation size, infrastructure, and manure management are difficult to assess. Modeling is a viable option to estimate gaseous emission and nutrient flows from CAFOs. These models use a decomposition rate constant for carbon mineralization. However, this constant is usually determined assuming a homogenous mix of manure, ignoring the effects of emerging manure treatments. The aim of this study was to measure and compare the decomposition rate constants of dairy manure in single and three-pool decomposition models, and to develop an empirical model based on chemical composition of manure for prediction of a decomposition rate constant. Decomposition rate constants of manure before and after an anaerobic digester (AD), following coarse fiber separation, and fine solids removal were determined under anaerobic conditions for single and three-pool decomposition models. The decomposition rates of treated manure effluents differed significantly from untreated manure for both single and three-pool decomposition models. In the single-pool decomposition model, AD effluent containing only suspended solids had a relatively high decomposition rate of 0.060 d(-1), while liquid with coarse fiber and fine solids removed had the lowest rate of 0.013 d(-1). In the three-pool decomposition model, fast and slow decomposition rate constants (0.25 d(-1) and 0.016 d(-1) respectively) of untreated AD influent were also significantly different from treated manure fractions. A regression model to predict the decomposition rate of treated dairy manure fitted well (R(2) = 0.83) to observed data. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fatigue Analyses Under Constant- and Variable-Amplitude Loading Using Small-Crack Theory

NASA Technical Reports Server (NTRS)

Newman, J. C., Jr.; Phillips, E. P.; Everett, R. A., Jr.

1999-01-01

Studies on the growth of small cracks have led to the observation that fatigue life of many engineering materials is primarily "crack growth" from micro-structural features, such as inclusion particles, voids, slip-bands or from manufacturing defects. This paper reviews the capabilities of a plasticity-induced crack-closure model to predict fatigue lives of metallic materials using "small-crack theory" under various loading conditions. Constraint factors, to account for three-dimensional effects, were selected to correlate large-crack growth rate data as a function of the effective stress-intensity factor range (delta-Keff) under constant-amplitude loading. Modifications to the delta-Keff-rate relations in the near-threshold regime were needed to fit measured small-crack growth rate behavior. The model was then used to calculate small-and large-crack growth rates, and to predict total fatigue lives, for notched and un-notched specimens under constant-amplitude and spectrum loading. Fatigue lives were predicted using crack-growth relations and micro-structural features like those that initiated cracks in the fatigue specimens for most of the materials analyzed. Results from the tests and analyses agreed well.

Electron attachment to CF3 and CF3Br at temperatures up to 890 K: experimental test of the kinetic modeling approach.

PubMed

Shuman, Nicholas S; Miller, Thomas M; Viggiano, Albert A; Troe, Jürgen

2013-05-28

Thermal rate constants and product branching fractions for electron attachment to CF3Br and the CF3 radical have been measured over the temperature range 300-890 K, the upper limit being restricted by thermal decomposition of CF3Br. Both measurements were made in Flowing Afterglow Langmuir Probe apparatuses; the CF3Br measurement was made using standard techniques, and the CF3 measurement using the Variable Electron and Neutral Density Attachment Mass Spectrometry technique. Attachment to CF3Br proceeds exclusively by the dissociative channel yielding Br(-), with a rate constant increasing from 1.1 × 10(-8) cm(3) s(-1) at 300 K to 5.3 × 10(-8) cm(3) s(-1) at 890 K, somewhat lower than previous data at temperatures up to 777 K. CF3 attachment proceeds through competition between associative attachment yielding CF3 (-) and dissociative attachment yielding F(-). Prior data up to 600 K showed the rate constant monotonically increasing, with the partial rate constant of the dissociative channel following Arrhenius behavior; however, extrapolation of the data using a recently proposed kinetic modeling approach predicted the rate constant to turn over at higher temperatures, despite being only ~5% of the collision rate. The current data agree well with the previous kinetic modeling extrapolation, providing a demonstration of the predictive capabilities of the approach.

Effect of Load Rate on Ultimate Tensile Strength of Ceramic Matrix Composites at Elevated Temperatures

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Gyekenyesi, John P.

2001-01-01

The strengths of three continuous fiber-reinforced ceramic composites, including SiC/CAS-II, SiC/MAS-5 and SiC/SiC, were determined as a function of test rate in air at 1100 to 1200 C. All three composite materials exhibited a strong dependency of strength on test rate, similar to the behavior observed in many advanced monolithic ceramics at elevated temperatures. The application of the preloading technique as well as the prediction of life from one loading configuration (constant stress-rate) to another (constant stress loading) suggested that the overall macroscopic failure mechanism of the composites would be the one governed by a power-law type of damage evolution/accumulation, analogous to slow crack growth commonly observed in advanced monolithic ceramics. It was further found that constant stress-rate testing could be used as an alternative to life prediction test methodology even for composite materials, at least for short range of lifetimes and when ultimate strength is used as the failure criterion.

Fatigue life and crack growth prediction methodology

NASA Technical Reports Server (NTRS)

Newman, J. C., Jr.; Phillips, E. P.; Everett, R. A., Jr.

1993-01-01

The capabilities of a plasticity-induced crack-closure model and life-prediction code to predict fatigue crack growth and fatigue lives of metallic materials are reviewed. Crack-tip constraint factors, to account for three-dimensional effects, were selected to correlate large-crack growth rate data as a function of the effective-stress-intensity factor range (delta(K(sub eff))) under constant-amplitude loading. Some modifications to the delta(K(sub eff))-rate relations were needed in the near threshold regime to fit small-crack growth rate behavior and endurance limits. The model was then used to calculate small- and large-crack growth rates, and in some cases total fatigue lives, for several aluminum and titanium alloys under constant-amplitude, variable-amplitude, and spectrum loading. Fatigue lives were calculated using the crack growth relations and microstructural features like those that initiated cracks. Results from the tests and analyses agreed well.

The computational analysis and modelling of substitution effects on hydrolysis of formanilides in acidic aqueous solutions

NASA Astrophysics Data System (ADS)

Lukeš, Vladimír; Škorňa, Peter; Michalík, Martin; Klein, Erik

2017-11-01

Various para, meta and ortho substituted formanilides have been theoretically studied. For trans and cis-isomers of non-substituted formanilide, the calculated B3LYP vibration normal modes were analyzed. Substituent effect on the selected normal modes was described and the comparison with the available experimental data is presented. The calculated B3LYP proton affinities were correlated with Hammett constants, Fujita-Nishioka equation and the rate constants of the hydrolysis in 1 M HCl. Found linear dependences allow predictions of dissociation constants (pKBH+) and hydrolysis rate constants. Obtained results indicate that protonation of amide group may represent the rate determining step of acid catalyzed hydrolysis.

Computation of Kinetics for the Hydrogen/Oxygen System Using the Thermodynamic Method

NASA Technical Reports Server (NTRS)

Marek, C. John

1996-01-01

A new method for predicting chemical rate constants using thermodynamics has been applied to the hydrogen/oxygen system. This method is based on using the gradient of the Gibbs free energy and a single proportionality constant D to determine the kinetic rate constants. Using this method the rate constants for any gas phase reaction can be computed from thermodynamic properties. A modified reaction set for the H/O system is determined. A11 of the third body efficiencies M are taken to be unity. Good agreement was obtained between the thermodynamic method and the experimental shock tube data. In addition, the hydrogen bromide experimental data presented in previous work is recomputed with M's of unity.

Analyses of Fatigue and Fatigue-Crack Growth under Constant- and Variable-Amplitude Loading

NASA Technical Reports Server (NTRS)

Newman, J. C., Jr.

1999-01-01

Studies on the growth of small cracks have led to the observation that fatigue life of many engineering materials is primarily crack growth from micro-structural features, such as inclusion particles, voids, slip-bands or from manufacturing defects. This paper reviews the capabilities of a plasticity-induced crack-closure model to predict fatigue lives of metallic materials using small-crack theory under various loading conditions. Constraint factors, to account for three-dimensional effects, were selected to correlate large-crack growth rate data as a function of the effective stress-intensity factor range (delta K(sub eff)) under constant-amplitude loading. Modifications to the delta K(sub eff)-rate relations in the near-threshold regime were needed to fit measured small-crack growth rate behavior. The model was then used to calculate small- and large-crack growth rates, and to predict total fatigue lives, for notched and un-notched specimens under constant-amplitude and spectrum loading. Fatigue lives were predicted using crack-growth relations and micro-structural features like those that initiated cracks in the fatigue specimens for most of the materials analyzed. Results from the tests and analyses agreed well.

Experimental and Estimated Rate Constants for the Reactions of Hydroxyl Radicals with Several Halocarbons

NASA Technical Reports Server (NTRS)

DeMore, W.B.

1996-01-01

Relative rate experiments are used to measure rate constants and temperature dependencies of the reactions of OH with CH3F (41), CH2FCl (31), CH2BrCl (30B1), CH2Br2 (3OB2), CHBr3 (2OB3), CF2BrCHFCl (123aBl(alpha)), and CF2ClCHCl2 (122). Rate constants for additional compounds of these types are estimated using an empirical rate constant estimation method which is based on measured rate constants for a wide range of halocarbons. The experimental data are combined with the estimated and previously reported rate constants to illustrate the effects of F, Cl, and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes. Application of the estimation technique is further illustrated for some higher hydrofluorocarbons (HFCs), including CHF2CF2CF2CF2H (338pcc), CF3CHFCHFCF2CF3 (43-10mee), CF3CH2CH2CF3 (356ffa), CF3CH2CF2CH2CF3 (458mfcf), CF3CH2CHF2 (245fa), and CF3CH2CF2CH3 (365mfc). The predictions are compared with literature data for these compounds.

Prediction of Chain Propagation Rate Constants of Polymerization Reactions in Aqueous NIPAM/BIS and VCL/BIS Systems.

PubMed

Kröger, Leif C; Kopp, Wassja A; Leonhard, Kai

2017-04-06

Microgels have a wide range of possible applications and are therefore studied with increasing interest. Nonetheless, the microgel synthesis process and some of the resulting properties of the microgels, such as the cross-linker distribution within the microgels, are not yet fully understood. An in-depth understanding of the synthesis process is crucial for designing tailored microgels with desired properties. In this work, rate constants and reaction enthalpies of chain propagation reactions in aqueous N-isopropylacrylamide/N,N'-methylenebisacrylamide and aqueous N-vinylcaprolactam/N,N'-methylenebisacrylamide systems are calculated to identify the possible sources of an inhomogeneous cross-linker distribution in the resulting microgels. Gas-phase reaction rate constants are calculated from B2PLYPD3/aug-cc-pVTZ energies and B3LYPD3/tzvp geometries and frequencies. Then, solvation effects based on COSMO-RS are incorporated into the rate constants to obtain the desired liquid-phase reaction rate constants. The rate constants agree with experiments within a factor of 2-10, and the reaction enthalpies deviate less than 5 kJ/mol. Further, the effect of rate constants on the microgel growth process is analyzed, and it is shown that differences in the magnitude of the reaction rate constants are a source of an inhomogeneous cross-linker distribution within the resulting microgel.

A framework for establishing predictive relationships between specific bacterial 16S rRNA sequence abundances and biotransformation rates.

PubMed

Helbling, Damian E; Johnson, David R; Lee, Tae Kwon; Scheidegger, Andreas; Fenner, Kathrin

2015-03-01

The rates at which wastewater treatment plant (WWTP) microbial communities biotransform specific substrates can differ by orders of magnitude among WWTP communities. Differences in taxonomic compositions among WWTP communities may predict differences in the rates of some types of biotransformations. In this work, we present a novel framework for establishing predictive relationships between specific bacterial 16S rRNA sequence abundances and biotransformation rates. We selected ten WWTPs with substantial variation in their environmental and operational metrics and measured the in situ ammonia biotransformation rate constants in nine of them. We isolated total RNA from samples from each WWTP and analyzed 16S rRNA sequence reads. We then developed multivariate models between the measured abundances of specific bacterial 16S rRNA sequence reads and the ammonia biotransformation rate constants. We constructed model scenarios that systematically explored the effects of model regularization, model linearity and non-linearity, and aggregation of 16S rRNA sequences into operational taxonomic units (OTUs) as a function of sequence dissimilarity threshold (SDT). A large percentage (greater than 80%) of model scenarios resulted in well-performing and significant models at intermediate SDTs of 0.13-0.14 and 0.26. The 16S rRNA sequences consistently selected into the well-performing and significant models at those SDTs were classified as Nitrosomonas and Nitrospira groups. We then extend the framework by applying it to the biotransformation rate constants of ten micropollutants measured in batch reactors seeded with the ten WWTP communities. We identified phylogenetic groups that were robustly selected into all well-performing and significant models constructed with biotransformation rates of isoproturon, propachlor, ranitidine, and venlafaxine. These phylogenetic groups can be used as predictive biomarkers of WWTP microbial community activity towards these specific micropollutants. This work is an important step towards developing tools to predict biotransformation rates in WWTPs based on taxonomic composition. Copyright © 2014 Elsevier Ltd. All rights reserved.

Rate constants for proteins binding to substrates with multiple binding sites using a generalized forward flux sampling expression

NASA Astrophysics Data System (ADS)

Vijaykumar, Adithya; ten Wolde, Pieter Rein; Bolhuis, Peter G.

2018-03-01

To predict the response of a biochemical system, knowledge of the intrinsic and effective rate constants of proteins is crucial. The experimentally accessible effective rate constant for association can be decomposed in a diffusion-limited rate at which proteins come into contact and an intrinsic association rate at which the proteins in contact truly bind. Reversely, when dissociating, bound proteins first separate into a contact pair with an intrinsic dissociation rate, before moving away by diffusion. While microscopic expressions exist that enable the calculation of the intrinsic and effective rate constants by conducting a single rare event simulation of the protein dissociation reaction, these expressions are only valid when the substrate has just one binding site. If the substrate has multiple binding sites, a bound enzyme can, besides dissociating into the bulk, also hop to another binding site. Calculating transition rate constants between multiple states with forward flux sampling requires a generalized rate expression. We present this expression here and use it to derive explicit expressions for all intrinsic and effective rate constants involving binding to multiple states, including rebinding. We illustrate our approach by computing the intrinsic and effective association, dissociation, and hopping rate constants for a system in which a patchy particle model enzyme binds to a substrate with two binding sites. We find that these rate constants increase as a function of the rotational diffusion constant of the particles. The hopping rate constant decreases as a function of the distance between the binding sites. Finally, we find that blocking one of the binding sites enhances both association and dissociation rate constants. Our approach and results are important for understanding and modeling association reactions in enzyme-substrate systems and other patchy particle systems and open the way for large multiscale simulations of such systems.

Concepts, challenges, and successes in modeling thermodynamics of metabolism.

PubMed

Cannon, William R

2014-01-01

The modeling of the chemical reactions involved in metabolism is a daunting task. Ideally, the modeling of metabolism would use kinetic simulations, but these simulations require knowledge of the thousands of rate constants involved in the reactions. The measurement of rate constants is very labor intensive, and hence rate constants for most enzymatic reactions are not available. Consequently, constraint-based flux modeling has been the method of choice because it does not require the use of the rate constants of the law of mass action. However, this convenience also limits the predictive power of constraint-based approaches in that the law of mass action is used only as a constraint, making it difficult to predict metabolite levels or energy requirements of pathways. An alternative to both of these approaches is to model metabolism using simulations of states rather than simulations of reactions, in which the state is defined as the set of all metabolite counts or concentrations. While kinetic simulations model reactions based on the likelihood of the reaction derived from the law of mass action, states are modeled based on likelihood ratios of mass action. Both approaches provide information on the energy requirements of metabolic reactions and pathways. However, modeling states rather than reactions has the advantage that the parameters needed to model states (chemical potentials) are much easier to determine than the parameters needed to model reactions (rate constants). Herein, we discuss recent results, assumptions, and issues in using simulations of state to model metabolism.

Flame Chemiluminescence Rate Constants for Quantitative Microgravity Combustion Diagnostics

NASA Technical Reports Server (NTRS)

Luque, Jorge; Smith, Gregory P.; Jeffries, Jay B.; Crosley, David R.; Weiland, Karen (Technical Monitor)

2001-01-01

Absolute excited state concentrations of OH(A), CH(A), and C2(d) were determined in three low pressure premixed methane-air flames. Two dimensional images of chemiluminescence from these states were recorded by a filtered CCD camera, processed by Abel inversion, and calibrated against Rayleigh scattering, Using a previously validated 1-D flame model with known chemistry and excited state quenching rate constants, rate constants are extracted for the reactions CH + O2 (goes to) OH(A) + CO and C2H + O (goes to) CH(A) + CO at flame temperatures. Variations of flame emission intensities with stoichiometry agree well with model predictions.

Electron attachment to CF{sub 3} and CF{sub 3}Br at temperatures up to 890 K: Experimental test of the kinetic modeling approach

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

Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, Albert A.

Thermal rate constants and product branching fractions for electron attachment to CF{sub 3}Br and the CF{sub 3} radical have been measured over the temperature range 300-890 K, the upper limit being restricted by thermal decomposition of CF{sub 3}Br. Both measurements were made in Flowing Afterglow Langmuir Probe apparatuses; the CF{sub 3}Br measurement was made using standard techniques, and the CF{sub 3} measurement using the Variable Electron and Neutral Density Attachment Mass Spectrometry technique. Attachment to CF{sub 3}Br proceeds exclusively by the dissociative channel yielding Br{sup -}, with a rate constant increasing from 1.1 Multiplication-Sign 10{sup -8} cm{sup 3} s{sup -1}more » at 300 K to 5.3 Multiplication-Sign 10{sup -8} cm{sup 3} s{sup -1} at 890 K, somewhat lower than previous data at temperatures up to 777 K. CF{sub 3} attachment proceeds through competition between associative attachment yielding CF{sub 3}{sup -} and dissociative attachment yielding F{sup -}. Prior data up to 600 K showed the rate constant monotonically increasing, with the partial rate constant of the dissociative channel following Arrhenius behavior; however, extrapolation of the data using a recently proposed kinetic modeling approach predicted the rate constant to turn over at higher temperatures, despite being only {approx}5% of the collision rate. The current data agree well with the previous kinetic modeling extrapolation, providing a demonstration of the predictive capabilities of the approach.« less

Hadron mass and decays constant predictions of the valence approximation to lattice QCD

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

Weingarten, D.

1993-05-01

A key goal of the lattice formulation of QCD is to reproduce the masses and decay constants of the low-lying baryons and mesons. Lattice QCD mass and decay constant predictions for the real world are supposed to be obtained from masses and decay constants calculated with finite lattice spacing and finite lattice volume by taking the limits of zero spacing and infinite volume. In addition, since the algorithms used for hadron mass and decay constant calculations become progressively slower for small quark masses, results are presently found with quark masses much larger than the expected values of the up andmore » down quark masses. Predictions for the properties of hadrons containing up and down quarks then require a further extrapolation to small quark masses. The author reports here mass and decay constant predictions combining all three extrapolations for Wilson quarks in the valence (quenched) approximation. This approximation may be viewed as replacing the momentum and frequency dependent color dielectric constant arising from quark-antiquark vacuum polarization with its zero-momentum, zero-frequency limit. These calculations used approximately one year of machine time on the GF11 parallel computer running at a sustained rate of between 5 and 7 Gflops.« less

Theory of bi-molecular association dynamics in 2D for accurate model and experimental parameterization of binding rates

PubMed Central

Yogurtcu, Osman N.; Johnson, Margaret E.

2015-01-01

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 to dense systems. PMID:26328828

Role of effluent organic matter in the photochemical degradation of compounds of wastewater origin.

PubMed

Bodhipaksha, Laleen C; Sharpless, Charles M; Chin, Yu-Ping; MacKay, Allison A

2017-03-01

The photoreactivity of treated wastewater effluent organic matter differs from that of natural organic matter, and the indirect phototransformation rates of micropollutants originating in wastewater are expected to depend on the fractional contribution of wastewater to total stream flow. Photodegradation rates of four common compounds of wastewater origin (sulfamethoxazole, sulfadimethoxine, cimetidine and caffeine) were measured in river water, treated municipal wastewater effluent and mixtures of both to simulate various effluent-stream water mixing conditions that could occur in environmental systems. Compounds were chosen for their unique photodegradation pathways with the photochemically produced reactive intermediates, triplet-state excited organic matter ( 3 OM*), singlet oxygen ( 1 O 2 ), and hydroxyl radicals (OH). For all compounds, higher rates of photodegradation were observed in effluent relative to upstream river water. Sulfamethoxazole degraded primarily via direct photolysis, with some contribution from OH and possibly from carbonate radicals and other unidentified reactive intermediates in effluent-containing samples. Sulfadimethoxine also degraded mainly by direct photolysis, and natural organic matter appeared to inhibit this process to a greater extent than predicted by light screening. In the presence of effluent organic matter, sulfadimethoxine showed additional reactions with OH and 1 O 2 . In all water samples, cimetidine degraded by reaction with 1 O 2 (>95%) and caffeine by reaction with OH (>95%). In river water mixtures, photodegradation rate constants for all compounds increased with increasing fractions of effluent. A conservative mixing model was able to predict reaction rate constants in the case of hydroxyl radical reactions, but it overestimated rate constants in the case of 3 OM* and 1 O 2 pathways. Finally, compound degradation rate constants normalized to the rate of light absorption by water correlated with E 2 /E 3 ratios (sample absorbance at 254 nm divided by sample absorbance at 365 nm), suggesting that organic matter optical properties may hold promise to predict indirect compound photodegradation rates for various effluent mixing ratios. Copyright © 2016 Elsevier Ltd. All rights reserved.

Elongational flow of polymer melts at constant strain rate, constant stress and constant force

NASA Astrophysics Data System (ADS)

Wagner, Manfred H.; Rolón-Garrido, Víctor H.

2013-04-01

Characterization of polymer melts in elongational flow is typically performed at constant elongational rate or rarely at constant tensile stress conditions. One of the disadvantages of these deformation modes is that they are hampered by the onset of "necking" instabilities according to the Considère criterion. Experiments at constant tensile force have been performed even more rarely, in spite of the fact that this deformation mode is free from necking instabilities and is of considerable industrial relevance as it is the correct analogue of steady fiber spinning. It is the objective of the present contribution to present for the first time a full experimental characterization of a long-chain branched polyethylene melt in elongational flow. Experiments were performed at constant elongation rate, constant tensile stress and constant tensile force by use of a Sentmanat Extensional Rheometer (SER) in combination with an Anton Paar MCR301 rotational rheometer. The accessible experimental window and experimental limitations are discussed. The experimental data are modelled by using the Wagner I model. Predictions of the steady-start elongational viscosity in constant strain rate and creep experiments are found to be identical, albeit only by extrapolation of the experimental data to Hencky strains of the order of 6. For constant stress experiments, a minimum in the strain rate and a corresponding maximum in the elongational viscosity is found at a Hencky strain of the order of 3, which, although larger than the steady-state value, follows roughly the general trend of the steady-state elongational viscosity. The constitutive analysis also reveals that constant tensile force experiments indicate a larger strain hardening potential than seen in constant elongation rate or constant tensile stress experiments. This may be indicative of the effect of necking under constant elongation rate or constant tensile stress conditions according to the Considère criterion.

Rationalizing 5000-Fold Differences in Receptor-Binding Rate Constants of Four Cytokines

PubMed Central

Pang, Xiaodong; Qin, Sanbo; Zhou, Huan-Xiang

2011-01-01

The four cytokines erythropoietin (EPO), interleukin-4 (IL4), human growth hormone (hGH), and prolactin (PRL) all form four-helix bundles and bind to type I cytokine receptors. However, their receptor-binding rate constants span a 5000-fold range. Here, we quantitatively rationalize these vast differences in rate constants by our transient-complex theory for protein-protein association. In the transient complex, the two proteins have near-native separation and relative orientation, but have yet to form the short-range specific interactions of the native complex. The theory predicts the association rate constant as ka=ka0exp(−ΔGel∗/kBT) where ka0 is the basal rate constant for reaching the transient complex by random diffusion, and the Boltzmann factor captures the rate enhancement due to electrostatic attraction. We found that the vast differences in receptor-binding rate constants of the four cytokines arise mostly from the differences in charge complementarity among the four cytokine-receptor complexes. The basal rate constants (ka0) of EPO, IL4, hGH, and PRL were similar (5.2 × 105 M−1s−1, 2.4 × 105 M−1s−1, 1.7 × 105 M−1s−1, and 1.7 × 105 M−1s−1, respectively). However, the average electrostatic free energies (ΔGe1∗) were very different (−4.2 kcal/mol, −2.4 kcal/mol, −0.1 kcal/mol, and −0.5 kcal/mol, respectively, at ionic strength = 160 mM). The receptor-binding rate constants predicted without adjusting any parameters, 6.2 × 108 M−1s−1, 1.3 × 107 M−1s−1, 2.0 × 105 M−1s−1, and 7.6 × 104 M−1s−1, respectively, for EPO, IL4, hGH, and PRL agree well with experimental results. We uncover that these diverse rate constants are anticorrelated with the circulation concentrations of the cytokines, with the resulting cytokine-receptor binding rates very close to the limits set by the half-lives of the receptors, suggesting that these binding rates are functionally relevant and perhaps evolutionarily tuned. Our calculations also reproduced well-observed effects of mutations and ionic strength on the rate constants and produced a set of mutations on the complex of hGH with its receptor that putatively enhances the rate constant by nearly 100-fold through increasing charge complementarity. To quantify charge complementarity, we propose a simple index based on the charge distribution within the binding interface, which shows good correlation with ΔGe1∗. Together these results suggest that protein charges can be manipulated to tune ka and control biological function. PMID:21889455

Slow Crack Growth Analysis of Advanced Structural Ceramics Under Combined Loading Conditions: Damage Assessment in Life Prediction Testing

NASA Technical Reports Server (NTRS)

Choi, S. R.; Gyekenyesi, J. P.

2001-01-01

Slow crack growth analysis was performed with three different loading histories including constant stress- rate/constant stress-rate testing (Case I loading), constant stress/constant stress-rate testing (Case II loading), and cyclic stress/constant stress-rate testing (Case III loading). Strength degradation due to slow crack growth and/or damage accumulation was determined numerically as a function of percentage of interruption time between the two loading sequences for a given loading history. The numerical solutions were examined with the experimental data determined at elevated temperatures using four different advanced ceramic materials, two silicon nitrides, one silicon carbide and one alumina for the Case I loading history, and alumina for the Case II loading history. The numerical solutions were in reasonable agreement with the experimental data, indicating that notwithstanding some degree of creep deformation presented for some test materials slow crack growth was a governing mechanism associated with failure for all the rest materials.

Slow Crack Growth Analysis of Advanced Structural Ceramics Under Combined Loading Conditions: Damage Assessment in Life Prediction Testing

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Gyekenyesi, John P.

2000-01-01

Slow crack growth analysis was performed with three different loading histories including constant stress-rate/constant stress-rate testing (Case 1 loading), constant stress/constant stress-rate testing (Case 2 loading), and cyclic stress/constant stress-rate testing (Case 2 loading). Strength degradation due to slow crack growth and/or damage accumulation was determined numerically as a function of percentage of interruption time between the two loading sequences for a given loading history. The numerical solutions were examined with the experimental data determined at elevated temperatures using four different advanced ceramic materials, two silicon nitrides, one silicon carbide and one alumina for the Case 1 loading history, and alumina for the Case 3 loading history. The numerical solutions were in reasonable agreement with the experimental data, indicating that notwithstanding some degree of creep deformation presented for some test materials slow crack growth was a governing mechanism associated with failure for all the test materials.

Slow Crack Growth Analysis of Advanced Structural Ceramics Under Combined Loading Conditions: Damage Assessment in Life Prediction Testing

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Gyekenyesi, John P.

2000-01-01

Slow crack growth analysis was performed with three different loading histories including constant stress-rate/constant stress-rate testing (Case I loading), constant stress/constant stress-rate testing (Case II loading), and cyclic stress/constant stress-rate testing (Case III loading). Strength degradation due to slow crack growth arid/or damage accumulation was determined numerically as a Function of percentage of interruption time between the two loading sequences for a given loading history. The numerical solutions were examined with the experimental data determined at elevated temperatures using four different advanced ceramic materials, two silicon nitrides, one silicon carbide and one alumina for the Case I loading history, and alumina for the Case II loading history. The numerical solutions were in reasonable agreement with the experimental data, indicating that notwithstanding some degree of creep deformation presented for some test materials slow crack growth was a governing mechanism associated with failure for all the test material&

Non-steady state mass action dynamics without rate constants: dynamics of coupled reactions using chemical potentials

NASA Astrophysics Data System (ADS)

Cannon, William R.; Baker, Scott E.

2017-10-01

Comprehensive and predictive simulation of coupled reaction networks has long been a goal of biology and other fields. Currently, metabolic network models that utilize enzyme mass action kinetics have predictive power but are limited in scope and application by the fact that the determination of enzyme rate constants is laborious and low throughput. We present a statistical thermodynamic formulation of the law of mass action for coupled reactions at both steady states and non-stationary states. The formulation uses chemical potentials instead of rate constants. When used to model deterministic systems, the method corresponds to a rescaling of the time dependent reactions in such a way that steady states can be reached on the same time scale but with significantly fewer computational steps. The relationships between reaction affinities, free energy changes and generalized detailed balance are central to the discussion. The significance for applications in systems biology are discussed as is the concept and assumption of maximum entropy production rate as a biological principle that links thermodynamics to natural selection.

The uncertainty of biodegradation rate constants of emerging organic compounds in soil and groundwater - A compilation of literature values for 82 substances.

PubMed

Greskowiak, Janek; Hamann, Enrico; Burke, Victoria; Massmann, Gudrun

2017-12-01

The present study reports on biodegradation rate constants of emerging organic compounds (EOCs) in soil and groundwater available in the literature. The major aim of this compilation was to provide an assessment of the uncertainty of hydrological models with respect to the fate of EOCs. The literature search identified a total number of 82 EOCs for which 1st-order rate constants could be derived. It was found that for the majority of compounds degradation rate constants vary over more than three orders of magnitude. Correlation to factors that are well known to affect the degradation rate, such as temperature or redox condition was weak. No correlation at all was found with results from available quantitative structure-activity relationship models. This suggests that many unknown site specific or experimentally specific factors influence the degradation behavior of EOCs in the environment. Thus, local and catchment scale predictive models to estimate EOC concentration at receptors, e.g., receiving waters or drinking water wells, need to consider the large uncertainty in 1st-order rate constants. As a consequence, applying rate constants that were derived from one experiment or field site investigation to other experiments or field sites should be done with extreme caution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Prediction of failure pressure and leak rate of stress corrosion.

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

Majumdar, S.; Kasza, K.; Park, J. Y.

2002-06-24

An ''equivalent rectangular crack'' approach was employed to predict rupture pressures and leak rates through laboratory generated stress corrosion cracks and steam generator tubes removed from the McGuire Nuclear Station. Specimen flaws were sized by post-test fractography in addition to a pre-test advanced eddy current technique. The predicted and observed test data on rupture and leak rate are compared. In general, the test failure pressures and leak rates are closer to those predicted on the basis of fractography than on nondestructive evaluation (NDE). However, the predictions based on NDE results are encouraging, particularly because they have the potential to determinemore » a more detailed geometry of ligamented cracks, from which failure pressure and leak rate can be more accurately predicted. One test specimen displayed a time-dependent increase of leak rate under constant pressure.« less

The effect of solvent relaxation time constants on free energy gap law for ultrafast charge recombination following photoinduced charge separation.

PubMed

Mikhailova, Valentina A; Malykhin, Roman E; Ivanov, Anatoly I

2018-05-16

To elucidate the regularities inherent in the kinetics of ultrafast charge recombination following photoinduced charge separation in donor-acceptor dyads in solutions, the simulations of the kinetics have been performed within the stochastic multichannel point-transition model. Increasing the solvent relaxation time scales has been shown to strongly vary the dependence of the charge recombination rate constant on the free energy gap. In slow relaxing solvents the non-equilibrium charge recombination occurring in parallel with solvent relaxation is very effective so that the charge recombination terminates at the non-equilibrium stage. This results in a crucial difference between the free energy gap laws for the ultrafast charge recombination and the thermal charge transfer. For the thermal reactions the well-known Marcus bell-shaped dependence of the rate constant on the free energy gap is realized while for the ultrafast charge recombination only a descending branch is predicted in the whole area of the free energy gap exceeding 0.2 eV. From the available experimental data on the population kinetics of the second and first excited states for a series of Zn-porphyrin-imide dyads in toluene and tetrahydrofuran solutions, an effective rate constant of the charge recombination into the first excited state has been calculated. The obtained rate constant being very high is nearly invariable in the area of the charge recombination free energy gap from 0.2 to 0.6 eV that supports the theoretical prediction.

Modeling the reactivities of hydroxyl radical and ozone towards atmospheric organic chemicals using quantitative structure-reactivity relationship approaches.

PubMed

Gupta, Shikha; Basant, Nikita; Mohan, Dinesh; Singh, Kunwar P

2016-07-01

The persistence and the removal of organic chemicals from the atmosphere are largely determined by their reactions with the OH radical and O3. Experimental determinations of the kinetic rate constants of OH and O3 with a large number of chemicals are tedious and resource intensive and development of computational approaches has widely been advocated. Recently, ensemble machine learning (EML) methods have emerged as unbiased tools to establish relationship between independent and dependent variables having a nonlinear dependence. In this study, EML-based, temperature-dependent quantitative structure-reactivity relationship (QSRR) models have been developed for predicting the kinetic rate constants for OH (kOH) and O3 (kO3) reactions with diverse chemicals. Structural diversity of chemicals was evaluated using a Tanimoto similarity index. The generalization and prediction abilities of the constructed models were established through rigorous internal and external validation performed employing statistical checks. In test data, the EML QSRR models yielded correlation (R (2)) of ≥0.91 between the measured and the predicted reactivities. The applicability domains of the constructed models were determined using methods based on descriptors range, Euclidean distance, leverage, and standardization approaches. The prediction accuracies for the higher reactivity compounds were relatively better than those of the low reactivity compounds. Proposed EML QSRR models performed well and outperformed the previous reports. The proposed QSRR models can make predictions of rate constants at different temperatures. The proposed models can be useful tools in predicting the reactivities of chemicals towards OH radical and O3 in the atmosphere.

ESTER HYDROLYSIS RATE CONSTANT PREDICTION FROM INFRARED INTERFEROGRAMS

EPA Science Inventory

A method for predicting reactivity parameters of organic chemicals from spectroscopic data is being developed to assist in assessing the environmental fate of pollutants. he prototype system, which employs multiple linear regression analysis using selected points from the Fourier...

Revised estimates for ozone reduction by shuttle operation

NASA Technical Reports Server (NTRS)

Potter, A. E.

1978-01-01

Previous calculations by five different modeling groups of the effect of space shuttle operations on the ozone layer yielded an estimate of 0.2 percent ozone reduction for the Northern Hemisphere at 60 launches per year. Since these calculations were made, the accepted rate constant for the reaction between hydroperoxyl and nitric oxide to yield hydroxyl and nitrogen dioxide, HO2 + NO yields OH + NO2, was revised upward by more than an order of magnitude, with a resultant increase in the predicted ozone reduction for chlorofluoromethanes by a factor of approximately 2. New calculations of the shuttle effect were made with use of the new rate constant data, again by five different modeling groups. The new value of the shuttle effect on the ozone layer was found to be 0.25 percent. The increase resulting from the revised rate constant is considerably less for space shuttle operations than for chlorofluoromethane production, because the new rate constant also increases the calculated rate of downward transport of shuttle exhaust products out of the stratosphere.

Uncertainty analysis of multi-rate kinetics of uranium desorption from sediments

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

Zhang, Xiaoying; Liu, Chongxuan; Hu, Bill X.

2014-01-01

A multi-rate expression for uranyl [U(VI)] surface complexation reactions has been proposed to describe diffusion-limited U(VI) sorption/desorption in heterogeneous subsurface sediments. An important assumption in the rate expression is that its rate constants follow a certain type probability distribution. In this paper, a Bayes-based, Differential Evolution Markov Chain method was used to assess the distribution assumption and to analyze parameter and model structure uncertainties. U(VI) desorption from a contaminated sediment at the US Hanford 300 Area, Washington was used as an example for detail analysis. The results indicated that: 1) the rate constants in the multi-rate expression contain uneven uncertaintiesmore » with slower rate constants having relative larger uncertainties; 2) the lognormal distribution is an effective assumption for the rate constants in the multi-rate model to simualte U(VI) desorption; 3) however, long-term prediction and its uncertainty may be significantly biased by the lognormal assumption for the smaller rate constants; and 4) both parameter and model structure uncertainties can affect the extrapolation of the multi-rate model with a larger uncertainty from the model structure. The results provide important insights into the factors contributing to the uncertainties of the multi-rate expression commonly used to describe the diffusion or mixing-limited sorption/desorption of both organic and inorganic contaminants in subsurface sediments.« less

Kinetics and mechanism studies of switching and association reactions involving Na + -ligand complexes

NASA Astrophysics Data System (ADS)

Yang, X.; Castleman, A. W., Jr.

1990-08-01

The kinetics and mechanisms of the reactions of Na+ṡ(X)n=0-3, X=water, ammonia, and methanol with CH3CN, CH3COCH3, CH3CHO, CH3COOH, CH3COOCH3, NH3, CH3OH, and CH3-O-C2H4-O-CH3(DMOE) were studied at ambient temperature under different pressures. All of the switching (substitution) reactions proceed at near-collision rate and show little dependence on the flow tube pressure, the nature and size of the ligand, or the type of core ions. Interestingly, all of the measured rate constants agree well with predictions based on the parametrized trajectory calculations of Su and Chesnavich [J. Chem. Phys. 76, 5183 (1982)]. The reactions of the bare sodium ion with all neutrals proceed via a three-body association mechanism and the measured rate constants cover a large range from a slow association reaction with NH3, to a near-collision rate with DMOE. The lifetimes and the dissociation rate constants of the intermediate complexes deduced using the parametrized trajectory results, combined with the experimentally determined rates, compare fairly well with predictions based on RRKM theory. The calculations also account for the large isotope effect observed for the clustering of ND3 and NH3 to Na+.

On rate-state and Coulomb failure models

USGS Publications Warehouse

Gomberg, J.; Beeler, N.; Blanpied, M.

2000-01-01

We examine the predictions of Coulomb failure stress and rate-state frictional models. We study the change in failure time (clock advance) Δt due to stress step perturbations (i.e., coseismic static stress increases) added to "background" stressing at a constant rate (i.e., tectonic loading) at time t0. The predictability of Δt implies a predictable change in seismicity rate r(t)/r0, testable using earthquake catalogs, where r0 is the constant rate resulting from tectonic stressing. Models of r(t)/r0, consistent with general properties of aftershock sequences, must predict an Omori law seismicity decay rate, a sequence duration that is less than a few percent of the mainshock cycle time and a return directly to the background rate. A Coulomb model requires that a fault remains locked during loading, that failure occur instantaneously, and that Δt is independent of t0. These characteristics imply an instantaneous infinite seismicity rate increase of zero duration. Numerical calculations of r(t)/r0 for different state evolution laws show that aftershocks occur on faults extremely close to failure at the mainshock origin time, that these faults must be "Coulomb-like," and that the slip evolution law can be precluded. Real aftershock population characteristics also may constrain rate-state constitutive parameters; a may be lower than laboratory values, the stiffness may be high, and/or normal stress may be lower than lithostatic. We also compare Coulomb and rate-state models theoretically. Rate-state model fault behavior becomes more Coulomb-like as constitutive parameter a decreases relative to parameter b. This is because the slip initially decelerates, representing an initial healing of fault contacts. The deceleration is more pronounced for smaller a, more closely simulating a locked fault. Even when the rate-state Δt has Coulomb characteristics, its magnitude may differ by some constant dependent on b. In this case, a rate-state model behaves like a modified Coulomb failure model in which the failure stress threshold is lowered due to weakening, increasing the clock advance. The deviation from a non-Coulomb response also depends on the loading rate, elastic stiffness, initial conditions, and assumptions about how state evolves.

Minimum reaction network necessary to describe Ar/CF4 plasma etch

NASA Astrophysics Data System (ADS)

Helpert, Sofia; Chopra, Meghali; Bonnecaze, Roger T.

2018-03-01

Predicting the etch and deposition profiles created using plasma processes is challenging due to the complexity of plasma discharges and plasma-surface interactions. Volume-averaged global models allow for efficient prediction of important processing parameters and provide a means to quickly determine the effect of a variety of process inputs on the plasma discharge. However, global models are limited based on simplifying assumptions to describe the chemical reaction network. Here a database of 128 reactions is compiled and their corresponding rate constants collected from 24 sources for an Ar/CF4 plasma using the platform RODEo (Recipe Optimization for Deposition and Etching). Six different reaction sets were tested which employed anywhere from 12 to all 128 reactions to evaluate the impact of the reaction database on particle species densities and electron temperature. Because many the reactions used in our database had conflicting rate constants as reported in literature, we also present a method to deal with those uncertainties when constructing the model which includes weighting each reaction rate and filtering outliers. By analyzing the link between a reaction's rate constant and its impact on the predicted plasma densities and electron temperatures, we determine the conditions at which a reaction is deemed necessary to the plasma model. The results of this study provide a foundation for determining which minimal set of reactions must be included in the reaction set of the plasma model.

Prediction of micropollutant elimination during ozonation of a hospital wastewater effluent.

PubMed

Lee, Yunho; Kovalova, Lubomira; McArdell, Christa S; von Gunten, Urs

2014-11-01

Determining optimal ozone doses for organic micropollutant elimination during wastewater ozonation is challenged by the presence of a large number of structurally diverse micropollutants for varying wastewater matrice compositions. A chemical kinetics approach based on ozone and hydroxyl radical (·OH) rate constant and measurements of ozone and ·OH exposures is proposed to predict the micropollutant elimination efficiency. To further test and validate the chemical kinetics approach, the elimination efficiency of 25 micropollutants present in a hospital wastewater effluent from a pilot-scale membrane bioreactor (MBR) were determined at pH 7.0 and 8.5 in bench-scale experiments with ozone alone and ozone combined with H2O2 as a function of DOC-normalized specific ozone doses (gO3/gDOC). Furthermore, ozone and ·OH exposures, ·OH yields, and ·OH consumption rates were determined. Consistent eliminations as a function of gO3/gDOC were observed for micropollutants with similar ozone and ·OH rate constants. They could be classified into five groups having characteristic elimination patterns. By increasing the pH from 7.0 to 8.5, the elimination levels increased for the amine-containing micropollutants due to the increased apparent second-order ozone rate constants while decreased for most micropollutants due to the diminished ozone or ·OH exposures. Increased ·OH quenching by effluent organic matter and carbonate with increasing pH was responsible for the lower ·OH exposures. Upon H2O2 addition, the elimination levels of the micropollutants slightly increased at pH 7 (<8%) while decreased considerably at pH 8.5 (up to 31%). The elimination efficiencies of the selected micropollutants could be predicted based on their ozone and ·OH rate constants (predicted or taken from literature) and the determined ozone and ·OH exposures. Reasonable agreements between the measured and predicted elimination levels were found, demonstrating that the proposed chemical kinetics method can be used for a generalized prediction of micropollutant elimination during wastewater ozonation. Out of 67 analyzed micropollutants, 56 were present in the tested hospital wastewater effluent. Two-thirds of the present micropollutants were found to be ozone-reactive and efficiently eliminated at low ozone doses (e.g., >80% for gO3/gDOC = 0.5). Copyright © 2014 Elsevier Ltd. All rights reserved.

Accuracy of the energy-corrected sudden (ECS) scaling procedure for rotational excitation of CO by collisions with Ar

NASA Technical Reports Server (NTRS)

Green, S.; Cochrane, D. L.; Truhlar, D. G.

1986-01-01

The utility of the energy-corrected sudden (ECS) scaling method is evaluated on the basis of how accurately it predicts the entire matrix of state-to-state rate constants, when the fundamental rate constants are independently known. It is shown for the case of Ar-CO collisions at 500 K that when a critical impact parameter is about 1.75-2.0 A, the ECS method yields excellent excited state rates on the average and has an rms error of less than 20 percent.

Evaluation of procedures for estimating ruminal particle turnover and diet digestibility in ruminant animals

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

Cochran, R.C.

1985-01-01

Procedures used in estimating ruminal particle turnover and diet digestibility were evaluated in a series of independent experiments. Experiment 1 and 2 evaluated the influence of sampling site, mathematical model and intraruminal mixing on estimates of ruminal particle turnover in beef steers grazing crested wheatgrass or offered ad libitum levels of prairie hay once daily, respectively. Particle turnover rate constants were estimated by intraruminal administration (via rumen cannula) of ytterbium (Yb)-labeled forage, followed by serial collection of rumen digesta or fecal samples. Rumen Yb concentrations were transformed to natural logarithms and regressed on time. Influence of sampling site (rectum versusmore » rumen) on turnover estimates was modified by the model used to fit fecal marker excretion curves in the grazing study. In contrast, estimated turnover rate constants from rumen sampling were smaller (P < 0.05) than rectally derived rate constants, regardless of fecal model used, when steers were fed once daily. In Experiment 3, in vitro residues subjected to acid or neutral detergent fiber extraction (IVADF and IVNDF), acid detergent fiber incubated in cellulase (ADFIC) and acid detergent lignin (ADL) were evaluated as internal markers for predicting diet digestibility. Both IVADF and IVNDF displayed variable accuracy for prediction of in vivo digestibility whereas ADL and ADFIC inaccurately predicted digestibility of all diets.« less

Fatigue-Life Prediction Methodology Using Small-Crack Theory

NASA Technical Reports Server (NTRS)

Newmann, James C., Jr.; Phillips, Edward P.; Swain, M. H.

1997-01-01

This paper reviews the capabilities of a plasticity-induced crack-closure model to predict fatigue lives of metallic materials using 'small-crack theory' for various materials and loading conditions. Crack-tip constraint factors, to account for three-dimensional state-of-stress effects, were selected to correlate large-crack growth rate data as a function of the effective-stress-intensity factor range (delta K(eff)) under constant-amplitude loading. Some modifications to the delta k(eff)-rate relations were needed in the near-threshold regime to fit measured small-crack growth rate behavior and fatigue endurance limits. The model was then used to calculate small- and large-crack growth rates, and to predict total fatigue lives, for notched and un-notched specimens made of two aluminum alloys and a steel under constant-amplitude and spectrum loading. Fatigue lives were calculated using the crack-growth relations and microstructural features like those that initiated cracks for the aluminum alloys and steel for edge-notched specimens. An equivalent-initial-flaw-size concept was used to calculate fatigue lives in other cases. Results from the tests and analyses agreed well.

Prediction of Metabolite Concentrations, Rate Constants and Post-Translational Regulation Using Maximum Entropy-Based Simulations with Application to Central Metabolism of Neurospora crassa

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

Cannon, William; Zucker, Jeremy; Baxter, Douglas

We report the application of a recently proposed approach for modeling biological systems using a maximum entropy production rate principle in lieu of having in vivo rate constants. The method is applied in four steps: (1) a new ODE-based optimization approach based on Marcelin’s 1910 mass action equation is used to obtain the maximum entropy distribution, (2) the predicted metabolite concentrations are compared to those generally expected from experiment using a loss function from which post-translational regulation of enzymes is inferred, (3) the system is re-optimized with the inferred regulation from which rate constants are determined from the metabolite concentrationsmore » and reaction fluxes, and finally (4) a full ODE-based, mass action simulation with rate parameters and allosteric regulation is obtained. From the last step, the power characteristics and resistance of each reaction can be determined. The method is applied to the central metabolism of Neurospora crassa and the flow of material through the three competing pathways of upper glycolysis, the non-oxidative pentose phosphate pathway, and the oxidative pentose phosphate pathway are evaluated as a function of the NADP/NADPH ratio. It is predicted that regulation of phosphofructokinase (PFK) and flow through the pentose phosphate pathway are essential for preventing an extreme level of fructose 1, 6-bisphophate accumulation. Such an extreme level of fructose 1,6-bisphophate would otherwise result in a glassy cytoplasm with limited diffusion, dramatically decreasing the entropy and energy production rate and, consequently, biological competitiveness.« less

Improving Accuracy in Arrhenius Models of Cell Death: Adding a Temperature-Dependent Time Delay.

PubMed

Pearce, John A

2015-12-01

The Arrhenius formulation for single-step irreversible unimolecular reactions has been used for many decades to describe the thermal damage and cell death processes. Arrhenius predictions are acceptably accurate for structural proteins, for some cell death assays, and for cell death at higher temperatures in most cell lines, above about 55 °C. However, in many cases--and particularly at hyperthermic temperatures, between about 43 and 55 °C--the particular intrinsic cell death or damage process under study exhibits a significant "shoulder" region that constant-rate Arrhenius models are unable to represent with acceptable accuracy. The primary limitation is that Arrhenius calculations always overestimate the cell death fraction, which leads to severely overoptimistic predictions of heating effectiveness in tumor treatment. Several more sophisticated mathematical model approaches have been suggested and show much-improved performance. But simpler models that have adequate accuracy would provide useful and practical alternatives to intricate biochemical analyses. Typical transient intrinsic cell death processes at hyperthermic temperatures consist of a slowly developing shoulder region followed by an essentially constant-rate region. The shoulder regions have been demonstrated to arise chiefly from complex functional protein signaling cascades that generate delays in the onset of the constant-rate region, but may involve heat shock protein activity as well. This paper shows that acceptably accurate and much-improved predictions in the simpler Arrhenius models can be obtained by adding a temperature-dependent time delay. Kinetic coefficients and the appropriate time delay are obtained from the constant-rate regions of the measured survival curves. The resulting predictions are seen to provide acceptably accurate results while not overestimating cell death. The method can be relatively easily incorporated into numerical models. Additionally, evidence is presented to support the application of compensation law behavior to the cell death processes--that is, the strong correlation between the kinetic coefficients, ln{A} and E(a), is confirmed.

Influence of humic acid addition on the degradation of pharmaceuticals by biofilms in effluent wastewater.

PubMed

Tang, Kai; Escola Casas, Monica; Ooi, Gordon T H; Kaarsholm, Kamilla M S; Bester, Kai; Andersen, Henrik R

2017-05-01

The degradation of organic micropollutants in wastewater treatment is suspected to depend on co-degradation i.e. be dependent on concentrations of substrate. This complicates predicting and modelling their fate. The effect of humic acid, as a model for complex organic substrate, was investigated in relation to the biodegradation of pharmaceuticals by suspended biofilm carriers adapted to polishing effluent water from a tertiary sewage treatment plant. Twelve out of 22 investigated pharmaceuticals were significantly biodegradable. The biodegradation rate constants of ten of those compounds were increasing with increased humic acid concentrations. At the highest humic acid concentration (30mgC/L), the biodegradation rate constants were four times higher than the biodegradation rate constants without added humic acid. This shows that the presence of complex substrate stimulates degradation via a co-metabolism-like mechanism and competitive inhibition does not occur. Increases of rate constant per mgC/L are tentatively calculated. Copyright © 2017 Elsevier GmbH. All rights reserved.

A theoretical and shock tube kinetic study on hydrogen abstraction from phenyl formate.

PubMed

Ning, Hongbo; Liu, Dapeng; Wu, Junjun; Ma, Liuhao; Ren, Wei; Farooq, Aamir

2018-06-12

The hydrogen abstraction reactions of phenyl formate (PF) by different radicals (H/O(3P)/OH/HO2) were theoretically investigated. We calculated the reaction energetics for PF + H/O/OH using the composite method ROCBS-QB3//M06-2X/cc-pVTZ and that for PF + HO2 at the M06-2X/cc-pVTZ level of theory. The high-pressure limit rate constants were calculated using the transition state theory in conjunction with the 1-D hindered rotor approximation and tunneling correction. Three-parameter Arrhenius expressions of rate constants were provided over the temperature range of 500-2000 K. To validate the theoretical calculations, the overall rate constants of PF + OH → Products were measured in shock tube experiments at 968-1128 K and 1.16-1.25 atm using OH laser absorption. The predicted overall rate constants agree well with the shock tube data (within 15%) over the entire experimental conditions. Rate constant analysis indicates that the H-abstraction at the formic acid site dominates the PF consumption, whereas the contribution of H-abstractions at the aromatic ring increases with temperature. Additionally, comparisons of site-specific H-abstractions from PF with methyl formate, ethyl formate, benzene, and toluene were performed to understand the effects of the aromatic ring and side-chain substituent on H-abstraction rate constants.

Ab Initio Chemical Kinetics for the CH3 + O((3)P) Reaction and Related Isomerization-Decomposition of CH3O and CH2OH Radicals.

PubMed

Xu, Z F; Raghunath, P; Lin, M C

2015-07-16

The kinetics and mechanism of the CH3 + O reaction and related isomerization-decomposition of CH3O and CH2OH radicals have been studied by ab initio molecular orbital theory based on the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ, CCSD/aug-cc-pVDZ, and G2M//B3LYP/6-311+G(3df,2p) levels of theory. The predicted potential energy surface of the CH3 + O reaction shows that the CHO + H2 products can be directly generated from CH3O by the TS3 → LM1 → TS7 → LM2 → TS4 path, in which both LM1 and LM2 are very loose and TS7 is roaming-like. The result for the CH2O + H reaction shows that there are three low-energy barrier processes including CH2O + H → CHO + H2 via H-abstraction and CH2O + H → CH2OH and CH2O + H → CH3O by addition reactions. The predicted enthalpies of formation of the CH2OH and CH3O radicals at 0 K are in good agreement with available experimental data. Furthermore, the rate constants for the forward and some key reverse reactions have been predicted at 200-3000 K under various pressures. Based on the new reaction pathway for CH3 + O, the rate constants for the CH2O + H and CHO + H2 reactions were predicted with the microcanonical variational transition-state/Rice-Ramsperger-Kassel-Marcus (VTST/RRKM) theory. The predicted total and individual product branching ratios (i.e., CO versus CH2O) are in good agreement with experimental data. The rate constant for the hydrogen abstraction reaction of CH2O + H has been calculated by the canonical variational transition-state theory with quantum tunneling and small-curvature corrections to be k(CH2O + H → CHO + H2) = 2.28 × 10(-19) T(2.65) exp(-766.5/T) cm(3) molecule(-1) s(-1) for the 200-3000 K temperature range. The rate constants for the addition giving CH3O and CH2OH and the decomposition of the two radicals have been calculated by the microcanonical RRKM theory with the time-dependent master equation solution of the multiple quantum well system in the 200-3000 K temperature range at 1 Torr to 100 atm. The predicted rate constants are in good agreement with most of the available data.

The effect of ionic interactions on the oxidation of metals in natural waters

NASA Astrophysics Data System (ADS)

Millero, Frank J.

1985-02-01

The effect of ionic interactions of the major components of natural waters on the oxidation of Cu(I) and Fe(II) has been examined. The various ion pairs of these metals have been shown to have different rates of oxidation. For Fe(II), the chloride and sulfate ion pairs are not easily oxidized. The measured decrease in the rate constant at a fixed pH in chloride and sulfate solutions agrees very well with the values predicted. The effect of pH (6 to 8) on the oxidation of Fe(II) in water and seawater have been shown to follow the rate equation -d in [Fe(II)]/dt = k 1β 1α Fe/[H +] + k 2β 2α Fe/[H +] 2 where k1 and k2 are the pseudo first order rate constants, β1 and β2 are the hydrolysis constants for Fe(OH) + and Fe(OH) 0. The value of αFE is the fraction of free Fe 2+. The value of k1 (2.0 ±0.5 min-1) in water and seawater are similar within experimental error. The value of k2 (1.2 × 10 5 min -1) in seawater is 28% of its value in water in reasonable agreement with predictions using an ion pairing model. For the oxidation of Cu(I) a rate equation of the form -d ln [Cu(I)]/dt = k 0α Cu+ k 1β 1α Cu[Cl] was found where k0 (14.1 sec -1) and k1 (3.9 sec -1) are the pseudo first order rate constants for the oxidation of Cu + and CuCl 0, β1 is the formation constant for CuCl 0 and αCu is the fraction of free Cu +. Thus, unlike the results for Fe(II), Cu(I) chloride complexes have measurable rates of oxidation.

Reaction of SO2 with OH in the atmosphere.

PubMed

Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G

2017-03-15

The OH + SO 2 reaction plays a critical role in understanding the oxidation of SO 2 in the atmosphere, and its rate constant is critical for clarifying the fate of SO 2 in the atmosphere. The rate constant of the OH + SO 2 reaction is calculated here by using beyond-CCSDT correlation energy calculations for a benchmark, validated density functional methods for direct dynamics, canonical variational transition state theory with anharmonicity and multidimensional tunneling for the high-pressure rate constant, and system-specific quantum RRK theory for pressure effects; the combination of these methods can compete in accuracy with experiments. There has been a long-term debate in the literature about whether the OH + SO 2 reaction is barrierless, but our calculations indicate a positive barrier with an transition structure that has an enthalpy of activation of 0.27 kcal mol -1 at 0 K. Our results show that the high-pressure limiting rate constant of the OH + SO 2 reaction has a positive temperature dependence, but the rate constant at low pressures has a negative temperature dependence. The computed high-pressure limiting rate constant at 298 K is 1.25 × 10 -12 cm 3 molecule -1 s -1 , which agrees excellently with the value (1.3 × 10 -12 cm 3 molecule -1 s -1 ) recommended in the most recent comprehensive evaluation for atmospheric chemistry. We show that the atmospheric lifetime of SO 2 with respect to oxidation by OH depends strongly on altitude (in the range 0-50 km) due to the falloff effect. We introduce a new interpolation procedure for fitting the combined temperature and pressure dependence of the rate constant, and it fits the calculated rate constants over the whole range with a mean unsigned error of only 7%. The present results provide reliable kinetics data for this specific reaction, and also they demonstrate convenient theoretical methods that can be reliable for predicting rate constants of other gas-phase reactions.

Determination of Chemical Kinetic Rate Constants of a Model for Carbothermal Processing of Lunar Regolith Simulant Using Methane

NASA Technical Reports Server (NTRS)

Balasubramaniam, R; Gokoglu, S.; Hegde, U.

2009-01-01

We have previously developed a chemical conversion model of the carbothermal processing of lunar regolith using methane to predict the rate of production of carbon monoxide. In this carbothermal process, gaseous methane is pyrolyzed as it flows over the hot surface of a molten zone of lunar regolith and is converted to carbon and hydrogen. Hydrogen is carried away by the exiting stream of gases and carbon is deposited on the melt surface. The deposited carbon mixes with the melt and reacts with the metal oxides in it to produce carbon monoxide that bubbles out of the melt. In our model, we assume that the flux of carbon deposited is equal to the product of the surface reaction rate constant gamma and the concentration of methane adjacent to the melt surface. Similarly, the rate of consumption of carbon per unit volume in the melt is equal to the product of the melt reaction rate constant k and the concentrations of carbon and metal oxide in the melt. In this paper, we describe our effort to determine gamma and k by comparison of the predictions from our model with test data obtained by ORBITEC (Orbital Technologies Corporation). The concentration of methane adjacent to the melt surface is a necessary input to the model. It is inferred from the test data by a mass balance of methane, adopting the usual assumptions of the continuously-stirred-tank-reactor model, whereby the average concentration of a given gaseous species equals its exit concentration. The reaction rates gamma and k have been determined by a non-linear least-squares fit to the test data for the production of carbon monoxide and the fraction of the incoming methane that is converted. The comparison of test data with our model predictions using the determined chemical kinetic rate constants provides a consistent interpretation of the process over the full range of temperatures, pressures, and methane flow rates used in the tests, thereby increasing our confidence to use the model for scale-up purposes.

Constant-roll (quasi-)linear inflation

NASA Astrophysics Data System (ADS)

Karam, A.; Marzola, L.; Pappas, T.; Racioppi, A.; Tamvakis, K.

2018-05-01

In constant-roll inflation, the scalar field that drives the accelerated expansion of the Universe is rolling down its potential at a constant rate. Within this framework, we highlight the relations between the Hubble slow-roll parameters and the potential ones, studying in detail the case of a single-field Coleman-Weinberg model characterised by a non-minimal coupling of the inflaton to gravity. With respect to the exact constant-roll predictions, we find that assuming an approximate slow-roll behaviour yields a difference of Δ r = 0.001 in the tensor-to-scalar ratio prediction. Such a discrepancy is in principle testable by future satellite missions. As for the scalar spectral index ns, we find that the existing 2-σ bound constrains the value of the non-minimal coupling to ξphi ~ 0.29–0.31 in the model under consideration.

Using a reactive transport model to elucidate differences between laboratory and field dissolution rates in regolith

NASA Astrophysics Data System (ADS)

Moore, Joel; Lichtner, Peter C.; White, Art F.; Brantley, Susan L.

2012-09-01

The reactive transport model FLOTRAN was used to forward-model weathering profiles developed on granitic outwash alluvium over 40-3000 ka from the Merced, California (USA) chronosequence as well as deep granitic regolith developed over 800 ka near Davis Run, Virginia (USA). Baseline model predictions that used laboratory rate constants (km), measured fluid flow velocities (v), and BET volumetric surface areas for the parent material (AB,mo) were not consistent with measured profiles of plagioclase, potassium feldspar, and quartz. Reaction fronts predicted by the baseline model are deeper and thinner than the observed, consistent with faster rates of reaction in the model. Reaction front depth in the model depended mostly upon saturated versus unsaturated hydrologic flow conditions, rate constants controlling precipitation of secondary minerals, and the average fluid flow velocity (va). Unsaturated hydrologic flow conditions (relatively open with respect to CO2(g)) resulted in the prediction of deeper reaction fronts and significant differences in the separation between plagioclase and potassium feldspar reaction fronts compared to saturated hydrologic flow (relatively closed with respect to CO2(g)). Under saturated or unsaturated flow conditions, the rate constant that controls precipitation rates of secondary minerals must be reduced relative to laboratory rate constants to match observed reaction front depths and measured pore water chemistry. Additionally, to match the observed reaction front depths, va was set lower than the measured value, v, for three of the four profiles. The reaction front gradients in mineralogy and pore fluid chemistry could only be modeled accurately by adjusting values of the product kmAB,mo. By assuming km values were constrained by laboratory data, field observations were modeled successfully with TST-like rate equations by dividing measured values of AB,mo by factors from 50 to 1700. Alternately, with sigmoidal or Al-inhibition rate models, this adjustment factor ranges from 5 to 170. Best-fit models of the wetter, hydrologically saturated Davis Run profile required a smaller adjustment to AB,mo than the drier hydrologically unsaturated Merced profiles. We attributed the need for large adjustments in va and AB,mo necessary for the Merced models to more complex hydrologic flow that decreased the reactive surface area in contact with bulk flow water, e.g., dead-end pore spaces containing fluids that are near or at chemical equilibrium. Thus, rate models from the laboratory can successfully predict weathering over millions of years, but work is needed to understand how to incorporate changes in what controls the relationship between reactive surface area and hydrologic flow.

Modelling the charring behaviour of structural lumber

Treesearch

Peter W.C. Lau; Robert White; Ineke Van Zealand

1999-01-01

Charring rates for large-section timber based on experimental data have been generally established. The established rates may not be appropriately used for the prediction of failure times of lumber members which are small by comparison. It is questionable whether a constant rate can be safely assumed for lumber members since the rate is likely to increase once the...

An investigation of the thermoviscoplastic behavior of a metal matrix composite at elevated temperatures

NASA Technical Reports Server (NTRS)

Rogacki, John R.; Tuttle, Mark E.

1992-01-01

This research investigates the response of a fiberless 13 layer hot isostatically pressed Ti-15-3 laminate to creep, constant strain rate, and cyclic constant strain rate loading at temperatures ranging from 482C to 649C. Creep stresses from 48 to 260 MPa and strain rates of .0001 to .01 m/m/sec were used. Material parameters for three unified constitutive models (Bodner-Partom, Miller, and Walker models) were determined for Ti-15-3 from the experimental data. Each of the three models was subsequently incorporated into a rule of mixtures and evaluated for accuracy and ease of use in predicting the thermoviscoplastic response of unidirectional metal matrix composite laminates (both 0 and 90). The laminates were comprised of a Ti-15-3 matrix with 29 volume percent SCS6 fibers. The predicted values were compared to experimentally determined creep and constant strain rate data. It was found that all three models predicted the viscoplastic response of the 0 specimens reasonably well, but seriously underestimated the viscoplastic response of the 90 specimens. It is believed that this discrepancy is due to compliant and/or weak fiber-matrix interphase. In general, it was found that of the three models studied, the Bodner-Partom model was easiest to implement, primarily because this model does not require the use of cyclic constant strain rate tests to determine the material parameters involved. However, the version of the Bodner-Partom model used in this study does not include back stress as an internal state variable, and hence may not be suitable for use with materials which exhibit a pronounced Baushinger effect. The back stress is accounted for in both the Walker and Miller models; determination of the material parameters associated with the Walker model was somewhat easier than in the Miller model.

A thermal NO(x) prediction model - Scalar computation module for CFD codes with fluid and kinetic effects

NASA Technical Reports Server (NTRS)

Mcbeath, Giorgio; Ghorashi, Bahman; Chun, Kue

1993-01-01

A thermal NO(x) prediction model is developed to interface with a CFD, k-epsilon based code. A converged solution from the CFD code is the input to the postprocessing model for prediction of thermal NO(x). The model uses a decoupled analysis to estimate the equilibrium level of (NO(x))e which is the constant rate limit. This value is used to estimate the flame (NO(x)) and in turn predict the rate of formation at each node using a two-step Zeldovich mechanism. The rate is fixed on the NO(x) production rate plot by estimating the time to reach equilibrium by a differential analysis based on the reaction: O + N2 = NO + N. The rate is integrated in the nonequilibrium time space based on the residence time at each node in the computational domain. The sum of all nodal predictions yields the total NO(x) level.

Galaxy Formation Efficiency and the Multiverse Explanation of the Cosmological Constant with EAGLE Simulations

NASA Astrophysics Data System (ADS)

Barnes, Luke A.; Elahi, Pascal J.; Salcido, Jaime; Bower, Richard G.; Lewis, Geraint F.; Theuns, Tom; Schaller, Matthieu; Crain, Robert A.; Schaye, Joop

2018-04-01

Models of the very early universe, including inflationary models, are argued to produce varying universe domains with different values of fundamental constants and cosmic parameters. Using the cosmological hydrodynamical simulation code from the EAGLE collaboration, we investigate the effect of the cosmological constant on the formation of galaxies and stars. We simulate universes with values of the cosmological constant ranging from Λ = 0 to Λ0 × 300, where Λ0 is the value of the cosmological constant in our Universe. Because the global star formation rate in our Universe peaks at t = 3.5 Gyr, before the onset of accelerating expansion, increases in Λ of even an order of magnitude have only a small effect on the star formation history and efficiency of the universe. We use our simulations to predict the observed value of the cosmological constant, given a measure of the multiverse. Whether the cosmological constant is successfully predicted depends crucially on the measure. The impact of the cosmological constant on the formation of structure in the universe does not seem to be a sharp enough function of Λ to explain its observed value alone.

Galaxy formation efficiency and the multiverse explanation of the cosmological constant with EAGLE simulations

NASA Astrophysics Data System (ADS)

Barnes, Luke A.; Elahi, Pascal J.; Salcido, Jaime; Bower, Richard G.; Lewis, Geraint F.; Theuns, Tom; Schaller, Matthieu; Crain, Robert A.; Schaye, Joop

2018-07-01

Models of the very early Universe, including inflationary models, are argued to produce varying universe domains with different values of fundamental constants and cosmic parameters. Using the cosmological hydrodynamical simulation code from the EAGLE collaboration, we investigate the effect of the cosmological constant on the formation of galaxies and stars. We simulate universes with values of the cosmological constant ranging from Λ = 0 to Λ0 × 300, where Λ0 is the value of the cosmological constant in our Universe. Because the global star formation rate in our Universe peaks at t = 3.5 Gyr, before the onset of accelerating expansion, increases in Λ of even an order of magnitude have only a small effect on the star formation history and efficiency of the universe. We use our simulations to predict the observed value of the cosmological constant, given a measure of the multiverse. Whether the cosmological constant is successfully predicted depends crucially on the measure. The impact of the cosmological constant on the formation of structure in the universe does not seem to be a sharp enough function of Λ to explain its observed value alone.

Laboratory constraints on models of earthquake recurrence

NASA Astrophysics Data System (ADS)

Beeler, N. M.; Tullis, Terry; Junger, Jenni; Kilgore, Brian; Goldsby, David

2014-12-01

In this study, rock friction "stick-slip" experiments are used to develop constraints on models of earthquake recurrence. Constant rate loading of bare rock surfaces in high-quality experiments produces stick-slip recurrence that is periodic at least to second order. When the loading rate is varied, recurrence is approximately inversely proportional to loading rate. These laboratory events initiate due to a slip-rate-dependent process that also determines the size of the stress drop and, as a consequence, stress drop varies weakly but systematically with loading rate. This is especially evident in experiments where the loading rate is changed by orders of magnitude, as is thought to be the loading condition of naturally occurring, small repeating earthquakes driven by afterslip, or low-frequency earthquakes loaded by episodic slip. The experimentally observed stress drops are well described by a logarithmic dependence on recurrence interval that can be cast as a nonlinear slip predictable model. The fault's rate dependence of strength is the key physical parameter. Additionally, even at constant loading rate the most reproducible laboratory recurrence is not exactly periodic, unlike existing friction recurrence models. We present example laboratory catalogs that document the variance and show that in large catalogs, even at constant loading rate, stress drop and recurrence covary systematically. The origin of this covariance is largely consistent with variability of the dependence of fault strength on slip rate. Laboratory catalogs show aspects of both slip and time predictability, and successive stress drops are strongly correlated indicating a "memory" of prior slip history that extends over at least one recurrence cycle.

Tensile properties of AZ11A-0 magnesium-alloy sheet under rapid-heating and constant temperature

NASA Technical Reports Server (NTRS)

Kurg, Ivo M

1956-01-01

Specimens of AZ31A-0 magnesium alloy sheet were heated to rupture at nominal rates of 0.2 F to 100 F per second under constant tensile load conditions. The data are presented and compared with the results of conventional tensile stress-strain tests at elevated temperatures after 1.2-hour exposure. A temperature-rate parameter was used to construct master curves from which stresses and temperatures for yield and rupture can be predicted under rapid-heating conditions. A comparison of the elevated-temperature tensile properties of AZ31A-0 and HK31XA-H24 magnesium-alloy sheet under both constant-temperature and rapid-heating conditions is included.

Efficient quantum-classical method for computing thermal rate constant of recombination: application to ozone formation.

PubMed

Ivanov, Mikhail V; Babikov, Dmitri

2012-05-14

Efficient method is proposed for computing thermal rate constant of recombination reaction that proceeds according to the energy transfer mechanism, when an energized molecule is formed from reactants first, and is stabilized later by collision with quencher. The mixed quantum-classical theory for the collisional energy transfer and the ro-vibrational energy flow [M. Ivanov and D. Babikov, J. Chem. Phys. 134, 144107 (2011)] is employed to treat the dynamics of molecule + quencher collision. Efficiency is achieved by sampling simultaneously (i) the thermal collision energy, (ii) the impact parameter, and (iii) the incident direction of quencher, as well as (iv) the rotational state of energized molecule. This approach is applied to calculate third-order rate constant of the recombination reaction that forms the (16)O(18)O(16)O isotopomer of ozone. Comparison of the predicted rate vs. experimental result is presented.

A novel frame-level constant-distortion bit allocation for smooth H.264/AVC video quality

NASA Astrophysics Data System (ADS)

Liu, Li; Zhuang, Xinhua

2009-01-01

It is known that quality fluctuation has a major negative effect on visual perception. In previous work, we introduced a constant-distortion bit allocation method [1] for H.263+ encoder. However, the method in [1] can not be adapted to the newest H.264/AVC encoder directly as the well-known chicken-egg dilemma resulted from the rate-distortion optimization (RDO) decision process. To solve this problem, we propose a new two stage constant-distortion bit allocation (CDBA) algorithm with enhanced rate control for H.264/AVC encoder. In stage-1, the algorithm performs RD optimization process with a constant quantization QP. Based on prediction residual signals from stage-1 and target distortion for smooth video quality purpose, the frame-level bit target is allocated by using a close-form approximations of ratedistortion relationship similar to [1], and a fast stage-2 encoding process is performed with enhanced basic unit rate control. Experimental results show that, compared with original rate control algorithm provided by H.264/AVC reference software JM12.1, the proposed constant-distortion frame-level bit allocation scheme reduces quality fluctuation and delivers much smoother PSNR on all testing sequences.

Prediction of Rate Constant for Supramolecular Systems with Multiconfigurations.

PubMed

Guo, Tao; Li, Haiyan; Wu, Li; Guo, Zhen; Yin, Xianzhen; Wang, Caifen; Sun, Lixin; Shao, Qun; Gu, Jingkai; York, Peter; Zhang, Jiwen

2016-02-25

The control of supramolecular systems requires a thorough understanding of their dynamics, especially on a molecular level. It is extremely difficult to determine the thermokinetic parameters of supramolecular systems, such as drug-cyclodextrin complexes with fast association/dissociation processes by experimental techniques. In this paper, molecular modeling combined with novel mathematical relationships integrating the thermodynamic/thermokinetic parameters of a series of isomeric multiconfigurations to predict the overall parameters in a range of pH values have been employed to study supramolecular dynamics at the molecular level. A suitable form of Eyring's equation was derived and a two-stage model was introduced. The new approach enabled accurate prediction of the apparent dissociation/association (k(off)/k(on)) and unbinding/binding (k-r/kr) rate constants of the ubiquitous multiconfiguration complexes of the supramolecular system. The pyronine Y (PY) was used as a model system for the validation of the presented method. Interestingly, the predicted k(off) value ((40 ± 1) × 10(5) s(-1), 298 K) of PY is largely in agreement with that previously determined by fluorescence correlation spectroscopy ((5 ± 3) × 10(5) s(-1), 298 K). Moreover, the k(off)/k(on) and k-r/kr for flurbiprofen-β-cylcodextrin and ibuprofen-β-cyclodextrin systems were also predicted and suggested that the association processes are diffusion-controlled. The methodology is considered to be especially useful in the design and selection of excipients for a supramolecular system with preferred association and dissociation rate constants and understanding their mechanisms. It is believed that this new approach could be applicable to a wide range of ligand-receptor supramolecular systems and will surely help in understanding their complex mechanism.

Evaluation of three statistical prediction models for forensic age prediction based on DNA methylation.

PubMed

Smeers, Inge; Decorte, Ronny; Van de Voorde, Wim; Bekaert, Bram

2018-05-01

DNA methylation is a promising biomarker for forensic age prediction. A challenge that has emerged in recent studies is the fact that prediction errors become larger with increasing age due to interindividual differences in epigenetic ageing rates. This phenomenon of non-constant variance or heteroscedasticity violates an assumption of the often used method of ordinary least squares (OLS) regression. The aim of this study was to evaluate alternative statistical methods that do take heteroscedasticity into account in order to provide more accurate, age-dependent prediction intervals. A weighted least squares (WLS) regression is proposed as well as a quantile regression model. Their performances were compared against an OLS regression model based on the same dataset. Both models provided age-dependent prediction intervals which account for the increasing variance with age, but WLS regression performed better in terms of success rate in the current dataset. However, quantile regression might be a preferred method when dealing with a variance that is not only non-constant, but also not normally distributed. Ultimately the choice of which model to use should depend on the observed characteristics of the data. Copyright © 2018 Elsevier B.V. All rights reserved.

Assessment of natural attenuation of aromatic hydrocarbons in groundwater near a former manufactured-gas plant, South Carolina, USA

USGS Publications Warehouse

Landmeyer, J.E.; Chapelle, F.H.; Petkewich, M.D.; Bradley, P.M.

1998-01-01

Shallow, anaerobic groundwater near a former manufactured-gas plant (MGP) in Charleston, South Carolina, USA, contains mono- and polycyclic aromatic hydrocarbons (MAHs and PAHs, respectively). Between 1994 and 1997, a combination of field, laboratory, and numerical-flow and transport-model investigations were made to assess natural attenuation processes affecting MAH and PAH distributions. This assessment included determination of adsorption coefficients (K(ad)) and first-order biodegradation rate constants (K(bio)) using aquifer material from the MGP site and adjacent properties. Naphthalene adsorption (K(ad) = 1.35 x 10-7 m3/mg) to aquifer sediments was higher than toluene adsorption (K(ad) = 9.34 x 10-10 m3/mg), suggesting preferential toluene transport relative to naphthalene. However, toluene and benzene distributions measured in January 1994 were smaller than the naphthalene distribution. This scenario can be explained, in part, by the differences between biodegradation rates of the compounds. Aerobic first-order rate constants of 14C-toluene, 14C-benzene, and 14C-naphthalene degradation were similar (-0.84, -0.03, and 0.88 day-1, respectively), but anaerobic rate constants were higher for toluene and benzene (-0.002 and -0.00014 day-1, respectively) than for naphthalene (-0.000046 day-1). Both areal and cross-sectional numerical simulations were used to test the hypothesis suggested by these rate differences that MAH compounds will be contained relative to PAHs. Predictive simulations indicated that the distributions of toluene and benzene reach steady-state conditions before groundwater flow lines discharge to an adjacent surface-water body, but do discharge low concentrations of naphthalene. Numerical predictions were 'audited' by measuring concentrations of naphthalene, toluene, and benzene at the site in early 1997. Measured naphthalene and toluene concentrations were substantially reduced and the areal extent of contamination smaller than was both observed in January 1994 and predicted for 1997. Measured 1997 benzene concentrations and distribution were shown to be relatively unchanged from those measured in 1994, and similar to predictions for 1997.The natural attenuation processes affecting mono- and polycyclic aromatic hydrocarbons (MAHs and PAHs, respectively) distributions in groundwater near a former manufactured-gas plant in South Carolina, USA was evaluated. This assessment included determination of adsorption coefficients and first-order biodegradation rate constants. Detailed results obtained in the study are presented.

A modified parallel artificial membrane permeability assay for evaluating the bioconcentration of highly hydrophobic chemicals in fish.

PubMed

Kwon, Jung-Hwan; Escher, Beate I

2008-03-01

Low cost in vitro tools are needed at the screening stage of assessment of bioaccumulation potential of new and existing chemicals because the number of chemical substances that needs to be tested highly exceeds the capacity of in vivo bioconcentration tests. Thus, the parallel artificial membrane permeability assay (PAMPA) system was modified to predict passive uptake/ elimination rate in fish. To overcome the difficulties associated with low aqueous solubility and high membrane affinity of highly hydrophobic chemicals, we measured the rate of permeation from the donor poly(dimethylsiloxane)(PDMS) disk to the acceptor PDMS disk through aqueous and PDMS membrane boundary layers and term the modified PAMPA system "PDMS-PAMPA". Twenty chemicals were selected for validation of PDMS-PAMPA. The measured permeability is proportional to the passive elimination rate constant in fish and was used to predict the "minimum" in vivo elimination rate constant. The in vivo data were very close to predicted values except for a few polar chemicals and metabolically active chemicals, such as pyrene and benzo[a]pyrene. Thus, PDMS-PAMPA can be an appropriate in vitro system for nonmetabolizable chemicals. Combination with metabolic clearance rates using a battery of metabolic degradation assays would enhance the applicability for metabolizable chemicals.

Uncertainty quantification of reaction mechanisms accounting for correlations introduced by rate rules and fitted Arrhenius parameters

DOE PAGES

Prager, Jens; Najm, Habib N.; Sargsyan, Khachik; ...

2013-02-23

We study correlations among uncertain Arrhenius rate parameters in a chemical model for hydrocarbon fuel-air combustion. We consider correlations induced by the use of rate rules for modeling reaction rate constants, as well as those resulting from fitting rate expressions to empirical measurements arriving at a joint probability density for all Arrhenius parameters. We focus on homogeneous ignition in a fuel-air mixture at constant-pressure. We also outline a general methodology for this analysis using polynomial chaos and Bayesian inference methods. Finally, we examine the uncertainties in both the Arrhenius parameters and in predicted ignition time, outlining the role of correlations,more » and considering both accuracy and computational efficiency.« less

POSTERIOR PREDICTIVE MODEL CHECKS FOR DISEASE MAPPING MODELS. (R827257)

EPA Science Inventory

Disease incidence or disease mortality rates for small areas are often displayed on maps. Maps of raw rates, disease counts divided by the total population at risk, have been criticized as unreliable due to non-constant variance associated with heterogeneity in base population si...

Kinetics of the addition of olefins to Si-centered radicals: the critical role of dispersion interactions revealed by theory and experiment.

PubMed

Johnson, Erin R; Clarkin, Owen J; Dale, Stephen G; DiLabio, Gino A

2015-06-04

Solution-phase rate constants for the addition of selected olefins to the triethylsilyl and tris(trimethylsilyl)silyl radicals are measured using laser-flash photolysis and competition kinetics. The results are compared with predictions from density functional theory (DFT) calculations, both with and without dispersion corrections obtained from the exchange-hole dipole moment (XDM) model. Without a dispersion correction, the rate constants are consistently underestimated; the errors increase with system size, up to 10(6) s(-1) for the largest system considered. Dispersion interactions preferentially stabilize the transition states relative to the separated reactants and bring the DFT-calculated rate constants into excellent agreement with experiment. Thus, dispersion interactions are found to play a key role in determining the kinetics for addition reactions, particularly those involving sterically bulky functional groups.

Isothermal-desorption-rate measurements in the vicinity of the Curie temperature for H2 chemisorbed on nickel films

NASA Technical Reports Server (NTRS)

Shanabarger, M. R.

1979-01-01

Measurements of the isothermal desorption rate of H2 chemisorbed onto polycrystalline nickel films made for temperatures spanning the Curie temperature of the nickel film are presented. Desorption kinetics were followed by measuring the decay of the change in resistance of the nickel film brought about by hydrogen chemisorption after gas-phase H2 had been rapidly evacuated. The desorption rate is found to undergo an anomalous decrease in the vicinity of the Curie temperature, accompanied by an increase in the desorption activation energy and the equilibrium constant for the chemisorbed hydrogen. The results are interpreted in terms of anomalous variations in rate constants for the formation of the precursor molecular adsorbed state and the chemisorbed atomic state due to the phase transition in the nickel. The changes in rate constants are also considered to be in qualitative agreement with theoretical predictions based on a spin coupling between the adatom and the magnetic substrate.

Dynamic shear-stress-enhanced rates of nutrient consumption in gas-liquid semi-continuous-flow suspensions

NASA Astrophysics Data System (ADS)

Belfiore, Laurence A.; Volpato, Fabio Z.; Paulino, Alexandre T.; Belfiore, Carol J.

2011-12-01

The primary objective of this investigation is to establish guidelines for generating significant mammalian cell density in suspension bioreactors when stress-sensitive kinetics enhance the rate of nutrient consumption. Ultra-low-frequency dynamic modulations of the impeller (i.e., 35104 Hz) introduce time-dependent oscillatory shear into this transient analysis of cell proliferation under semi-continuous creeping flow conditions. Greater nutrient consumption is predicted when the amplitude A of modulated impeller rotation increases, and stress-kinetic contributions to nutrient consumption rates increase linearly at higher modulation frequency via an application of fluctuation-dissipation response. Interphase mass transfer is required to replace dissolved oxygen as it is consumed by aerobic nutrient consumption in the liquid phase. The theory and predictions described herein could be important at small length scales in the creeping flow regime where viscous shear is significant at the interface between the nutrient medium and isolated cells in suspension. Two-dimensional flow around spherically shaped mammalian cells, suspended in a Newtonian culture medium, is analyzed to calculate the surface-averaged magnitude of the velocity gradient tensor and modify homogeneous rates of nutrient consumption that are stimulated by viscous shear, via the formalism of stress-kinetic reciprocal relations that obey Curie's theorem in non-equilibrium thermodynamics. Time constants for stress-free free and stress-sensitive stress nutrient consumption are defined and quantified to identify the threshold (i.e., stress,threshold) below which the effect of stress cannot be neglected in accurate predictions of bioreactor performance. Parametric studies reveal that the threshold time constant for stress-sensitive nutrient consumption stress,threshold decreases when the time constant for stress-free nutrient consumption free is shorter. Hence, stress,threshold depends directly on free. In other words, the threshold rate of stress-sensitive nutrient consumption is higher when the stress-free rate of nutrient consumption increases. Modulated rotation of the impeller, superimposed on steady shear, increases stress,threshold when free is constant, and stress,threshold depends directly on the amplitude A of these angular velocity modulations.

Radiation induced dissolution of UO 2 based nuclear fuel - A critical review of predictive modelling approaches

NASA Astrophysics Data System (ADS)

Eriksen, Trygve E.; Shoesmith, David W.; Jonsson, Mats

2012-01-01

Radiation induced dissolution of uranium dioxide (UO 2) nuclear fuel and the consequent release of radionuclides to intruding groundwater are key-processes in the safety analysis of future deep geological repositories for spent nuclear fuel. For several decades, these processes have been studied experimentally using both spent fuel and various types of simulated spent fuels. The latter have been employed since it is difficult to draw mechanistic conclusions from real spent nuclear fuel experiments. Several predictive modelling approaches have been developed over the last two decades. These models are largely based on experimental observations. In this work we have performed a critical review of the modelling approaches developed based on the large body of chemical and electrochemical experimental data. The main conclusions are: (1) the use of measured interfacial rate constants give results in generally good agreement with experimental results compared to simulations where homogeneous rate constants are used; (2) the use of spatial dose rate distributions is particularly important when simulating the behaviour over short time periods; and (3) the steady-state approach (the rate of oxidant consumption is equal to the rate of oxidant production) provides a simple but fairly accurate alternative, but errors in the reaction mechanism and in the kinetic parameters used may not be revealed by simple benchmarking. It is essential to use experimentally determined rate constants and verified reaction mechanisms, irrespective of whether the approach is chemical or electrochemical.

Theory for rates, equilibrium constants, and Brønsted slopes in F1-ATPase single molecule imaging experiments

PubMed Central

Volkán-Kacsó, Sándor; Marcus, Rudolph A.

2015-01-01

A theoretical model of elastically coupled reactions is proposed for single molecule imaging and rotor manipulation experiments on F1-ATPase. Stalling experiments are considered in which rates of individual ligand binding, ligand release, and chemical reaction steps have an exponential dependence on rotor angle. These data are treated in terms of the effect of thermodynamic driving forces on reaction rates, and lead to equations relating rate constants and free energies to the stalling angle. These relations, in turn, are modeled using a formalism originally developed to treat electron and other transfer reactions. During stalling the free energy profile of the enzymatic steps is altered by a work term due to elastic structural twisting. Using biochemical and single molecule data, the dependence of the rate constant and equilibrium constant on the stall angle, as well as the Børnsted slope are predicted and compared with experiment. Reasonable agreement is found with stalling experiments for ATP and GTP binding. The model can be applied to other torque-generating steps of reversible ligand binding, such as ADP and Pi release, when sufficient data become available. PMID:26483483

Evaluation Of Landfill Gas Decay Constant For Municipal Solid Waste Landfills Operated As Bioreactors

EPA Science Inventory

Prediction of the rate of gas production from bioreactor landfills is important to optimize energy recovery and to estimate greenhouse gas emissions. Landfill gas (LFG) composition and flow rate were monitored for four years for a conventional and two bioreactor landfill landfil...

Thermal decomposition of ethanol. 4. Ab initio chemical kinetics for reactions of H atoms with CH3CH2O and CH3CHOH radicals.

PubMed

Xu, Z F; Xu, Kun; Lin, M C

2011-04-21

The potential energy surfaces of H-atom reactions with CH(3)CH(2)O and CH(3)CHOH, two major radicals in the decomposition and oxidation of ethanol, have been studied at the CCSD(T)/6-311+G(3df,2p) level of theory with geometric optimization carried out at the BH&HLYP/6-311+G(3df,2p) level. The direct hydrogen abstraction channels and the indirect association/decomposition channels from the chemically activated ethanol molecule have been considered for both reactions. The rate constants for both reactions have been calculated at 100-3000 K and 10(-4) Torr to 10(3) atm Ar pressure by microcanonical VTST/RRKM theory with master equation solution for all accessible product channels. The results show that the major product channel of the CH(3)CH(2)O + H reaction is CH(3) + CH(2)OH under atmospheric pressure conditions. Only at high pressure and low temperature, the rate constant for CH(3)CH(2)OH formation by collisonal deactivation becomes dominant. For CH(3)CHOH + H, there are three major product channels; at high temperatures, CH(3)+CH(2)OH production predominates at low pressures (P < 100 Torr), while the formation of CH(3)CH(2)OH by collisional deactivation becomes competitive at high pressures and low temperatures (T < 500 K). At high temperatures, the direct hydrogen abstraction reaction producing CH(2)CHOH + H(2) becomes dominant. Rate constants for all accessible product channels in both systems have been predicted and tabulated for modeling applications. The predicted value for CH(3)CHOH + H at 295 K and 1 Torr pressure agrees closely with available experimental data. For practical modeling applications, the rate constants for the thermal unimolecular decomposition of ethanol giving key accessible products have been predicted; those for the two major product channels taking place by dehydration and C-C breaking agree closely with available literature data.

Ab initio chemical kinetics for the ClOO + NO reaction: Effects of temperature and pressure on product branching formation

NASA Astrophysics Data System (ADS)

Raghunath, P.; Lin, M. C.

2012-07-01

The kinetics and mechanism for the reaction of ClOO with NO have been investigated by ab initio molecular orbital theory calculations based on the CCSD(T)/6-311+G(3df)//PW91PW91/6-311+G(3df) method, employed to evaluate the energetics for the construction of potential energy surfaces and prediction of reaction rate constants. The results show that the reaction can produce two key low energy products ClNO + 3O2 via the direct triplet abstraction path and ClO + NO2 via the association and decomposition mechanism through long-lived singlet pc-ClOONO and ClONO2 intermediates. The yield of ClNO + O2 (1△) from any of the singlet intermediates was found to be negligible because of their high barriers and tight transition states. As both key reactions initially occur barrierlessly, their rate constants were evaluated with a canonical variational approach in our transition state theory and Rice-Ramspergen-Kassel-Marcus/master equation calculations. The rate constants for ClNO + 3O2 and ClO + NO2 production from ClOO + NO can be given by 2.66 × 10-16 T1.91 exp(341/T) (200-700 K) and 1.48 × 10-24 T3.99 exp(1711/T) (200-600 K), respectively, independent of pressure below atmospheric pressure. The predicted total rate constant and the yields of ClNO and NO2 in the temperature range of 200-700 K at 10-760 Torr pressure are in close agreement with available experimental results.

Computational Simulation of the High Strain Rate Tensile Response of Polymer Matrix Composites

NASA Technical Reports Server (NTRS)

Goldberg, Robert K.

2002-01-01

A research program is underway to develop strain rate dependent deformation and failure models for the analysis of polymer matrix composites subject to high strain rate impact loads. Under these types of loading conditions, the material response can be highly strain rate dependent and nonlinear. State variable constitutive equations based on a viscoplasticity approach have been developed to model the deformation of the polymer matrix. The constitutive equations are then combined with a mechanics of materials based micromechanics model which utilizes fiber substructuring to predict the effective mechanical and thermal response of the composite. To verify the analytical model, tensile stress-strain curves are predicted for a representative composite over strain rates ranging from around 1 x 10(exp -5)/sec to approximately 400/sec. The analytical predictions compare favorably to experimentally obtained values both qualitatively and quantitatively. Effective elastic and thermal constants are predicted for another composite, and compared to finite element results.

Laboratory constraints on models of earthquake recurrence

USGS Publications Warehouse

Beeler, Nicholas M.; Tullis, Terry; Junger, Jenni; Kilgore, Brian D.; Goldsby, David L.

2014-01-01

In this study, rock friction ‘stick-slip’ experiments are used to develop constraints on models of earthquake recurrence. Constant-rate loading of bare rock surfaces in high quality experiments produces stick-slip recurrence that is periodic at least to second order. When the loading rate is varied, recurrence is approximately inversely proportional to loading rate. These laboratory events initiate due to a slip rate-dependent process that also determines the size of the stress drop [Dieterich, 1979; Ruina, 1983] and as a consequence, stress drop varies weakly but systematically with loading rate [e.g., Gu and Wong, 1991; Karner and Marone, 2000; McLaskey et al., 2012]. This is especially evident in experiments where the loading rate is changed by orders of magnitude, as is thought to be the loading condition of naturally occurring, small repeating earthquakes driven by afterslip, or low-frequency earthquakes loaded by episodic slip. As follows from the previous studies referred to above, experimentally observed stress drops are well described by a logarithmic dependence on recurrence interval that can be cast as a non-linear slip-predictable model. The fault’s rate dependence of strength is the key physical parameter. Additionally, even at constant loading rate the most reproducible laboratory recurrence is not exactly periodic, unlike existing friction recurrence models. We present example laboratory catalogs that document the variance and show that in large catalogs, even at constant loading rate, stress drop and recurrence co-vary systematically. The origin of this covariance is largely consistent with variability of the dependence of fault strength on slip rate. Laboratory catalogs show aspects of both slip and time predictability and successive stress drops are strongly correlated indicating a ‘memory’ of prior slip history that extends over at least one recurrence cycle.

Validating Whole-Airway CFD Predictions of DPI Aerosol Deposition at Multiple Flow Rates.

PubMed

Longest, P Worth; Tian, Geng; Khajeh-Hosseini-Dalasm, Navvab; Hindle, Michael

2016-12-01

The objective of this study was to compare aerosol deposition predictions of a new whole-airway CFD model with available in vivo data for a dry powder inhaler (DPI) considered across multiple inhalation waveforms, which affect both the particle size distribution (PSD) and particle deposition. The Novolizer DPI with a budesonide formulation was selected based on the availability of 2D gamma scintigraphy data in humans for three different well-defined inhalation waveforms. Initial in vitro cascade impaction experiments were conducted at multiple constant (square-wave) particle sizing flow rates to characterize PSDs. The whole-airway CFD modeling approach implemented the experimentally determined PSDs at the point of aerosol formation in the inhaler. Complete characteristic airway geometries for an adult were evaluated through the lobar bronchi, followed by stochastic individual pathway (SIP) approximations through the tracheobronchial region and new acinar moving wall models of the alveolar region. It was determined that the PSD used for each inhalation waveform should be based on a constant particle sizing flow rate equal to the average of the inhalation waveform's peak inspiratory flow rate (PIFR) and mean flow rate [i.e., AVG(PIFR, Mean)]. Using this technique, agreement with the in vivo data was acceptable with <15% relative differences averaged across the three regions considered for all inhalation waveforms. Defining a peripheral to central deposition ratio (P/C) based on alveolar and tracheobronchial compartments, respectively, large flow-rate-dependent differences were observed, which were not evident in the original 2D in vivo data. The agreement between the CFD predictions and in vivo data was dependent on accurate initial estimates of the PSD, emphasizing the need for a combination in vitro-in silico approach. Furthermore, use of the AVG(PIFR, Mean) value was identified as a potentially useful method for characterizing a DPI aerosol at a constant flow rate.

Validating Whole-Airway CFD Predictions of DPI Aerosol Deposition at Multiple Flow Rates

PubMed Central

Tian, Geng; Khajeh-Hosseini-Dalasm, Navvab; Hindle, Michael

2016-01-01

Abstract Background: The objective of this study was to compare aerosol deposition predictions of a new whole-airway CFD model with available in vivo data for a dry powder inhaler (DPI) considered across multiple inhalation waveforms, which affect both the particle size distribution (PSD) and particle deposition. Methods: The Novolizer DPI with a budesonide formulation was selected based on the availability of 2D gamma scintigraphy data in humans for three different well-defined inhalation waveforms. Initial in vitro cascade impaction experiments were conducted at multiple constant (square-wave) particle sizing flow rates to characterize PSDs. The whole-airway CFD modeling approach implemented the experimentally determined PSDs at the point of aerosol formation in the inhaler. Complete characteristic airway geometries for an adult were evaluated through the lobar bronchi, followed by stochastic individual pathway (SIP) approximations through the tracheobronchial region and new acinar moving wall models of the alveolar region. Results: It was determined that the PSD used for each inhalation waveform should be based on a constant particle sizing flow rate equal to the average of the inhalation waveform's peak inspiratory flow rate (PIFR) and mean flow rate [i.e., AVG(PIFR, Mean)]. Using this technique, agreement with the in vivo data was acceptable with <15% relative differences averaged across the three regions considered for all inhalation waveforms. Defining a peripheral to central deposition ratio (P/C) based on alveolar and tracheobronchial compartments, respectively, large flow-rate-dependent differences were observed, which were not evident in the original 2D in vivo data. Conclusions: The agreement between the CFD predictions and in vivo data was dependent on accurate initial estimates of the PSD, emphasizing the need for a combination in vitro–in silico approach. Furthermore, use of the AVG(PIFR, Mean) value was identified as a potentially useful method for characterizing a DPI aerosol at a constant flow rate. PMID:27082824

Development of an Austenitization Kinetics Model for 22MnB5 Steel

NASA Astrophysics Data System (ADS)

Di Ciano, M.; Field, N.; Wells, M. A.; Daun, K. J.

2018-03-01

This paper presents a first-order austenitization kinetics model for 22MnB5 steel, commonly used in hot forming die quenching. Model parameters are derived from constant heating rate dilatometry measurements. Vickers hardness measurements made on coupons that were quenched at intermediate stages of the process were used to verify the model, and the Ac 1 and Ac 3 temperatures inferred from dilatometry are consistent with correlations found in the literature. The austenitization model was extended to consider non-constant heating rates typical of industrial furnaces and again showed reasonable agreement between predictions and measurements. Finally, the model is used to predict latent heat evolution during industrial heating and is shown to be consistent with values inferred from thermocouple measurements of furnace-heated 22MnB5 coupons reported in the literature.

An experimental comparison of several current viscoplastic constitutive models at elevated temperature

NASA Technical Reports Server (NTRS)

James, G. H.; Imbrie, P. K.; Hill, P. S.; Allen, D. H.; Haisler, W. E.

1988-01-01

Four current viscoplastic models are compared experimentally for Inconel 718 at 593 C. This material system responds with apparent negative strain rate sensitivity, undergoes cyclic work softening, and is susceptible to low cycle fatigue. A series of tests were performed to create a data base from which to evaluate material constants. A method to evaluate the constants is developed which draws on common assumptions for this type of material, recent advances by other researchers, and iterative techniques. A complex history test, not used in calculating the constants, is then used to compare the predictive capabilities of the models. The combination of exponentially based inelastic strain rate equations and dynamic recovery is shown to model this material system with the greatest success. The method of constant calculation developed was successfully applied to the complex material response encountered. Backstress measuring tests were found to be invaluable and to warrant further development.

Strain-rate/temperature behavior of high density polyethylene in compression

NASA Technical Reports Server (NTRS)

Clements, L. L.; Sherby, O. D.

1978-01-01

The compressive strain rate/temperature behavior of highly linear, high density polyethylene was analyzed in terms of the predictive relations developed for metals and other crystalline materials. For strains of 5 percent and above, the relationship between applied strain rate, dotted epsilon, and resulting flow stress, sigma, was found to be: dotted epsilon exp times (Q sub f/RT) = k'(sigma/sigma sub c) to the nth power; the left-hand side is the activation-energy-compensated strain rate, where Q sub f is activation energy for flow, R is gas constant, and T is temperature; k is a constant, n is temperature-independent stress exponent, and sigma/sigma sub c is structure-compensated stress. A master curve resulted from a logarithmic plot of activation-energy-compensated strain rate versus structure-compensated stress.

Modeling Hybridization Kinetics of Gene Probes in a DNA Biochip Using FEMLAB

PubMed Central

Munir, Ahsan; Waseem, Hassan; Williams, Maggie R.; Stedtfeld, Robert D.; Gulari, Erdogan; Tiedje, James M.; Hashsham, Syed A.

2017-01-01

Microfluidic DNA biochips capable of detecting specific DNA sequences are useful in medical diagnostics, drug discovery, food safety monitoring and agriculture. They are used as miniaturized platforms for analysis of nucleic acids-based biomarkers. Binding kinetics between immobilized single stranded DNA on the surface and its complementary strand present in the sample are of interest. To achieve optimal sensitivity with minimum sample size and rapid hybridization, ability to predict the kinetics of hybridization based on the thermodynamic characteristics of the probe is crucial. In this study, a computer aided numerical model for the design and optimization of a flow-through biochip was developed using a finite element technique packaged software tool (FEMLAB; package included in COMSOL Multiphysics) to simulate the transport of DNA through a microfluidic chamber to the reaction surface. The model accounts for fluid flow, convection and diffusion in the channel and on the reaction surface. Concentration, association rate constant, dissociation rate constant, recirculation flow rate, and temperature were key parameters affecting the rate of hybridization. The model predicted the kinetic profile and signal intensities of eighteen 20-mer probes targeting vancomycin resistance genes (VRGs). Predicted signal intensities and hybridization kinetics strongly correlated with experimental data in the biochip (R2 = 0.8131). PMID:28555058

Modeling Hybridization Kinetics of Gene Probes in a DNA Biochip Using FEMLAB.

PubMed

Munir, Ahsan; Waseem, Hassan; Williams, Maggie R; Stedtfeld, Robert D; Gulari, Erdogan; Tiedje, James M; Hashsham, Syed A

2017-05-29

Microfluidic DNA biochips capable of detecting specific DNA sequences are useful in medical diagnostics, drug discovery, food safety monitoring and agriculture. They are used as miniaturized platforms for analysis of nucleic acids-based biomarkers. Binding kinetics between immobilized single stranded DNA on the surface and its complementary strand present in the sample are of interest. To achieve optimal sensitivity with minimum sample size and rapid hybridization, ability to predict the kinetics of hybridization based on the thermodynamic characteristics of the probe is crucial. In this study, a computer aided numerical model for the design and optimization of a flow-through biochip was developed using a finite element technique packaged software tool (FEMLAB; package included in COMSOL Multiphysics) to simulate the transport of DNA through a microfluidic chamber to the reaction surface. The model accounts for fluid flow, convection and diffusion in the channel and on the reaction surface. Concentration, association rate constant, dissociation rate constant, recirculation flow rate, and temperature were key parameters affecting the rate of hybridization. The model predicted the kinetic profile and signal intensities of eighteen 20-mer probes targeting vancomycin resistance genes (VRGs). Predicted signal intensities and hybridization kinetics strongly correlated with experimental data in the biochip (R² = 0.8131).

Voicing produced by a constant velocity lung source

PubMed Central

Howe, M. S.; McGowan, R. S.

2013-01-01

An investigation is made of the influence of subglottal boundary conditions on the prediction of voiced sounds. It is generally assumed in mathematical models of voicing that vibrations of the vocal folds are maintained by a constant subglottal mean pressure pI, whereas voicing is actually initiated by contraction of the chest cavity until the subglottal pressure becomes large enough to separate the vocal folds. The problem is reformulated to determine voicing characteristics in terms of a prescribed volumetric flow rate Qo of air from the lungs—the evolution of the resulting time-dependent subglottal mean pressure p¯_(t) is then governed by glottal mechanics, the aeroacoustics of the vocal tract, and the influence of continued contraction of the lungs. The new problem is analyzed in detail for an idealized mechanical vocal system that permits precise specification of all boundary conditions. Predictions of the glottal volume velocity pulse shape are found to be in good general agreement with the traditional constant-pI theory when pI is set equal to the time averaged value of p¯_(t). But, in all cases examined the constant-pI approximation yields values of the mean flow rates Qo and sound pressure levels that are smaller by as much as 10%. PMID:23556600

The kinetics of competitive antagonists on guinea-pig ileum.

PubMed Central

Roberts, F; Stephenson, R P

1976-01-01

1 The kinetics of action of some competitive muscarinic and histamine antagonists were examined on guinea-pig isolated ileum and their behaviour compared with the predictions of the interaction-limited model described by Paton (1961). 2 The kinetics of antagonism were not consistent with the predictions of this model: (1) The apparent dissociation rate constant calculated from the decrease in occupancy on washout was not independent of the concentration of antagonist. (2) The dissociation rate constant of a 'slow' antagonist calculated from the change in occupancy when a 'fast' antagonist was superimposed varied with the concentration of fast antagonist. (3) If the concentration of slow antagonist was increased when the fast antagonist was superimposed so that the equilibrium occupancy of the 'slow' was the same as before, a transitional phase was observed. 3 The kinetics of antagonism were observed in longitudinal muscle strips and intact pieces of ileum, bathed in Tyrode or Krebs solution, and with isometric and isotonic recording. No evidence was found that the discrepancies between the interaction-limited model and the observed kinetics could be accounted for by the experimental method used. 4 It is therefore concluded that either access is rate-limiting in these circumstances or, if interaction is rate-limiting, some alternative interaction-limited model is required to describe the kinetics of antagonism. In either case it would seem unwise at this time to calculate antagonist-receptor rate constants from the observed kinetics of antagonism. PMID:974378

Effect of thermal profile on cyclic flaw growth in aluminum

NASA Technical Reports Server (NTRS)

Engstrom, W. L.

1975-01-01

Surface flawed and single edge notch tension specimens of 2219-T851 and -T87 aluminum were tested to determine static fracture characteristics and base line (constant amplitude, constant temperature) cyclic flaw growth behavior. Subsequent testing was then conducted in which flawed specimens were subjected to a thermal profile in which the applied stress was varied simultaneously with the temperature. The profile used represents a simplified space shuttle orbiter load/temperature flight cycle. Test temperatures included the range from 144K (-200 F) up to 450K (350 F). The measured flaw growth rates obtained from the thermal profile tests were then compared with rates predicted by assuming linear cumulative damage of base line rates.

Star formation in the multiverse

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

Bousso, Raphael; Leichenauer, Stefan

2009-03-15

We develop a simple semianalytic model of the star formation rate as a function of time. We estimate the star formation rate for a wide range of values of the cosmological constant, spatial curvature, and primordial density contrast. Our model can predict such parameters in the multiverse, if the underlying theory landscape and the cosmological measure are known.

Toward elimination of discrepancies between theory and experiment: The rate constant of the atmospheric conversion of SO3 to H2SO4

PubMed Central

Loerting, Thomas; Liedl, Klaus R.

2000-01-01

The hydration rate constant of sulfur trioxide to sulfuric acid is shown to depend sensitively on water vapor pressure. In the 1:1 SO3-H2O complex, the rate is predicted to be slower by about 25 orders of magnitude compared with laboratory results [Lovejoy, E. R., Hanson, D. R. & Huey, L. G. (1996) J. Phys. Chem. 100, 19911–19916; Jayne, J. T., Pöschl, U., Chen, Y.-m., Dai, D., Molina, L. T., Worsnop, D. R., Kolb, C. E. & Molina, M. J. (1997) J. Phys. Chem. A 101, 10000–10011]. This discrepancy is removed mostly by allowing a second and third water molecule to participate. An asynchronous water-mediated double proton transfer concerted with the nucleophilic attack and a double proton transfer accompanied by a transient H3O+ rotation are predicted to be the fastest reaction mechanisms. Comparison of the predicted negative apparent “activation” energies with the experimental finding indicates that in our atmosphere, different reaction paths involving two and three water molecules are taken in the process of forming sulfate aerosols and consequently acid rain. PMID:10922048

New perspectives on constant-roll inflation

NASA Astrophysics Data System (ADS)

Cicciarella, Francesco; Mabillard, Joel; Pieroni, Mauro

2018-01-01

We study constant-roll inflation using the β-function formalism. We show that the constant rate of the inflaton roll is translated into a first order differential equation for the β-function which can be solved easily. The solutions to this equation correspond to the usual constant-roll models. We then construct, by perturbing these exact solutions, more general classes of models that satisfy the constant-roll equation asymptotically. In the case of an asymptotic power law solution, these corrections naturally provide an end to the inflationary phase. Interestingly, while from a theoretical point of view (in particular in terms of the holographic interpretation) these models are intrinsically different from standard slow-roll inflation, they may have phenomenological predictions in good agreement with present cosmological data.

Effects of packaging and heat transfer kinetics on drug-product stability during storage under uncontrolled temperature conditions.

PubMed

Nakamura, Toru; Yamaji, Takayuki; Takayama, Kozo

2013-05-01

To predict the stability of pharmaceutical preparations under uncontrolled temperature conditions accurately, a method to compute the average reaction rate constant taking into account the heat transfer from the atmosphere to the product was developed. The average reaction rate constants computed with taken into consideration heat transfer (κ(re) ) were then compared with those computed without taking heat transfer into consideration (κ(in) ). The apparent thermal diffusivity (κ(a) ) exerted some influence on the average reaction rate constant ratio (R, R = κ(re) /κ(in) ). In the regions where the κ(a) was large (above 1 h(-1) ) or very small, the value of R was close to 1. On the contrary, in the middle region (0.001-1 h(-1) ), the value of R was less than 1.The κ(a) of the central part of a large-size container and that of the central part of a paper case of 10 bottles of liquid medicine (100 mL) fell within this middle region. On the basis of the above-mentioned considerations, heat transfer may need to be taken into consideration to enable a more accurate prediction of the stability of actual pharmaceutical preparations under nonisothermal atmospheres. Copyright © 2013 Wiley Periodicals, Inc.

Theory of single-molecule controlled rotation experiments, predictions, tests, and comparison with stalling experiments in F1-ATPase.

PubMed

Volkán-Kacsó, Sándor; Marcus, Rudolph A

2016-10-25

A recently proposed chemomechanical group transfer theory of rotary biomolecular motors is applied to treat single-molecule controlled rotation experiments. In these experiments, single-molecule fluorescence is used to measure the binding and release rate constants of nucleotides by monitoring the occupancy of binding sites. It is shown how missed events of nucleotide binding and release in these experiments can be corrected using theory, with F 1 -ATP synthase as an example. The missed events are significant when the reverse rate is very fast. Using the theory the actual rate constants in the controlled rotation experiments and the corrections are predicted from independent data, including other single-molecule rotation and ensemble biochemical experiments. The effective torsional elastic constant is found to depend on the binding/releasing nucleotide, and it is smaller for ADP than for ATP. There is a good agreement, with no adjustable parameters, between the theoretical and experimental results of controlled rotation experiments and stalling experiments, for the range of angles where the data overlap. This agreement is perhaps all the more surprising because it occurs even though the binding and release of fluorescent nucleotides is monitored at single-site occupancy concentrations, whereas the stalling and free rotation experiments have multiple-site occupancy.

Extension of the master sintering curve for constant heating rate modeling

NASA Astrophysics Data System (ADS)

McCoy, Tammy Michelle

The purpose of this work is to extend the functionality of the Master Sintering Curve (MSC) such that it can be used as a practical tool for predicting sintering schemes that combine both a constant heating rate and an isothermal hold. Rather than just being able to predict a final density for the object of interest, the extension to the MSC will actually be able to model a sintering run from start to finish. Because the Johnson model does not incorporate this capability, the work presented is an extension of what has already been shown in literature to be a valuable resource in many sintering situations. A predicted sintering curve that incorporates a combination of constant heating rate and an isothermal hold is more indicative of what is found in real-life sintering operations. This research offers the possibility of predicting the sintering schedule for a material, thereby having advanced information about the extent of sintering, the time schedule for sintering, and the sintering temperature with a high degree of accuracy and repeatability. The research conducted in this thesis focuses on the development of a working model for predicting the sintering schedules of several stabilized zirconia powders having the compositions YSZ (HSY8), 10Sc1CeSZ, 10Sc1YSZ, and 11ScSZ1A. The compositions of the four powders are first verified using x-ray diffraction (XRD) and the particle size and surface area are verified using a particle size analyzer and BET analysis, respectively. The sintering studies were conducted on powder compacts using a double pushrod dilatometer. Density measurements are obtained both geometrically and using the Archimedes method. Each of the four powders is pressed into ¼" diameter pellets using a manual press with no additives, such as a binder or lubricant. Using a double push-rod dilatometer, shrinkage data for the pellets is obtained over several different heating rates. The shrinkage data is then converted to reflect the change in relative density of the pellets based on the green density and the theoretical density of each of the compositions. The Master Sintering Curve (MSC) model is then utilized to generate data that can be utilized to predict the final density of the respective powder over a range of heating rates. The Elton Master Sintering Curve Extension (EMSCE) is developed to extend the functionality of the MSC tool. The parameters generated from the original MSC are used in tandem with the solution to the closed integral, theta ≡ 1cTo T1Texp -QRT dT, over a set range of temperatures. The EMSCE is used to generate a set of sintering curves having both constant heating rate and isothermal hold portions. The EMSCE extends the usefulness of the MSC by allowing this generation of a complete sintering schedule rather than just being able to predict the final relative density of a given material. The EMSCE is verified by generating a set of curves having both constant heating rate and an isothermal hold for the heat-treatment. The modeled curves are verified experimentally and a comparison of the model and experimental results are given for a selected composition. Porosity within the final product can hinder the product from sintering to full density. It is shown that some of the compositions studied did not sinter to full density because of the presence of large porosity that could not be eliminated in a reasonable amount of time. A statistical analysis of the volume fraction of porosity is completed to show the significance of the presence in the final product. The reason this is relevant to the MSC is that the model does not take into account the presence of porosity and assumes that the samples sinter to full density. When this does not happen, the model actually under-predicts the final density of the material.

Constancy of local spread rates for buffelgrass (Pennisetum ciliare L.) in the Arizona Upland of the Sonoran Desert

USGS Publications Warehouse

Olsson, Aaryn D.; Betancourt, Julio L.; Crimmins, Michael A.; Marsh, Stuart E.

2012-01-01

In North American deserts, grass invasions threaten native vegetation via competition and altered fire regimes. Accurate prediction and successful mitigation of these invasions hinge on estimation of spread rates and their degree of constancy in time and space. We used high-resolution aerial photographs from 11 sites in the Santa Catalina Mountains, southern Arizona to reconstruct the spread of buffelgrass (Pennisetum ciliare), a C4 perennial bunchgrass, since 1980. The total area infested was fit to a logistic model and residuals of the model were compared to climatic factors of the corresponding and lagged time periods. Infestations grew from small colonizing patches in the 1980s to 66 ha in 2008, doubling every 2.26–7.04 years since 1988. Although buffelgrass germination, establishment and distribution are favored by wet summers and warm winters, climate variables did not predict spread rates. Buffelgrass has grown at a constant rate, at least since 1988, when much of its expansion took place. In the study area, minimum requirements are met almost every year for germination and reproduction, establishing a consistent baseline for spread that manifests as a constant spread rate.

Consequences of genetic change in farm animals on food intake and feeding behaviour.

PubMed

Emmans, G; Kyriazakis, I

2001-02-01

Selection in commercial populations on aspects of output, such as for growth rate in poultry. against fatness and for growth rate in pigs, and for milk yield in cows, has had very barge effects on such outputs over the past 50 years. Partly because of the cost of recording intake, there has been little or no selection for food intake or feeding behaviour. In order to predict the effects of such past, and future, selection on intake it is necessary to have some suitable theoretical framework. Intake needs to be predicted in order to make rational feeding and environmental decisions. The idea that an animal will eat 'to meet its requirements' has proved useful and continues to be fruitful. An important part of the idea is that the animal (genotype) can be described in a way that is sufficient for the accurate prediction of its outputs over time. Such descriptions can be combined with a set of nutritional constants to calculate requirements. There appears to have been no change in the nutritional constants under selection for output. Under such selection it is simplest to assume that changes in intake follow from the changes in output rates, so that intake changes become entirely predictable. It is suggested that other ways that have been proposed for predicting intake cannot be successful in predicting the effects of selection. Feeding behaviour is seen as being the means that the animal uses to attain its intake rather than being the means by which that intake can be predicted. Thus, the organisation of feeding behaviour can be used to predict neither intake nor the effects of selection on it.

Validity of the two-level model for Viterbi decoder gap-cycle performance

NASA Technical Reports Server (NTRS)

Dolinar, S.; Arnold, S.

1990-01-01

A two-level model has previously been proposed for approximating the performance of a Viterbi decoder which encounters data received with periodically varying signal-to-noise ratio. Such cyclically gapped data is obtained from the Very Large Array (VLA), either operating as a stand-alone system or arrayed with Goldstone. This approximate model predicts that the decoder error rate will vary periodically between two discrete levels with the same period as the gap cycle. It further predicts that the length of the gapped portion of the decoder error cycle for a constraint length K decoder will be about K-1 bits shorter than the actual duration of the gap. The two-level model for Viterbi decoder performance with gapped data is subjected to detailed validation tests. Curves showing the cyclical behavior of the decoder error burst statistics are compared with the simple square-wave cycles predicted by the model. The validity of the model depends on a parameter often considered irrelevant in the analysis of Viterbi decoder performance, the overall scaling of the received signal or the decoder's branch-metrics. Three scaling alternatives are examined: optimum branch-metric scaling and constant branch-metric scaling combined with either constant noise-level scaling or constant signal-level scaling. The simulated decoder error cycle curves roughly verify the accuracy of the two-level model for both the case of optimum branch-metric scaling and the case of constant branch-metric scaling combined with constant noise-level scaling. However, the model is not accurate for the case of constant branch-metric scaling combined with constant signal-level scaling.

A relation to describe rate-dependent material failure.

PubMed

Voight, B

1989-01-13

The simple relation OmegaOmega-alpha = 0, where Omega is a measurable quantity such as strain and A and alpha are empirical constants, describes the behavior of materials in terminal stages of failure under conditions of approximately constant stress and temperature. Applicable to metals and alloys, ice, concrete, polymers, rock, and soil, the relation may be extended to conditions of variable and multiaxial stress and may be used to predict time to failure.

A crack-closure model for predicting fatigue-crack growth under aircraft spectrum loading

NASA Technical Reports Server (NTRS)

Newman, J. C., Jr.

1981-01-01

The development and application of an analytical model of cycle crack growth is presented that includes the effects of crack closure. The model was used to correlate crack growth rates under constant amplitude loading and to predict crack growth under aircraft spectrum loading on 2219-T851 aluminum alloy sheet material. The predicted crack growth lives agreed well with experimental data. The ratio of predicted to experimental lives ranged from 0.66 to 1.48. These predictions were made using data from an ASTM E24.06.01 Round Robin.

Rapid and accurate prediction of degradant formation rates in pharmaceutical formulations using high-performance liquid chromatography-mass spectrometry.

PubMed

Darrington, Richard T; Jiao, Jim

2004-04-01

Rapid and accurate stability prediction is essential to pharmaceutical formulation development. Commonly used stability prediction methods include monitoring parent drug loss at intended storage conditions or initial rate determination of degradants under accelerated conditions. Monitoring parent drug loss at the intended storage condition does not provide a rapid and accurate stability assessment because often <0.5% drug loss is all that can be observed in a realistic time frame, while the accelerated initial rate method in conjunction with extrapolation of rate constants using the Arrhenius or Eyring equations often introduces large errors in shelf-life prediction. In this study, the shelf life prediction of a model pharmaceutical preparation utilizing sensitive high-performance liquid chromatography-mass spectrometry (LC/MS) to directly quantitate degradant formation rates at the intended storage condition is proposed. This method was compared to traditional shelf life prediction approaches in terms of time required to predict shelf life and associated error in shelf life estimation. Results demonstrated that the proposed LC/MS method using initial rates analysis provided significantly improved confidence intervals for the predicted shelf life and required less overall time and effort to obtain the stability estimation compared to the other methods evaluated. Copyright 2004 Wiley-Liss, Inc. and the American Pharmacists Association.

The Oxidation of Ascorbic Acid by Hexacyanoferrate(III) Ion in Acidic Aqueous Media.

ERIC Educational Resources Information Center

Martins, Luis J. A.; da Costa, J. Barbosa

1988-01-01

Describes a kinetic and mechanistic investigation of ascorbic acid by a substitution-inert complex in acidic medium suitable for the undergraduate level. Discusses obtaining the second order rate constant for the rate determining step at a given temperature and comparison with the value predicted on the basis of the Marcus cross-relation. (CW)

Effect of work and recovery durations on W' reconstitution during intermittent exercise.

PubMed

Skiba, Philip F; Jackman, Sarah; Clarke, David; Vanhatalo, Anni; Jones, Andrew M

2014-07-01

We recently presented an integrating model of the curvature constant of the hyperbolic power-time relationship (W') that permits the calculation of the W' balance (W'BAL) remaining at any time during intermittent exercise. Although a relationship between recovery power and the rate of W' recovery was demonstrated, the effect of the length of work or recovery intervals remains unclear. After determining VO2max, critical power, and W', 11 subjects completed six separate exercise tests on a cycle ergometer on different days, and in random order. Tests consisted of a period of intermittent severe-intensity exercise until the subject depleted approximately 50% of their predicted W'BAL, followed by a constant work rate (CWR) exercise bout until exhaustion. Work rates were kept constant between trials; however, either work or recovery durations during intermittent exercise were varied. The actual W' measured during the CWR (W'ACT) was compared with the amount of W' predicted to be available by the W'BAL model. Although some differences between W'BAL and W'ACT were noted, these amounted to only -1.6 ± 1.1 kJ when averaged across all conditions. The W'ACT was linearly correlated with the difference between VO2 at the start of CWR and VO2max (r = 0.79, P < 0.01). The W'BAL model provided a generally robust prediction of CWR W'. There may exist a physiological optimum formulation of work and recovery intervals such that baseline VO2 can be minimized, leading to an enhancement of subsequent exercise tolerance. These results may have important implications for athletic training and racing.

Fate of chemical warfare agents and toxic industrial chemicals in landfills.

PubMed

Bartelt-Hunt, Shannon L; Barlaz, Morton A; Knappe, Detlef R U; Kjeldsen, Peter

2006-07-01

One component of preparedness for a chemical attack is planning for the disposal of contaminated debris. To assess the feasibility of contaminated debris disposal in municipal solid waste (MSW) landfills, the fate of selected chemical warfare agents (CWAs) and toxic industrial chemicals (TICs) in MSW landfills was predicted with a mathematical model. Five blister agents [sulfur mustard (HD), nitrogen mustard (HN-2), lewisite (L), ethyldichloroarsine (ED), and phosgene oxime (CX)], eight nerve agents [tabun (GA), sarin (GB), soman (GD), GE, GF, VX, VG, and VM], one riot-control agent [CS], and two TICs [furan and carbon disulfide] were studied. The effects of both infiltration (climate) and contaminant biodegradability on fate predictions were assessed. Model results showed that hydrolysis and gas-phase advection were the principal fate pathways for CWAs and TICs, respectively. Apart from CX and the TICs, none of the investigated compounds was predicted to persist in a landfill for more than 5 years. Climate had little impact on CWA/TIC fate, and biodegradability was only important for compounds with long hydrolysis half-lives. Monte Carlo simulations were performed to assess the influence of uncertainty in model input parameters on CWA/TIC fate predictions. Correlation analyses showed that uncertainty in hydrolysis rate constants was the primary contributor to variance of CWA fate predictions, while uncertainty in the Henry's Law constant and landfill gas-production rate accounted for most of the variance of TIC fate predictions. CWA hydrolysates were more persistent than the parent CWAs, but limited information is available on abiotic or biotic transformation rates for these chemicals.

DCE-MRI-Derived Volume Transfer Constant (Ktrans) and DWI Apparent Diffusion Coefficient as Predictive Markers of Short- and Long-Term Efficacy of Chemoradiotherapy in Patients With Esophageal Cancer.

PubMed

Ye, Zhi-Min; Dai, Shu-Jun; Yan, Feng-Qin; Wang, Lei; Fang, Jun; Fu, Zhen-Fu; Wang, Yue-Zhen

2018-01-01

This study aimed to evaluate both the short- and long-term efficacies of chemoradiotherapy in relation to the treatment of esophageal cancer . This was achieved through the use of dynamic contrast-enhanced magnetic resonance imaging-derived volume transfer constant and diffusion weighted imaging-derived apparent diffusion coefficient . Patients with esophageal cancer were assigned into the sensitive and resistant groups based on respective efficacies in chemoradiotherapy. Dynamic contrast-enhanced magnetic resonance imaging and diffusion weighted imaging were used to measure volume transfer constant and apparent diffusion coefficient, while computed tomography was used to calculate tumor size reduction rate. Pearson correlation analyses were conducted to analyze correlation between volume transfer constant, apparent diffusion coefficient, and the tumor size reduction rate. Receiver operating characteristic curve was constructed to analyze the short-term efficacy of volume transfer constant and apparent diffusion coefficient, while Kaplan-Meier curve was employed for survival rate analysis. Cox proportional hazard model was used for the risk factors for prognosis of patients with esophageal cancer. Our results indicated reduced levels of volume transfer constant, while increased levels were observed in ADC min , ADC mean , and ADC max following chemoradiotherapy. A negative correlation was determined between ADC min , ADC mean , and ADC max , as well as in the tumor size reduction rate prior to chemoradiotherapy, whereas a positive correlation was uncovered postchemoradiotherapy. Volume transfer constant was positively correlated with tumor size reduction rate both before and after chemoradiotherapy. The 5-year survival rate of patients with esophageal cancer having high ADC min , ADC mean , and ADC max and volume transfer constant before chemoradiotherapy was greater than those with respectively lower values. According to the Cox proportional hazard model, ADC mean , clinical stage, degree of differentiation, and tumor stage were all confirmed as being independent risk factors in regard to the prognosis of patients with EC. The findings of this study provide evidence suggesting that volume transfer constant and apparent diffusion coefficient as being tools allowing for the evaluation of both the short- and long-term efficacies of chemoradiotherapy esophageal cancer treatment.

Tensile Properties of 17-7 PH and 12 MoV Stainless-Steel Sheet under Rapid-Heating and Constant-Temperature Conditions

NASA Technical Reports Server (NTRS)

Manning, Charles R., Jr.; Price, Howard L.

1961-01-01

Results are presented of rapid-heating tests of 17-7 PH and 12 MoV stainless-steel sheet heated to failure at temperature rates from about 1 F to 170 F per second under constant-load conditions. Yield and rupture strengths obtained from rapid-heating tests are compared with yield and tensile strengths obtained from short-time elevated-temperature tensile tests (30-minute exposure). A rate-temperature parameter was used to construct master curves from which yield and rupture stresses or temperatures can be predicted. A method for measuring strain by optical means is described.

Tensile properties of HK31XA-H24 magnesium-alloy sheet under rapid-heating conditions and constant elevated temperatures

NASA Technical Reports Server (NTRS)

Gibbs, Thomas W

1956-01-01

Specimens of HK31XA-H24 magnesium-alloy sheet from an experimental batch were heated to failure at nominal temperature rates from 0.2 F to 100 F per second under constant-load conditions. Rapid-heating yield and rupture stresses are presented and compared with the yield and ultimate stresses from elevated-temperature tensile stress-strain tests for 1/2-hour exposure. Linear temperature-rate parameters were used to correlate rapid-heating results by constructing master curves which can be used for predicting yield stresses and temperatures and for estimating rupture stresses and temperatures.

Eight-dimensional quantum reaction rate calculations for the H+CH{sub 4} and H{sub 2}+CH{sub 3} reactions on recent potential energy surfaces

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

Zhou, Yong; Zhang, Dong H., E-mail: zhangdh@dicp.ac.cn

2014-11-21

Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH{sub 4} reaction and the H{sub 2}+CH{sub 3} reaction are calculated. Simulations of the H+CH{sub 4} reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable highmore » accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH{sub 4} rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H{sub 2}+CH{sub 3} reaction are found to be in good consistency with experimental observations.« less

Rates of Change in Naturalistic Psychotherapy: Contrasting Dose-Effect and Good-Enough Level Models of Change

ERIC Educational Resources Information Center

Baldwin, Scott A.; Berkeljon, Arjan; Atkins, David C.; Olsen, Joseph A.; Nielsen, Stevan L.

2009-01-01

Most research on the dose-effect model of change has combined data across patients who vary in their total dose of treatment and has implicitly assumed that the rate of change during therapy is constant across doses. In contrast, the good-enough level model predicts that rate of change will be related to total dose of therapy. In this study, the…

Linear and non-linear regression analysis for the sorption kinetics of methylene blue onto activated carbon.

PubMed

Kumar, K Vasanth

2006-10-11

Batch kinetic experiments were carried out for the sorption of methylene blue onto activated carbon. The experimental kinetics were fitted to the pseudo first-order and pseudo second-order kinetics by linear and a non-linear method. The five different types of Ho pseudo second-order expression have been discussed. A comparison of linear least-squares method and a trial and error non-linear method of estimating the pseudo second-order rate kinetic parameters were examined. The sorption process was found to follow a both pseudo first-order kinetic and pseudo second-order kinetic model. Present investigation showed that it is inappropriate to use a type 1 and type pseudo second-order expressions as proposed by Ho and Blanachard et al. respectively for predicting the kinetic rate constants and the initial sorption rate for the studied system. Three correct possible alternate linear expressions (type 2 to type 4) to better predict the initial sorption rate and kinetic rate constants for the studied system (methylene blue/activated carbon) was proposed. Linear method was found to check only the hypothesis instead of verifying the kinetic model. Non-linear regression method was found to be the more appropriate method to determine the rate kinetic parameters.

Longer guts and higher food quality increase energy intake in migratory swans.

PubMed

van Gils, Jan A; Beekman, Jan H; Coehoorn, Pieter; Corporaal, Els; Dekkers, Ten; Klaassen, Marcel; van Kraaij, Rik; de Leeuw, Rinze; de Vries, Peter P

2008-11-01

1. Within the broad field of optimal foraging, it is increasingly acknowledged that animals often face digestive constraints rather than constraints on rates of food collection. This therefore calls for a formalization of how animals could optimize food absorption rates. 2. Here we generate predictions from a simple graphical optimal digestion model for foragers that aim to maximize their (true) metabolizable food intake over total time (i.e. including nonforaging bouts) under a digestive constraint. 3. The model predicts that such foragers should maintain a constant food retention time, even if gut length or food quality changes. For phenotypically flexible foragers, which are able to change the size of their digestive machinery, this means that an increase in gut length should go hand in hand with an increase in gross intake rate. It also means that better quality food should be digested more efficiently. 4. These latter two predictions are tested in a large avian long-distance migrant, the Bewick's swan (Cygnus columbianus bewickii), feeding on grasslands in its Dutch wintering quarters. 5. Throughout winter, free-ranging Bewick's swans, growing a longer gut and experiencing improved food quality, increased their gross intake rate (i.e. bite rate) and showed a higher digestive efficiency. These responses were in accordance with the model and suggest maintenance of a constant food retention time. 6. These changes doubled the birds' absorption rate. Had only food quality changed (and not gut length), then absorption rate would have increased by only 67%; absorption rate would have increased by only 17% had only gut length changed (and not food quality). 7. The prediction that gross intake rate should go up with gut length parallels the mechanism included in some proximate models of foraging that feeding motivation scales inversely to gut fullness. We plea for a tighter integration between ultimate and proximate foraging models.

Oxidative elimination of cyanotoxins: comparison of ozone, chlorine, chlorine dioxide and permanganate.

PubMed

Rodríguez, Eva; Onstad, Gretchen D; Kull, Tomas P J; Metcalf, James S; Acero, Juan L; von Gunten, Urs

2007-08-01

As the World Health Organization (WHO) progresses with provisional Drinking Water Guidelines of 1 microg/L for microcystin-LR and a proposed Guideline of 1 microg/L for cylindrospermopsin, efficient treatment strategies are needed to prevent cyanotoxins such as these from reaching consumers. A kinetic database has been compiled for the oxidative treatment of three cyanotoxins: microcystin-LR (MC-LR), cylindrospermopsin (CYN), and anatoxin-a (ANTX) with ozone, chlorine, chlorine dioxide and permanganate. This kinetic database contains rate constants not previously reported and determined in the present work (e.g. for permanganate oxidation of ANTX and chlorine dioxide oxidation of CYN and ANTX), together with previously published rate constants for the remaining oxidation processes. Second-order rate constants measured in pure aqueous solutions of these toxins could be used in a kinetic model to predict the toxin oxidation efficiency of ozone, chlorine, chlorine dioxide and permanganate when applied to natural waters. Oxidants were applied to water from a eutrophic Swiss lake (Lake Greifensee) in static-dose testing and dynamic time-resolved experiments to confirm predictions from the kinetic database, and to investigate the effects of a natural matrix on toxin oxidation and by-product formation. Overall, permanganate can effectively oxidize ANTX and MC-LR, while chlorine will oxidize CYN and MC-LR and ozone is capable of oxidizing all three toxins with the highest rate. The formation of trihalomethanes (THMs) in the treated water may be a restriction to the application of sufficiently high-chlorine doses.

Reactive transport of uranium in fractured crystalline rock: Upscaling in time and distance

DOE PAGES

Dittrich, Timothy M.; Reimus, Paul W.

2015-09-29

In this study, batch adsorption and breakthrough column experiments were conducted to evaluate uranium transport through altered material that fills fractures in a granite rock system at the Grimsel Test Site in Switzerland at pH 6.9 and 7.9. The role of adsorption and desorption kinetics was evaluated with reactive transport modeling by comparing one-, two-, and three-site models. Emphasis was placed on describing long desorption tails that are important for upscaling in time and distance. The effect of increasing pH in injection solutions was also evaluated. For pH 6.9, a three-site model with forward rate constants between 0.07 and 0.8more » ml g –1 h –1, reverse rate constants between 0.001 and 0.06 h –1, and site densities of 1.3, 0.104, and 0.026 μmol g –1 for ‘weak/fast’, ‘strong/slow’, and ‘very strong/very slow’ sites provided the best fits. For pH 7.9, a three-site model with forward rate constants between 0.05 and 0.8 mL g –1 h –1, reverse rate constants between 0.001 and 0.6 h –1, and site densities of 1.3, 0.039, and 0.013 μmol g –1 for a ‘weak/fast’, ‘strong/slow’, and ‘very strong/very slow’ sites provided the best fits. Column retardation coefficients (R d) were 80 for pH 6.9 and 10.3 for pH 7.9. Model parameters determined from the batch and column experiments were used in 50 year large-scale simulations for continuous and pulse injections and indicated that a three-site model is necessary at pH 6.9, although a K d-type equilibrium partition model with one-site was adequate for large scale predictions at pH 7.9. Batch experiments were useful for predicting early breakthrough times in the columns while column experiments helped differentiate the relative importance of sorption sites and desorption rate constants on transport.« less

Multiaxial Temperature- and Time-Dependent Failure Model

NASA Technical Reports Server (NTRS)

Richardson, David; McLennan, Michael; Anderson, Gregory; Macon, David; Batista-Rodriquez, Alicia

2003-01-01

A temperature- and time-dependent mathematical model predicts the conditions for failure of a material subjected to multiaxial stress. The model was initially applied to a filled epoxy below its glass-transition temperature, and is expected to be applicable to other materials, at least below their glass-transition temperatures. The model is justified simply by the fact that it closely approximates the experimentally observed failure behavior of this material: The multiaxiality of the model has been confirmed (see figure) and the model has been shown to be applicable at temperatures from -20 to 115 F (-29 to 46 C) and to predict tensile failures of constant-load and constant-load-rate specimens with failure times ranging from minutes to months..

Analytical modeling of fire growth on fire-resistive wood-based materials with changing conditions

Treesearch

Mark A. Dietenberger

2006-01-01

Our analytical model of fire growth for the ASTM E 84 tunnel, which simultaneously predicts heat release rate, flame-over area, and pyrolysis area as functions of time for constant conditions, was documented in the 2001 BCC Symposium for different treated wood materials. The model was extended to predict ignition and fire growth on exterior fire-resistive structures...

Constitutive Model for Hot Deformation of the Cu-Zr-Ce Alloy

NASA Astrophysics Data System (ADS)

Zhang, Yi; Sun, Huili; Volinsky, Alex A.; Wang, Bingjie; Tian, Baohong; Liu, Yong; Song, Kexing

2018-02-01

Hot compressive deformation behavior of the Cu-Zr-Ce alloy has been investigated according to the hot deformation tests in the 550-900 °C temperature range and 0.001-10 s-1 strain rate range. Based on the true stress-true strain curves, the flow stress behavior of the Cu-Zr-Ce alloy was investigated. Microstructure evolution was observed by optical microscopy. Based on the experimental results, a constitutive equation, which reflects the relationships between the stress, strain, strain rate and temperature, has been established. Material constants n, α, Q and ln A were calculated as functions of strain. The equation predicting the flow stress combined with these materials constants has been proposed. The predicted stress is consistent with experimental stress, indicating that developed constitutive equation can adequately predict the flow stress of the Cu-Zr-Ce alloy. Dynamic recrystallization critical strain was determined using the work hardening rate method. According to the dynamic material model, the processing maps for the Cu-Zr and Cu-Zr-Ce alloy were obtained at 0.4 and 0.5 strain. Based on the processing maps and microstructure observations, the optimal processing parameters for the two alloys were determined, and it was found that the addition of Ce can promote the hot workability of the Cu-Zr alloy.

Studies on a novel doughnut-shaped minitablet for intraocular drug delivery.

PubMed

Choonara, Yahya E; Pillay, Viness; Carmichael, Trevor; Danckwerts, Michael P

2007-12-28

The objective of this study was to evaluate the effect of 2 independent formulation variables on the drug release from a novel doughnut-shaped minitablet (DSMT) in order to optimize formulations for intraocular drug delivery. Formulations were based on a 3(2) full-factorial design. The 2 independent variables were the concentration of Resomer (% wt/wt) and the type of Resomer grade (RG502, RG503, and RG504), respectively. The evaluated response was the drug release rate constant computed from a referenced marketed product and in vitro drug release data obtained at pH 7.4 in simulated vitreous humor. DSMT devices were prepared containing either of 2 model drugs, ganciclovir or foscarnet, using a Manesty F3 tableting press fitted with a novel central-rod, punch, and die setup. Dissolution data revealed biphasic drug release behavior with 55% to 60% drug released over 120 days. The inherent viscosity of the various Resomer grades and the concentration were significant to achieve optimum release rate constants. Using the resultant statistical relationships with the release rate constant as a response, the optimum formulation predicted for devices formulated with foscarnet was 70% wt/wt of Resomer RG504, while 92% wt/wt of Resomer RG503 was ideal for devices formulated with ganciclovir. The results of this study revealed that the full-factorial design was a suitable tool to predict an optimized formulation for prolonged intraocular drug delivery.

Photophysical and photochemical insights into the photodegradation of sulfapyridine in water: A joint experimental and theoretical study.

PubMed

Zhang, Heming; Wei, Xiaoxuan; Song, Xuedan; Shah, Shaheen; Chen, Jingwen; Liu, Jianhui; Hao, Ce; Chen, Zhongfang

2018-01-01

For organic pollutants, photodegradation, as a major abiotic elimination process and of great importance to the environmental fate and risk, involves rather complicated physical and chemical processes of excited molecules. Herein, we systematically studied the photophysical and photochemical processes of a widely used antibiotic, namely sulfapyridine. By means of density functional theory (DFT) computations, we examined the rate constants and the competition of both photophysical and photochemical processes, elucidated the photochemical reaction mechanism, calculated reaction quantum yield (Φ) based on both photophysical and photochemical processes, and subsequently estimated the photodegradation rate constant. We further conducted photolysis experiments to measure the photodegradation rate constant of sulfapyridine. Our computations showed that sulfapyridine at the lowest excited singlet state (S 1 ) mainly undergoes internal conversion to its ground state, and is difficult to transfer to the lowest excited triplet states (T 1 ) via intersystem crossing (ISC) and emit fluorescence. In T 1 state, compared with phosphorescence emission and ISC, chemical reaction is much easier to initiate. Encouragingly, the theoretically predicted photodegradation rate constant is close to the experimentally observed value, indicating that quantum chemistry computation is powerful enough to study photodegradation involving ultra-fast photophysical and photochemical processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

System analysis of the dynamic response of the coronary circulation to a sudden change in heart rate.

PubMed

Dankelman, J; Stassen, H G; Spaan, J A

1990-03-01

In this study the response of driving pressure/flow ration on an abrupt change in heart rate was analysed. The difference between the response obtained with constant pressure and constant flow perfusion was also studied. The responses show a fast initial reversed phase followed by a slow phase caused by regulation. To test whether the initial phase could be the result of mechanical changes in the coronary circulation, a model for regulation was extended by the addition of four different mechanical models originating from the literature. These extended models were able to explain the fast initial phase. However, the mechanical model consisting of an intramyocardial compliance (C = 0.08 ml mm Hg-1 100 g-1) with a variable venous resistance, and the model consisting of a waterfall and a small compliance (C = 0.007 ml mm Hg-1 100g-1) both explained these responses best. The analysis showed that there is no direct relationship between rate of change of vascular tone and rate of change of pressure/flow ratio. However, on the basis of the two extended models, it can be predicted that the half-time for the response of regulation to be complete is about 9s with constant pressure perfusion and 15 s with constant flow perfusion.

Steady-State Computation of Constant Rotational Rate Dynamic Stability Derivatives

NASA Technical Reports Server (NTRS)

Park, Michael A.; Green, Lawrence L.

2000-01-01

Dynamic stability derivatives are essential to predicting the open and closed loop performance, stability, and controllability of aircraft. Computational determination of constant-rate dynamic stability derivatives (derivatives of aircraft forces and moments with respect to constant rotational rates) is currently performed indirectly with finite differencing of multiple time-accurate computational fluid dynamics solutions. Typical time-accurate solutions require excessive amounts of computational time to complete. Formulating Navier-Stokes (N-S) equations in a rotating noninertial reference frame and applying an automatic differentiation tool to the modified code has the potential for directly computing these derivatives with a single, much faster steady-state calculation. The ability to rapidly determine static and dynamic stability derivatives by computational methods can benefit multidisciplinary design methodologies and reduce dependency on wind tunnel measurements. The CFL3D thin-layer N-S computational fluid dynamics code was modified for this study to allow calculations on complex three-dimensional configurations with constant rotation rate components in all three axes. These CFL3D modifications also have direct application to rotorcraft and turbomachinery analyses. The modified CFL3D steady-state calculation is a new capability that showed excellent agreement with results calculated by a similar formulation. The application of automatic differentiation to CFL3D allows the static stability and body-axis rate derivatives to be calculated quickly and exactly.

Hydrodynamic and Nonhydrodynamic Contributions to the Bimolecular Collision Rates of Solute Molecules in Supercooled Bulk Water

PubMed Central

2015-01-01

Bimolecular collision rate constants of a model solute are measured in water at T = 259–303 K, a range encompassing both normal and supercooled water. A stable, spherical nitroxide spin probe, perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, is studied using electron paramagnetic resonance spectroscopy (EPR), taking advantage of the fact that the rotational correlation time, τR, the mean time between successive spin exchanges within a cage, τRE, and the long-time-averaged spin exchange rate constants, Kex, of the same solute molecule may be measured independently. Thus, long- and short-time translational diffusion behavior may be inferred from Kex and τRE, respectively. In order to measure Kex, the effects of dipole–dipole interactions (DD) on the EPR spectra must be separated, yielding as a bonus the DD broadening rate constants that are related to the dephasing rate constant due to DD, Wdd. We find that both Kex and Wdd behave hydrodynamically; that is to say they vary monotonically with T/η or η/T, respectively, where η is the shear viscosity, as predicted by the Stokes–Einstein equation. The same is true of the self-diffusion of water. In contrast, τRE does not follow hydrodynamic behavior, varying rather as a linear function of the density reaching a maximum at 276 ± 2 K near where water displays a maximum density. PMID:24874024

Simultaneous saccharification and co-fermentation of paper sludge to ethanol by Saccharomyces cerevisiae RWB222--Part I: kinetic modeling and parameters.

PubMed

Zhang, Jiayi; Shao, Xiongjun; Townsend, Oliver V; Lynd, Lee R

2009-12-01

A kinetic model was developed to predict batch simultaneous saccharification and co-fermentation (SSCF) of paper sludge by the xylose-utilizing yeast Saccharomyces cerevisiae RWB222 and the commercial cellulase preparation Spezyme CP. The model accounts for cellulose and xylan enzymatic hydrolysis and competitive uptake of glucose and xylose. Experimental results show that glucan and xylan enzymatic hydrolysis are highly correlated, and that the low concentrations of xylose encountered during SSCF do not have a significant inhibitory effect on enzymatic hydrolysis. Ethanol is found to not only inhibit the specific growth rate, but also to accelerate cell death. Glucose and xylose uptake rates were found to be competitively inhibitory, but this did not have a large impact during SSCF because the sugar concentrations are low. The model was used to evaluate which constants had the greatest impact on ethanol titer for a fixed substrate loading, enzyme loading, and fermentation time. The cellulose adsorption capacity and cellulose hydrolysis rate constants were found to have the greatest impact among enzymatic hydrolysis related constants, and ethanol yield and maximum ethanol tolerance had the greatest impact among fermentation related constants.

APPLICATIONS FOR DNA PROBES IN BIODEGRADATION RESEARCH

EPA Science Inventory

The use of DNA:DNA hybridization technology in biodegradation studies is investigated. The rate constants for sediments exposed to synthetic oils could be calculated from the NAH(1+) genotypes and this approach would be useful in predicting the kinetics of aromatic hydrocarbon de...

Predicting dietborne metal toxicity from metal influxes

USGS Publications Warehouse

Croteau, M.-N.; Luoma, S.N.

2009-01-01

Dietborne metal uptake prevails for many species in nature. However, the links between dietary metal exposure and toxicity are not well understood. Sources of uncertainty include the lack of suitable tracers to quantify exposure for metals such as copper, the difficulty to assess dietary processes such as food ingestion rate, and the complexity to link metal bioaccumulation and effects. We characterized dietborne copper, nickel, and cadmium influxes in a freshwater gastropod exposed to diatoms labeled with enriched stable metal isotopes. Metal influxes in Lymnaea stagnalis correlated linearly with dietborne metal concentrations over a range encompassing most environmental exposures. Dietary Cd and Ni uptake rate constants (kuf) were, respectively, 3.3 and 2.3 times higher than that for Cu. Detoxification rate constants (k detox) were similar among metals and appeared 100 times higher than efflux rate constants (ke). Extremely high Cu concentrations reduced feeding rates, causing the relationship between exposure and influx to deviate from linearity; i.e., Cu uptake rates leveled off between 1500 and 1800 nmol g-1 day-1. L. stagnalis rapidly takes up Cu, Cd, and Ni from food but detoxifies the accumulated metals, instead of reducing uptake or intensifying excretion. Above a threshold uptake rate, however, the detoxification capabilities of L. stagnalis are overwhelmed.

Chemical weathering rates of a soil chronosequence on granitic alluvium: I. Quantification of mineralogical and surface area changes and calculation of primary silicate reaction rates

USGS Publications Warehouse

White, A.F.; Blum, A.E.; Schulz, M.S.; Bullen, T.D.; Harden, J.W.; Peterson, M.L.

1996-01-01

Mineral weathering rates are determined for a series of soils ranging in age from 0.2-3000 Ky developed on alluvial terraces near Merced in the Central Valley of California. Mineralogical and elemental abundances exhibit time-dependent trends documenting the chemical evolution of granitic sand to residual kaolinite and quartz. Mineral losses with time occur in the order: hornblende > plagioclase > K-feldspar. Maximum volume decreases of >50% occur in the older soils. BET surface areas of the bulk soils increase with age, as do specific surface areas of aluminosilicate mineral fractions such as plagioclase, which increases from 0.4-1.5 m2 g-1 over 600 Ky. Quartz surface areas are lower and change less with time (0.11-0.23 m2 g-1). BET surface areas correspond to increasing external surface roughness (?? = 10-600) and relatively constant internal surface area (??? 1.3 m2 g-1). SEM observations confirm both surface pitting and development of internal porosity. A numerical model describes aluminosilicate dissolution rates as a function of changes in residual mineral abundance, grain size distributions, and mineral surface areas with time. A simple geometric treatment, assuming spherical grains and no surface roughness, predicts average dissolution rates (plagioclase, 10-17.4; K-feldspar, 10-17.8; and hornblende, 10-17.5 mol cm-1 s-1) that are constant with time and comparable to previous estimates of soil weathering. Average rates, based on BET surface area measurements and variable surface roughnesses, are much slower (plagioclase, 10-19.9; K-feldspar, 10-20.5; and hornblende 10-20.1 mol cm-2 s-1). Rates for individual soil horizons decrease by a factor of 101.5 over 3000 Ky indicating that the surface reactivities of minerals decrease as the physical surface areas increase. Rate constants based on BET estimates for the Merced soils are factors of 103-104 slower than reported experimental dissolution rates determined from freshly prepared silicates with low surface roughness (?? <10). This study demonstrates that the utility of experimental rate constants to predict weathering in soils is limited without consideration of variable surface areas and processes that control the evolution of surface reactivity with time.

Metabolic biotransformation half-lives in fish: QSAR modeling and consensus analysis.

PubMed

Papa, Ester; van der Wal, Leon; Arnot, Jon A; Gramatica, Paola

2014-02-01

Bioaccumulation in fish is a function of competing rates of chemical uptake and elimination. For hydrophobic organic chemicals bioconcentration, bioaccumulation and biomagnification potential are high and the biotransformation rate constant is a key parameter. Few measured biotransformation rate constant data are available compared to the number of chemicals that are being evaluated for bioaccumulation hazard and for exposure and risk assessment. Three new Quantitative Structure-Activity Relationships (QSARs) for predicting whole body biotransformation half-lives (HLN) in fish were developed and validated using theoretical molecular descriptors that seek to capture structural characteristics of the whole molecule and three data set splitting schemes. The new QSARs were developed using a minimal number of theoretical descriptors (n=9) and compared to existing QSARs developed using fragment contribution methods that include up to 59 descriptors. The predictive statistics of the models are similar thus further corroborating the predictive performance of the different QSARs; Q(2)ext ranges from 0.75 to 0.77, CCCext ranges from 0.86 to 0.87, RMSE in prediction ranges from 0.56 to 0.58. The new QSARs provide additional mechanistic insights into the biotransformation capacity of organic chemicals in fish by including whole molecule descriptors and they also include information on the domain of applicability for the chemical of interest. Advantages of consensus modeling for improving overall prediction and minimizing false negative errors in chemical screening assessments, for identifying potential sources of residual error in the empirical HLN database, and for identifying structural features that are not well represented in the HLN dataset to prioritize future testing needs are illustrated. © 2013.

Single Droplet Combustion of Decane in Microgravity: Experiments and Numerical Modeling

NASA Technical Reports Server (NTRS)

Dietrich, D. L.; Struk, P. M.; Ikegam, M.; Xu, G.

2004-01-01

This paper presents experimental data on single droplet combustion of decane in microgravity and compares the results to a numerical model. The primary independent experiment variables are the ambient pressure and oxygen mole fraction, pressure, droplet size (over a relatively small range) and ignition energy. The droplet history (D(sup 2) history) is non-linear with the burning rate constant increasing throughout the test. The average burning rate constant, consistent with classical theory, increased with increasing ambient oxygen mole fraction and was nearly independent of pressure, initial droplet size and ignition energy. The flame typically increased in size initially, and then decreased in size, in response to the shrinking droplet. The flame standoff increased linearly for the majority of the droplet lifetime. The flame surrounding the droplet extinguished at a finite droplet size at lower ambient pressures and an oxygen mole fraction of 0.15. The extinction droplet size increased with decreasing pressure. The model is transient and assumes spherical symmetry, constant thermo-physical properties (specific heat, thermal conductivity and species Lewis number) and single step chemistry. The model includes gas-phase radiative loss and a spherically symmetric, transient liquid phase. The model accurately predicts the droplet and flame histories of the experiments. Good agreement requires that the ignition in the experiment be reasonably approximated in the model and that the model accurately predict the pre-ignition vaporization of the droplet. The model does not accurately predict the dependence of extinction droplet diameter on pressure, a result of the simplified chemistry in the model. The transient flame behavior suggests the potential importance of fuel vapor accumulation. The model results, however, show that the fractional mass consumption rate of fuel in the flame relative to fuel vaporized is close to 1.0 for all but the lowest ambient oxygen mole fractions.

Allometric growth in reef-building corals.

PubMed

Dornelas, Maria; Madin, Joshua S; Baird, Andrew H; Connolly, Sean R

2017-03-29

Predicting demographic rates is a critical part of forecasting the future of ecosystems under global change. Here, we test if growth rates can be predicted from morphological traits for a highly diverse group of colonial symbiotic organisms: scleractinian corals. We ask whether growth is isometric or allometric among corals, and whether most variation in coral growth rates occurs at the level of the species or morphological group. We estimate growth as change in planar area for 11 species, across five morphological groups and over 5 years. We show that coral growth rates are best predicted from colony size and morphology rather than species. Coral size follows a power scaling law with a constant exponent of 0.91. Despite being colonial organisms, corals have consistent allometric scaling in growth. This consistency simplifies the task of projecting community responses to disturbance and climate change. © 2017 The Author(s).

Modeling the pH and temperature dependence of aqueousphase hydroxyl radical reaction rate constants of organic micropollutants using QSPR approach.

PubMed

Gupta, Shikha; Basant, Nikita

2017-11-01

Designing of advanced oxidation process (AOP) requires knowledge of the aqueous phase hydroxyl radical ( ● OH) reactions rate constants (k OH ), which are strictly dependent upon the pH and temperature of the medium. In this study, pH- and temperature-dependent quantitative structure-property relationship (QSPR) models based on the decision tree boost (DTB) approach were developed for the prediction of k OH of diverse organic contaminants following the OECD guidelines. Experimental datasets (n = 958) pertaining to the k OH values of aqueous phase reactions at different pH (n = 470; 1.4 × 10 6 to 3.8 × 10 10  M -1  s -1 ) and temperature (n = 171; 1.0 × 10 7 to 2.6 × 10 10  M -1  s -1 ) were considered and molecular descriptors of the compounds were derived. The Sanderson scale electronegativity, topological polar surface area, number of double bonds, and halogen atoms in the molecule, in addition to the pH and temperature, were found to be the relevant predictors. The models were validated and their external predictivity was evaluated in terms of most stringent criteria parameters derived on the test data. High values of the coefficient of determination (R 2 ) and small root mean squared error (RMSE) in respective training (> 0.972, ≤ 0.12) and test (≥ 0.936, ≤ 0.16) sets indicated high generalization and predictivity of the developed QSPR model. Other statistical parameters derived from the training and test data also supported the robustness of the models and their suitability for screening new chemicals within the defined chemical space. The developed QSPR models provide a valuable tool for predicting the ● OH reaction rate constants of emerging new water contaminants for their susceptibility to AOPs.

Modeling and predicting the biofilm formation of Salmonella Virchow with respect to temperature and pH.

PubMed

Ariafar, M Nima; Buzrul, Sencer; Akçelik, Nefise

2016-03-01

Biofilm formation of Salmonella Virchow was monitored with respect to time at three different temperature (20, 25 and 27.5 °C) and pH (5.2, 5.9 and 6.6) values. As the temperature increased at a constant pH level, biofilm formation decreased while as the pH level increased at a constant temperature, biofilm formation increased. Modified Gompertz equation with high adjusted determination coefficient (Radj(2)) and low mean square error (MSE) values produced reasonable fits for the biofilm formation under all conditions. Parameters of the modified Gompertz equation could be described in terms of temperature and pH by use of a second order polynomial function. In general, as temperature increased maximum biofilm quantity, maximum biofilm formation rate and time of acceleration of biofilm formation decreased; whereas, as pH increased; maximum biofilm quantity, maximum biofilm formation rate and time of acceleration of biofilm formation increased. Two temperature (23 and 26 °C) and pH (5.3 and 6.3) values were used up to 24 h to predict the biofilm formation of S. Virchow. Although the predictions did not perfectly match with the data, reasonable estimates were obtained. In principle, modeling and predicting the biofilm formation of different microorganisms on different surfaces under various conditions could be possible.

Improved Predictions of Drug-Drug Interactions Mediated by Time-Dependent Inhibition of CYP3A.

PubMed

Yadav, Jaydeep; Korzekwa, Ken; Nagar, Swati

2018-05-07

Time-dependent inactivation (TDI) of cytochrome P450s (CYPs) is a leading cause of clinical drug-drug interactions (DDIs). Current methods tend to overpredict DDIs. In this study, a numerical approach was used to model complex CYP3A TDI in human-liver microsomes. The inhibitors evaluated included troleandomycin (TAO), erythromycin (ERY), verapamil (VER), and diltiazem (DTZ) along with the primary metabolites N-demethyl erythromycin (NDE), norverapamil (NV), and N-desmethyl diltiazem (NDD). The complexities incorporated into the models included multiple-binding kinetics, quasi-irreversible inactivation, sequential metabolism, inhibitor depletion, and membrane partitioning. The resulting inactivation parameters were incorporated into static in vitro-in vivo correlation (IVIVC) models to predict clinical DDIs. For 77 clinically observed DDIs, with a hepatic-CYP3A-synthesis-rate constant of 0.000 146 min -1 , the average fold difference between the observed and predicted DDIs was 3.17 for the standard replot method and 1.45 for the numerical method. Similar results were obtained using a synthesis-rate constant of 0.000 32 min -1 . These results suggest that numerical methods can successfully model complex in vitro TDI kinetics and that the resulting DDI predictions are more accurate than those obtained with the standard replot approach.

CN radical reactions with hydrogen cyanide and cyanogen - Comparison of theory and experiment

NASA Technical Reports Server (NTRS)

Yang, D. L.; Yu, T.; Lin, M. C.; Melius, C. F.

1992-01-01

The method of laser photolysis/laser-induced fluorescence is used to obtain absolute rate constants for CN radical reactions with HCN and C2N2. The rate constants were found to be temperature-dependent in the range 300-740 K and pressure independent in the range 100-600 Torr. Rice-Remsperger-Kassel-Marcus theory for both reactions employing the transition state parameters obtained by the BAC-MP4 method are made. These calculations yielded reasonable results for the CN + HCN reaction, predicting both the temperature dependence and pressure independence. No pressure effect was observed in the pressure range 100-1000 Torr at temperatures below 900 K, confirming the experimental results.

Investigation on temporal evolution of the grain refinement in copper under high strain rate loading via in-situ synchrotron measurement and predictive modeling

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

Shah, Pooja Nitin; Shin, Yung C.; Sun, Tao

Synchrotron X-rays are integrated with a modified Kolsky tension bar to conduct in situ tracking of the grain refinement mechanism operating during the dynamic deformation of metals. Copper with an initial average grain size of 36 μm is refined to 6.3 μm when loaded at a constant high strain rate of 1200 s -1. The synchrotron measurements revealed the temporal evolution of the grain refinement mechanism in terms of the initiation and rate of refinement throughout the loading test. A multiscale coupled probabilistic cellular automata based recrystallization model has been developed to predict the microstructural evolution occurring during dynamic deformationmore » processes. The model accurately predicts the initiation of the grain refinement mechanism with a predicted final average grain size of 2.4 μm. As a result, the model also accurately predicts the temporal evolution in terms of the initiation and extent of refinement when compared with the experimental results.« less

Investigation on temporal evolution of the grain refinement in copper under high strain rate loading via in-situ synchrotron measurement and predictive modeling

DOE PAGES

Shah, Pooja Nitin; Shin, Yung C.; Sun, Tao

2017-10-03

Synchrotron X-rays are integrated with a modified Kolsky tension bar to conduct in situ tracking of the grain refinement mechanism operating during the dynamic deformation of metals. Copper with an initial average grain size of 36 μm is refined to 6.3 μm when loaded at a constant high strain rate of 1200 s -1. The synchrotron measurements revealed the temporal evolution of the grain refinement mechanism in terms of the initiation and rate of refinement throughout the loading test. A multiscale coupled probabilistic cellular automata based recrystallization model has been developed to predict the microstructural evolution occurring during dynamic deformationmore » processes. The model accurately predicts the initiation of the grain refinement mechanism with a predicted final average grain size of 2.4 μm. As a result, the model also accurately predicts the temporal evolution in terms of the initiation and extent of refinement when compared with the experimental results.« less

A Fully Coupled Multi-Rigid-Body Fuel Slosh Dynamics Model Applied to the Triana Stack

NASA Technical Reports Server (NTRS)

London, K. W.

2001-01-01

A somewhat general multibody model is presented that accounts for energy dissipation associated with fuel slosh and which unifies some of the existing more specialized representations. This model is used to predict the mutation growth time constant for the Triana Spacecraft, or Stack, consisting of the Triana Observatory mated with the Gyroscopic Upper Stage of GUS (includes the solid rocket motor, SRM, booster). At the nominal spin rate of 60 rpm and with 145 kg of hydrazine propellant on board, a time constant of 116 s is predicted for worst case sloshing of a spherical slug model compared to 1,681 s (nominal), 1,043 s (worst case) for sloshing of a three degree of freedom pendulum model.

FORMAL UNCERTAINTY ANALYSIS OF A LAGRANGIAN PHOTOCHEMICAL AIR POLLUTION MODEL. (R824792)

EPA Science Inventory

This study applied Monte Carlo analysis with Latin
hypercube sampling to evaluate the effects of uncertainty
in air parcel trajectory paths, emissions, rate constants,
deposition affinities, mixing heights, and atmospheric stability
on predictions from a vertically...

Effectiveness of netilmicin and tobramycin against Pseudomonas aeruginosa in vitro and in an experimental tissue infection in mice.

PubMed

Moffie, B G; Hoogeterp, J J; Lim, T; Douwes-Idema, A E; Mattie, H

1993-03-01

The activity of netilmicin and tobramycin against Pseudomonas aeruginosa was assessed in vitro in the presence of constant and exponentially declining concentrations, and in mice in an experimental thigh infection. The activity in vitro at constant concentrations was expressed as the maximal killing rate (ER) during 3 h of exposure. On the basis of the quantitative relation between E(R) and the drug concentration, the numbers of cfu expected at consecutive times, at constant as well as at declining concentrations, were predicted. The relationship between observed numbers and predicted values of ERt were similar under both conditions for both drugs. On the same basis the numbers of cfu expected in the experimental thigh infection were predicted. There was indeed a significant linear relationship between observed numbers of cfu in homogenized muscle and the values predicted on the basis of the pharmacokinetics of the aminoglycosides, but the slope of this relationship was only 0.22. There was no difference in this respect between the two antibiotics. It is concluded that the efficacy of netilmicin and tobramycin against P. aeruginosa is considerably less in vivo than in vitro, but the relation is about the same for the two drugs; therefore the slightly higher activity of tobramycin in vitro is relevant in the in-vivo situation.

Temporal variations in volumetric magma eruption rates of Quaternary volcanoes in Japan

NASA Astrophysics Data System (ADS)

Yamamoto, Takahiro; Kudo, Takashi; Isizuka, Osamu

2018-04-01

Long-term evaluations of hazard and risk related to volcanoes rely on extrapolations from volcano histories, including the uniformity of their eruption rates. We calculated volumetric magma eruption rates, compiled from quantitative eruption histories of 29 Japanese Quaternary volcanoes, and analyzed them with respect to durations spanning 101-105 years. Calculated eruption rates vary greatly (101-10-4 km3 dense-rock equivalent/1000 years) between individual volcanoes. Although large basaltic stratovolcanoes tend to have high eruption rates and relatively constant repose intervals, these cases are not representative of the various types of volcanoes in Japan. At many Japanese volcanoes, eruption rates are not constant through time, but increase, decrease, or fluctuate. Therefore, it is important to predict whether eruption rates will increase or decrease for long-term risk assessment. Several temporal co-variations of eruption rate and magmatic evolution suggest that there are connections between them. In some cases, magma supply rates increased in response to changing magma-generation processes. On the other hand, stable plumbing systems without marked changes in magma composition show decreasing eruption rates through time.[Figure not available: see fulltext.

Prediction of in situ root decomposition rates in an interspecific context from chemical and morphological traits

PubMed Central

Aulen, Maurice; Shipley, Bill; Bradley, Robert

2012-01-01

Background and Aims We quantitatively relate in situ root decomposition rates of a wide range of trees and herbs used in agroforestry to root chemical and morphological traits in order to better describe carbon fluxes from roots to the soil carbon pool across a diverse group of plant species. Methods In situ root decomposition rates were measured over an entire year by an intact core method on ten tree and seven herb species typical of agroforestry systems and were quantified using decay constants (k values) from Olson's single exponential model. Decay constants were related to root chemical (total carbon, nitrogen, soluble carbon, cellulose, hemicellulose, lignin) and morphological (specific root length, specific root length) traits. Traits were measured for both absorbing and non-absorbing roots. Key Results From 61 to 77 % of the variation in the different root traits and 63 % of that in root decomposition rates was interspecific. N was positively correlated, but total carbon and lignin were negatively correlated with k values. Initial root traits accounted for 75 % of the variation in interspecific decomposition rates using partial least squares regressions; partial slopes attributed to each trait were consistent with functional ecology expectations. Conclusions Easily measured initial root traits can be used to predict rates of root decomposition in soils in an interspecific context. PMID:22003237

Oxidation and Volatilization of Silica-Formers in Water Vapor

NASA Technical Reports Server (NTRS)

Opila, E. J.; Gray, Hugh R. (Technical Monitor)

2002-01-01

At high temperatures SiC and Si3N4 react with water vapor to form a silica scale. Silica scales also react with water vapor to form a volatile Si(OH)4 species. These simultaneous reactions, one forming silica and the other removing silica, are described by paralinear kinetics. A steady state, in which these reactions occur at the same rate, is eventually achieved, After steady state is achieved, the oxide found on the surface is a constant thickness and recession of the underlying material occurs at a linear rate. The steady state oxide thickness, the time to achieve steady state, and the steady state recession rate can all be described in terms of the rate constants for the oxidation and volatilization reactions. In addition, the oxide thickness, the time to achieve steady state, and the recession rate can also be determined from parameters that describe a water vapor-containing environment. Accordingly, maps have been developed to show these steady state conditions as a function of reaction rate constants, pressure, and gas velocity. These maps can be used to predict the behavior of silica formers in water-vapor containing environments such as combustion environments. Finally, these maps are used to explore the limits of the paralinear oxidation model for SiC and Si3N4

Terminal base pairs of oligodeoxynucleotides: imino proton exchange and fraying.

PubMed

Nonin, S; Leroy, J L; Guéron, M

1995-08-22

We have estimated the dissociation constant of the terminal base pairs of the B-DNA duplexes formed by 5'-d(CGCGATCGCG) and 5'-d(TAGCGCTA) by two methods, one based on the change in imino proton chemical shift with temperature and the other on the apparent pK shift of the imino proton, as monitored by the change in chemical shift of aromatic protons. These methods do not rely on imino proton exchange, whose rate was also measured. (1) The effect of ammonia on the imino proton exchange rate of the terminal pair of the 5'-d(CGCGATCGCG) duplex is 67 times less than on the isolated nucleoside. This provides an upper limit on the exchange rate from the closed pair. In fact, the effect is just as predicted from the dissociation constant, assuming that there is no exchange at all from the closed pair and that, as has been argued previously, external catalysts act on the open state as they do on the isolated nucleoside. The inhibition of catalyzed proton exchange in the closed pair, despite exposure of one face of the pair to solvent, is a new feature of the exchange process. It will allow determination of the dissociation constant of terminal pairs from the exchange rate. (2) Intrinsic catalysis of proton exchange is less efficient for the terminal pair than for an internal one. A possible explanation is that proton transfer across the water bridge responsible for intrinsic catalysis is slower, as expected if the open-state separation of the bases is larger in a terminal pair. This observation may lead to a direct method for the study of fraying. (3) At 0 degrees C, the dissociation constant of the second pair of the 5'-d(CGCGATCGCG) duplex is close to the square of the constant for the terminal pair, as predicted from a simple model of fraying. The enthalpy and entropy of opening of the terminal pairs may be compared with those of nearest neighbor interactions derived from calorimetry [Breslauer, K. J., et al. (1986) Proc. Natl. Acad. Sci. U.S.A. 83, 3746-3750].

A Comparative Study of Spectral Auroral Intensity Predictions From Multiple Electron Transport Models

NASA Astrophysics Data System (ADS)

Grubbs, Guy; Michell, Robert; Samara, Marilia; Hampton, Donald; Hecht, James; Solomon, Stanley; Jahn, Jorg-Micha

2018-01-01

It is important to routinely examine and update models used to predict auroral emissions resulting from precipitating electrons in Earth's magnetotail. These models are commonly used to invert spectral auroral ground-based images to infer characteristics about incident electron populations when in situ measurements are unavailable. In this work, we examine and compare auroral emission intensities predicted by three commonly used electron transport models using varying electron population characteristics. We then compare model predictions to same-volume in situ electron measurements and ground-based imaging to qualitatively examine modeling prediction error. Initial comparisons showed differences in predictions by the GLobal airglOW (GLOW) model and the other transport models examined. Chemical reaction rates and radiative rates in GLOW were updated using recent publications, and predictions showed better agreement with the other models and the same-volume data, stressing that these rates are important to consider when modeling auroral processes. Predictions by each model exhibit similar behavior for varying atmospheric constants, energies, and energy fluxes. Same-volume electron data and images are highly correlated with predictions by each model, showing that these models can be used to accurately derive electron characteristics and ionospheric parameters based solely on multispectral optical imaging data.

The metabolic cost of changing walking speeds is significant, implies lower optimal speeds for shorter distances, and increases daily energy estimates.

PubMed

Seethapathi, Nidhi; Srinivasan, Manoj

2015-09-01

Humans do not generally walk at constant speed, except perhaps on a treadmill. Normal walking involves starting, stopping and changing speeds, in addition to roughly steady locomotion. Here, we measure the metabolic energy cost of walking when changing speed. Subjects (healthy adults) walked with oscillating speeds on a constant-speed treadmill, alternating between walking slower and faster than the treadmill belt, moving back and forth in the laboratory frame. The metabolic rate for oscillating-speed walking was significantly higher than that for constant-speed walking (6-20% cost increase for ±0.13-0.27 m s(-1) speed fluctuations). The metabolic rate increase was correlated with two models: a model based on kinetic energy fluctuations and an inverted pendulum walking model, optimized for oscillating-speed constraints. The cost of changing speeds may have behavioural implications: we predicted that the energy-optimal walking speed is lower for shorter distances. We measured preferred human walking speeds for different walking distances and found people preferred lower walking speeds for shorter distances as predicted. Further, analysing published daily walking-bout distributions, we estimate that the cost of changing speeds is 4-8% of daily walking energy budget. © 2015 The Author(s).

The metabolic cost of changing walking speeds is significant, implies lower optimal speeds for shorter distances, and increases daily energy estimates

PubMed Central

Seethapathi, Nidhi; Srinivasan, Manoj

2015-01-01

Humans do not generally walk at constant speed, except perhaps on a treadmill. Normal walking involves starting, stopping and changing speeds, in addition to roughly steady locomotion. Here, we measure the metabolic energy cost of walking when changing speed. Subjects (healthy adults) walked with oscillating speeds on a constant-speed treadmill, alternating between walking slower and faster than the treadmill belt, moving back and forth in the laboratory frame. The metabolic rate for oscillating-speed walking was significantly higher than that for constant-speed walking (6–20% cost increase for ±0.13–0.27 m s−1 speed fluctuations). The metabolic rate increase was correlated with two models: a model based on kinetic energy fluctuations and an inverted pendulum walking model, optimized for oscillating-speed constraints. The cost of changing speeds may have behavioural implications: we predicted that the energy-optimal walking speed is lower for shorter distances. We measured preferred human walking speeds for different walking distances and found people preferred lower walking speeds for shorter distances as predicted. Further, analysing published daily walking-bout distributions, we estimate that the cost of changing speeds is 4–8% of daily walking energy budget. PMID:26382072

Virus Sensitivity Index of UV disinfection.

PubMed

Tang, Walter Z; Sillanpää, Mika

2015-01-01

A new concept of Virus Sensitivity Index (VSI) is defined as the ratio between the first-order inactivation rate constant of a virus, ki, and that of MS2-phage during UV disinfection, kr. MS2-phage is chosen as the reference virus because it is recommended as a virus indicator during UV reactor design and validation by the US Environmental Protection Agency. VSI has wide applications in research, design, and validation of UV disinfection systems. For example, it can be used to rank the UV disinfection sensitivity of viruses in reference to MS2-phage. There are four major steps in deriving the equation between Hi/Hr and 1/VSI. First, the first-order inactivation rate constants are determined by regression analysis between Log I and fluence required. Second, the inactivation rate constants of MS2-phage are statistically analysed at 3, 4, 5, and 6 Log I levels. Third, different VSI values are obtained from the ki of different viruses dividing by the kr of MS2-phage. Fourth, correlation between Hi/Hr and 1/VSI is analysed by using linear, quadratic, and cubic models. As expected from the theoretical analysis, a linear relationship adequately correlates Hi/Hr and 1/VSI without an intercept. VSI is used to quantitatively predict the UV fluence required for any virus at any log inactivation (Log I). Four equations were developed at 3, 4, 5, and 6 Log I. These equations have been validated using external data which are not used for the virus development. At Log I less than 3, the equation tends to under-predict the required fluence at both low Log I such as 1 and 2 Log I. At Log I greater than 3 Log I, the equation tends to over-predict the fluence required. The reasons for these may very likely be due to the shoulder at the beginning and the tailing at the end of the collimated beam test experiments. At 3 Log I, the error percentage is less than 6%. The VSI is also used to predict inactivation rate constants under two different UV disinfection scenarios such as under sunlight and different virus aggregates. The correlation analysis shows that viruses will be about 40% more sensitive to sunlight than to UV254. On the other hand, virus size of 500 nm will reduce their VSI by 10%. This is the first attempt to use VSI to predict the required fluence at any given Log I. The equation can be used to quantitatively evaluate other parameters influencing UV disinfection. These factors include environmental species, antibiotic-resistant bacteria or genes, photo and dark repair, water quality such as suspended solids, and UV transmittance.

A theoretical study of the H-abstraction reactions from HOI by moist air radiolytic products (H, OH, and O (3P)) and iodine atoms (2P(3/2)).

PubMed

Hammaecher, Catherine; Canneaux, Sébastien; Louis, Florent; Cantrel, Laurent

2011-06-23

The rate constants of the reactions of HOI molecules with H, OH, O ((3)P), and I ((2)P(3/2)) atoms have been estimated over the temperature range 300-2500 K using four different levels of theory. Geometry optimizations and vibrational frequency calculations are performed using MP2 methods combined with two basis sets (cc-pVTZ and 6-311G(d,p)). Single-point energy calculations are performed with the highly correlated ab initio coupled cluster method in the space of single, double, and triple (pertubatively) electron excitations CCSD(T) using the cc-pVTZ, cc-pVQZ, 6-311+G(3df,2p), and 6-311++G(3df,3pd) basis sets. Reaction enthalpies at 0 K were calculated at the CCSD(T)/cc-pVnZ//MP2/cc-pVTZ (n = T and Q), CCSD(T)/6-311+G(3df,2p)//MP2/6-311G(d,p), and CCSD(T)/6-311++G(3df,3pd)//MP2/6-311G(d,p) levels of theory and compared to the experimental values taken from the literature. Canonical transition-state theory with an Eckart tunneling correction is used to predict the rate constants as a function of temperature. The computational procedure has been used to predict rate constants for H-abstraction elementary reactions because there are actually no literature data to which the calculated rate constants can be directly compared. The final objective is to implement kinetics of gaseous reactions in the ASTEC (accident source term evaluation code) program to improve speciation of fission products, which can be transported along the reactor coolant system (RCS) of a pressurized water reactor (PWR) in the case of a severe accident.

TiC growth in C fiber/Ti alloy composites during liquid infiltration

NASA Technical Reports Server (NTRS)

Warrier, S. G.; Lin, R. Y.

1993-01-01

A cylindrical model is developed for predicting the reaction zone thickness of carbon fiber-reinforced Ti-matrix composites, and good agreement is obtained between its predicted values and experimental results. The reaction-rate constant for TiC formation is estimated to be 1.5 x 10 exp -9 sq cm/sec. The model is extended to evaluate the relationship between C-coating thicknesses on SiC fibers and processing times.

Absolute rate constants for the reaction of OH with cyclopentane and cycloheptane from 233 to 351 K.

PubMed

Gennaco, Michael A; Huang, Yi-wen; Hannun, Reem A; Dransfield, Timothy J

2012-12-27

Absolute rate constant measurements for the reactions of OH with cyclopentane and cycloheptane in the gas phase in 6-8 Torr of nitrogen from 233 to 351 K in the Harvard University High-Pressure Flow System (HPFS) are reported. Hydroxyl concentrations were measured using laser-induced fluorescence, and alkane concentrations were measured using Fourier transform infrared spectroscopy. Results were fit to a modified Arrhenius equation based on transition state theory (ignoring tunneling): k(T) = B e(-E(a)/T)/T(1 - e(-1.44ν(1)/T))(2)(1 - e(-1.44ν(2)/T)), with ν(1) and ν(2) bending frequencies set to 280 and 500 cm(-1) . Results were as follows for E(a) (K) and k (298) (10(-12) cm(3) s(-1)): cyclopentane, 460 ± 32, 4.85; cycloheptane, 319 ± 36, 9.84. This work represents the second absolute temperature-dependent rate constant measurement reported for cycloheptane, and the third absolute temperature-dependent rate constant measurement reported near room temperature for the reaction of OH and cyclopentane. For the title reactions, the reaction barriers reported here are in agreement with the reaction barrier previously reported for cyclohexane and considerably higher than the barrier previously reported for cyclo-octane, a result that is not predicted by our current understanding of hydrocarbon reactivity.

Transient shear banding in the nematic dumbbell model of liquid crystalline polymers

NASA Astrophysics Data System (ADS)

Adams, J. M.; Corbett, D.

2018-05-01

In the shear flow of liquid crystalline polymers (LCPs) the nematic director orientation can align with the flow direction for some materials but continuously tumble in others. The nematic dumbbell (ND) model was originally developed to describe the rheology of flow-aligning semiflexible LCPs, and flow-aligning LCPs are the focus in this paper. In the shear flow of monodomain LCPs, it is usually assumed that the spatial distribution of the velocity is uniform. This is in contrast to polymer solutions, where highly nonuniform spatial velocity profiles have been observed in experiments. We analyze the ND model, with an additional gradient term in the constitutive model, using a linear stability analysis. We investigate the separate cases of constant applied shear stress and constant applied shear rate. We find that the ND model has a transient flow instability to the formation of a spatially inhomogeneous flow velocity for certain starting orientations of the director. We calculate the spatially resolved flow profile in both constant applied stress and constant applied shear rate in start up from rest, using a model with one spatial dimension to illustrate the flow behavior of the fluid. For low shear rates flow reversal can be seen as the director realigns with the flow direction, whereas for high shear rates the director reorientation occurs simultaneously across the gap. Experimentally, this inhomogeneous flow is predicted to be observed in flow reversal experiments in LCPs.

An approximate analytical solution for describing surface runoff and sediment transport over hillslope

NASA Astrophysics Data System (ADS)

Tao, Wanghai; Wang, Quanjiu; Lin, Henry

2018-03-01

Soil and water loss from farmland causes land degradation and water pollution, thus continued efforts are needed to establish mathematical model for quantitative analysis of relevant processes and mechanisms. In this study, an approximate analytical solution has been developed for overland flow model and sediment transport model, offering a simple and effective means to predict overland flow and erosion under natural rainfall conditions. In the overland flow model, the flow regime was considered to be transitional with the value of parameter β (in the kinematic wave model) approximately two. The change rate of unit discharge with distance was assumed to be constant and equal to the runoff rate at the outlet of the plane. The excess rainfall was considered to be constant under uniform rainfall conditions. The overland flow model developed can be further applied to natural rainfall conditions by treating excess rainfall intensity as constant over a small time interval. For the sediment model, the recommended values of the runoff erosion calibration constant (cr) and the splash erosion calibration constant (cf) have been given in this study so that it is easier to use the model. These recommended values are 0.15 and 0.12, respectively. Comparisons with observed results were carried out to validate the proposed analytical solution. The results showed that the approximate analytical solution developed in this paper closely matches the observed data, thus providing an alternative method of predicting runoff generation and sediment yield, and offering a more convenient method of analyzing the quantitative relationships between variables. Furthermore, the model developed in this study can be used as a theoretical basis for developing runoff and erosion control methods.

Key environmental processes affecting the fate of the insecticide chloropyrifos applied to leaves.

PubMed

Lester, Yaal; Sabach, Sara; Zivan, Ohad; Dubowski, Yael

2017-03-01

Chlorpyrifos (CP) is still a commonly employed organophosphorus insecticide worldwide. In semi-arid and Mediterranean climates, applied CP is expected to remain on leaves surfaces for relatively long time due to the lack of summer rains and common use of drip irrigation. The present work examines the loss rate of CP from leaves via different surface processes: evaporation, direct photolysis and reactions with ozone and OH radicals. Laboratory experiments showed that evaporation rate constant of CP increased from 0.109 to 0.492 h -1 with the increase in wind speed up to 4 m/s. First-order rate constant of direct photolysis, measured using a solar simulator, was k' UV  = 1.15 (±0.01) x 10 -20  cm 2 photon -1 . Second-order rate constants for the reaction of CP with ozone and OH were measured as 6 × 10 -20 and 6 × 10 -12  cm 3  molecule -1  s -1 , respectively. The above rate constants were applied successfully in an outdoor experiment to predict the disappearance of chloropyrifos under specific environmental conditions. Further modeling showed that the insecticide half-life time on exposed surfaces under typical Mediterranean environment will be in the range of 0.9-6.9 h. Evaporation is expected to be the dominant removal path under most environmental conditions, followed by direct photolysis and reaction with OH. Copyright © 2016 Elsevier Ltd. All rights reserved.

Slow Crack Growth of Brittle Materials With Exponential Crack-Velocity Formulation. Part 2; Constant Stress Rate Experiments

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Nemeth, Noel N.; Gyekenyesi, John P.

2002-01-01

The previously determined life prediction analysis based on an exponential crack-velocity formulation was examined using a variety of experimental data on glass and advanced structural ceramics in constant stress rate and preload testing at ambient and elevated temperatures. The data fit to the relation of strength versus the log of the stress rate was very reasonable for most of the materials. Also, the preloading technique was determined equally applicable to the case of slow-crack-growth (SCG) parameter n greater than 30 for both the power-law and exponential formulations. The major limitation in the exponential crack-velocity formulation, however, was that the inert strength of a material must be known a priori to evaluate the important SCG parameter n, a significant drawback as compared with the conventional power-law crack-velocity formulation.

Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ4H7 Potential Energy Surface.

PubMed

Li, Yang; Klippenstein, Stephen J; Zhou, Chong-Wen; Curran, Henry J

2017-10-12

The oxidation chemistry of the simplest conjugated hydrocarbon, 1,3-butadiene, can provide a first step in understanding the role of polyunsaturated hydrocarbons in combustion and, in particular, an understanding of their contribution toward soot formation. On the basis of our previous work on propene and the butene isomers (1-, 2-, and isobutene), it was found that the reaction kinetics of Ḣ-atom addition to the C═C double bond plays a significant role in fuel consumption kinetics and influences the predictions of high-temperature ignition delay times, product species concentrations, and flame speed measurements. In this study, the rate constants and thermodynamic properties for Ḣ-atom addition to 1,3-butadiene and related reactions on the Ċ 4 H 7 potential energy surface have been calculated using two different series of quantum chemical methods and two different kinetic codes. Excellent agreement is obtained between the two different kinetics codes. The calculated results including zero-point energies, single-point energies, rate constants, barrier heights, and thermochemistry are systematically compared among the two quantum chemical methods. 1-Methylallyl (Ċ 4 H 7 1-3) and 3-buten-1-yl (Ċ 4 H 7 1-4) radicals and C 2 H 4 + Ċ 2 H 3 are found to be the most important channels and reactivity-promoting products, respectively. We calculated that terminal addition is dominant (>80%) compared to internal Ḣ-atom addition at all temperatures in the range 298-2000 K. However, this dominance decreases with increasing temperature. The calculated rate constants for the bimolecular reaction C 4 H 6 + Ḣ → products and C 2 H 4 + Ċ 2 H 3 → products are in excellent agreement with both experimental and theoretical results from the literature. For selected C 4 species, the calculated thermochemical values are also in good agreement with literature data. In addition, the rate constants for H atom abstraction by Ḣ atoms have also been calculated, and it is found that abstraction from the central carbon atoms is the dominant channel (>70%) at temperatures in the range of 298-2000 K. Finally, by incorporating our calculated rate constants for both Ḣ atom addition and abstraction into our recently developed 1,3-butadiene model, we show that laminar flame speed predictions are significantly improved, emphasizing the value of this study.

Spatial and Temporal Dynamics of Dissolved Oxygen Concentrations and Bioactivity in the Hyporheic Zone

NASA Astrophysics Data System (ADS)

Reeder, W. Jeffery; Quick, Annika M.; Farrell, Tiffany B.; Benner, Shawn G.; Feris, Kevin P.; Tonina, Daniele

2018-03-01

Dissolved oxygen (DO) concentrations and consumption rates are primary indicators of heterotrophic respiration and redox conditions in the hyporheic zone (HZ). Due to the complexity of hyporheic flow and interactions between hyporheic hydraulics and the biogeochemical processes, a detailed, mechanistic, and predictive understanding of the biogeochemical activity in the HZ has not yet been developed. Previous studies of microbial activity in the HZ have treated the metabolic DO consumption rate constant (KDO) as a temporally fixed and spatially homogeneous property that is determined primarily by the concentration of bioavailable carbon. These studies have generally treated bioactivity as temporally steady state, failing to capture the temporal dynamics of a changeable system. We demonstrate that hyporheic hydraulics controls rate constants in a hyporheic system that is relatively abundant in bioavailable carbon, such that KDO is a linear function of the local downwelling flux. We further demonstrate that, for triangular dunes, the downwelling velocities are lognormally distributed, as are the KDO values. By comparing measured and modeled DO profiles, we demonstrate that treating KDO as a function of the downwelling flux yields a significant improvement in the accuracy of predicted DO profiles. Additionally, our results demonstrate the temporal effect of carbon consumption on microbial respiration rates.

SU-F-T-344: Commissioning Constant Dose Rate VMAT in the Raystation Treatment Planning System for a Varian Clinac IX

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

Pursley, J; Gueorguiev, G; Prichard, H

Purpose: To demonstrate the commissioning of constant dose rate volumetric modulated arc therapy (VMAT) in the Raystation treatment planning system for a Varian Clinac iX with Exact couch. Methods: Constant dose rate (CDR) VMAT is an option in the Raystation treatment planning system, enabling VMAT delivery on Varian linacs without a RapidArc upgrade. Raystation 4.7 was used to commission CDR-VMAT for a Varian Clinac iX. Raystation arc model parameters were selected to match machine deliverability characteristics. A Varian Exact couch model was added to Raystation 4.7 and commissioned for use in VMAT optimization. CDR-VMAT commissioning checks were performed on themore » linac, including patient-specific QA measurements for 10 test patients using both the ArcCHECK from Sun Nuclear Corporation and COMPASS from IBA Dosimetry. Multi-criteria optimization (MCO) in Raystation was used for CDR-VMAT planning. Results: Raystation 4.7 generated clinically acceptable and deliverable CDR-VMAT plans for the Varian Clinac. VMAT plans were optimized including a model of the Exact couch with both rails in the out positions. CDR-VMAT plans generated with MCO in Raystation were dosimetrically comparable to Raystation MCO-generated IMRT plans. Patient-specific QA measurements with the ArcCHECK on the couch showed good agreement with the treatment planning system prediction. Patient-specific, structure-specific, multi-statistical parameter 3D QA measurements with gantry-mounted COMPASS also showed good agreement. Conclusion: Constant dose rate VMAT was successfully modeled in Raystation 4.7 for a Varian Clinac iX, and Raystation’s multicriteria optimization generated constant dose rate VMAT plans which were deliverable and dosimetrically comparable to IMRT plans.« less

Wavelength-Resolved Photon Fluxes of Indoor Light Sources: Implications for HOx Production

NASA Astrophysics Data System (ADS)

Kowal, S.; Kahan, T.

2017-12-01

Only a handful of studies have considered photolytic reactions indoors because photon fluxes at short wavelengths are generally considered to be negligible. We have measured wavelength resolved photon fluxes from indoor light sources including incandescent, halogen, compact fluorescent (CFL), and light emitting diodes (LED). In addition, fluorescent tubes, used in many offices and industrial buildings, and sunlight through windows were measured. The measured photon fluxes were used to calculate photolysis rate constants for potential indoor hydroxyl and peroxy radical (OH and HO2, "HOx") precursors: acetaldehyde (CH3CHO), formaldehyde (HCHO), hydrogen peroxide (H2O2), nitrous acid (HONO) and ozone (O3). Rate constants in conjunction with typical indoor concentrations were used to predict HOx production rates under various lighting conditions. Our results illustrate that all light sources except LEDs emit light at high enough energy to photolyze HOx precursors. Under typical lighting conditions only fluorescent tubes and sunlight will initiate significant photochemical HOx formation, and HONO and HCHO will be the only molecules that will have a strong influence on HOx levels indoors. Data from our experiments can be used in indoor air models to better predict HOx levels indoors.

An improved kinetics approach to describe the physical stability of amorphous solid dispersions.

PubMed

Yang, Jiao; Grey, Kristin; Doney, John

2010-01-15

The recrystallization of amorphous solid dispersions may lead to a loss in the dissolution rate, and consequently reduce bioavailability. The purpose of this work is to understand factors governing the recrystallization of amorphous drug-polymer solid dispersions, and develop a kinetics model capable of accurately predicting their physical stability. Recrystallization kinetics was measured using differential scanning calorimetry for initially amorphous efavirenz-polyvinylpyrrolidone solid dispersions stored at controlled temperature and relative humidity. The experimental measurements were fitted by a new kinetic model to estimate the recrystallization rate constant and microscopic geometry of crystal growth. The new kinetics model was used to illustrate the governing factors of amorphous solid dispersions stability. Temperature was found to affect efavirenz recrystallization in an Arrhenius manner, while recrystallization rate constant was shown to increase linearly with relative humidity. Polymer content tremendously inhibited the recrystallization process by increasing the crystallization activation energy and decreasing the equilibrium crystallinity. The new kinetic model was validated by the good agreement between model fits and experiment measurements. A small increase in polyvinylpyrrolidone resulted in substantial stability enhancements of efavirenz amorphous solid dispersion. The new established kinetics model provided more accurate predictions than the Avrami equation.

INFRARED SPECTROSCOPY-BASED PROPERTY-REACTIVITY CORRELATIONS FOR PREDICTING ENVIRONMENTAL FATE OF ORGANIC CHEMICALS

EPA Science Inventory

A conventional structure-activity relationship (SAP) has been established between the alkaline hydrolysis rate constant (kOH) of 12 alkyl and aryl formates and acetates and the linear combination GE the frequencies of the and infrared (SR) absorbance peaks. he inability of this r...

Stability of colloidal gold and determination of the Hamaker constant

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

Demirci, S.; Enuestuen, B.V.; Turkevich, J.

1978-12-14

Previous computation of stability factors of colloidal gold from coagulation data was found to be in systematic error due to an underestimation of the particle concentration by electron microscopy. A new experimental technique was developed for determination of this concentration. Stability factors were recalculated from the previous data using the correct concentration. While most of the previously reported conclusions remain unchanged, the absolute rate of fast coagulation is found to agree with that predicted by the theory. A value of the Hamaker constant was determined from the corrected data.

Ultimate Tensile Strength as a Function of Test Rate for Various Ceramic Matrix Composites at Elevated Temperatures

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Bansal, Narottam P.; Gyekenyesi, John P.

2002-01-01

Ultimate tensile strength of five different continuous fiber-reinforced ceramic composites, including SiC/BSAS (2D 2 types), SiC/MAS-5 (2D), SiC/SiC (2D enhanced), and C/SiC(2D) was determined as a function of test rate at I 100 to 1200 'C in air. All five composite materials exhibited a significant dependency of ultimate strength on test rate such that the ultimate strength decreased with decreasing test rate, similar to the behavior observed in many advanced monolithic ceramics at elevated temperatures. The application of the preloading technique as well as the prediction of life from one loading configuration (constant stress rate) to another (constant stress loading) for SiC/BSAS suggested that the overall macroscopic failure mechanism of the composites would be the one governed by a power-law type of damage evolution/accumulation, analogous to slow crack growth commonly observed in advanced monolithic ceramics.

Reaction diffusion in the nickel-chromium-aluminum and cobalt-chromium-aluminum systems

NASA Technical Reports Server (NTRS)

Levine, S. R.

1977-01-01

The effects of MCrAl coating-substrate interdiffusion on oxidation life and the general mutliphase, multicomponent diffusion problem were examined. Semi-infinite diffusion couples that had sources representing coatings and sinks representing gas turbine alloys were annealed at 1,000, 1,095, 1,150, or 1,205 C for as long as 500 hours. The source and sink aluminum and chromium contents and the base metal (cobalt or nickel) determined the parabolic diffusion rate constants of the couples and predicted finite coating lives. The beta source strength concept provided a method (1) for correlating beta recession rate constants with composition; (2) for determining reliable average total, diffusion, and constitutional activation energies; and (3) for calculating interdiffusion coefficients.

Creep Behavior of Near-Stoichiometric Polycrystalline Binary NiAl

NASA Technical Reports Server (NTRS)

Raj, S. V.

2002-01-01

New and published constant load creep and constant engineering strain rate data on near-stoichiometric binary NiAl in the intermediate temperature range 700 to 1300 K are reviewed. Both normal and inverse primary creep curves are observed depending on stress and temperature. Other characteristics relating to creep of NiAl involving grain size, stress and temperature dependence are critically examined and discussed. At stresses below 25 MPa and temperatures above 1000 K, a new grain boundary sliding mechanism was observed with n approx. 2, Qc approx. 100 kJ/ mol and a grain size exponent of about 2. It is demonstrated that Coble creep and accommodated grain boundary sliding models fail to predict the experimental creep rates by several orders of magnitude.

Transverse relaxation in the rotating frame induced by chemical exchange.

PubMed

Michaeli, Shalom; Sorce, Dennis J; Idiyatullin, Djaudat; Ugurbil, Kamil; Garwood, Michael

2004-08-01

In the presence of radiofrequency irradiation, relaxation of magnetization aligned with the effective magnetic field is characterized by the time constant T1rho. On the other hand, the time constant T2rho characterizes the relaxation of magnetization that is perpendicular to the effective field. Here, it is shown that T2rho can be measured directly with Carr-Purcell sequences composed of a train of adiabatic full-passage (AFP) pulses. During adiabatic rotation, T2rho characterizes the relaxation of the magnetization, which under adiabatic conditions remains approximately perpendicular to the time-dependent effective field. Theory is derived to describe the influence of chemical exchange on T2rho relaxation in the fast-exchange regime, with time constant defined as T2rho,ex. The derived theory predicts the rate constant R2rho,ex (= 1/T2rho,ex) to be dependent on the choice of amplitude- and frequency-modulation functions used in the AFP pulses. Measurements of R2rho,ex of the water/ethanol exchanging system confirm the predicted dependence on modulation functions. The described theoretical framework and adiabatic methods represent new tools to probe exchanging systems. Copyright 2004 Elsevier Inc.

Micromolecular modeling

NASA Technical Reports Server (NTRS)

Guillet, J. E.

1984-01-01

A reaction kinetics based model of the photodegradation process, which measures all important rate constants, and a computerized model capable of predicting the photodegradation rate and failure modes of a 30 year period, were developed. It is shown that the computerized photodegradation model for polyethylene correctly predicts failure of ELVAX 15 and cross linked ELVAX 150 on outdoor exposure. It is indicated that cross linking ethylene vinyl acetate (EVA) does not significantly change its degradation rate. It is shown that the effect of the stabilizer package is approximately equivalent on both polymers. The computerized model indicates that peroxide decomposers and UV absorbers are the most effective stabilizers. It is found that a combination of UV absorbers and a hindered amine light stabilizer (HALS) is the most effective stabilizer system.

Evaluation of indoor air composition time variation in air-tight occupied spaces during night periods

NASA Astrophysics Data System (ADS)

Markov, Detelin

2012-11-01

This paper presents an easy-to-understand procedure for prediction of indoor air composition time variation in air-tight occupied spaces during the night periods. The mathematical model is based on the assumptions for homogeneity and perfect mixing of the indoor air, the ideal gas model for non-reacting gas mixtures, mass conservation equations for the entire system and for each species, a model for prediction of basal metabolic rate of humans as well as a model for prediction of O2 consumption rate and both CO2 and H2O generation rates by breathing. Time variation of indoor air composition is predicted at constant indoor air temperature for three scenarios based on the analytical solution of the mathematical model. The results achieved reveal both the most probable scenario for indoor air time variation in air-tight occupied spaces as well as the cause for morning tiredness after having a sleep in a modern energy efficient space.

Development of a model for predicting reaction rate constants of organic chemicals with ozone at different temperatures.

PubMed

Li, Xuehua; Zhao, Wenxing; Li, Jing; Jiang, Jingqiu; Chen, Jianji; Chen, Jingwen

2013-08-01

To assess the persistence and fate of volatile organic compounds in the troposphere, the rate constants for the reaction with ozone (kO3) are needed. As kO3 values are only available for hundreds of compounds, and experimental determination of kO3 is costly and time-consuming, it is of importance to develop predictive models on kO3. In this study, a total of 379 logkO3 values at different temperatures were used to develop and validate a model for the prediction of kO3, based on quantum chemical descriptors, Dragon descriptors and structural fragments. Molecular descriptors were screened by stepwise multiple linear regression, and the model was constructed by partial least-squares regression. The cross validation coefficient QCUM(2) of the model is 0.836, and the external validation coefficient Qext(2) is 0.811, indicating that the model has high robustness and good predictive performance. The most significant descriptor explaining logkO3 is the BELm2 descriptor with connectivity information weighted atomic masses. kO3 increases with increasing BELm2, and decreases with increasing ionization potential. The applicability domain of the proposed model was visualized by the Williams plot. The developed model can be used to predict kO3 at different temperatures for a wide range of organic chemicals, including alkenes, cycloalkenes, haloalkenes, alkynes, oxygen-containing compounds, nitrogen-containing compounds (except primary amines) and aromatic compounds. Copyright © 2013 Elsevier Ltd. All rights reserved.

Dissociation rate of bromine diatomics in an argon heat bath

NASA Technical Reports Server (NTRS)

Razner, R.; Hopkins, D.

1973-01-01

The evolution of a collection of 300 K bromine diatomics embedded in a heat bath of argon atoms at 1800 K was studied by computer, and a dissociation-rate constant for the reaction Br2 + BR + Ar yields Br + Ar was determined. Previously published probability distributions for energy and angular momentum transfers in classical three-dimensional Br2-Ar collisions were used in conjunction with a newly developed Monte Carlo scheme for this purpose. Results are compared with experimental shock-tube data and the predictions of several other theoretical models. A departure from equilibrium is obtained which is significantly greater than that predicted by any of these other theories.

Analysis of two-equation turbulence models for recirculating flows

NASA Technical Reports Server (NTRS)

Thangam, S.

1991-01-01

The two-equation kappa-epsilon model is used to analyze turbulent separated flow past a backward-facing step. It is shown that if the model constraints are modified to be consistent with the accepted energy decay rate for isotropic turbulence, the dominant features of the flow field, namely the size of the separation bubble and the streamwise component of the mean velocity, can be accurately predicted. In addition, except in the vicinity of the step, very good predictions for the turbulent shear stress, the wall pressure, and the wall shear stress are obtained. The model is also shown to provide good predictions for the turbulence intensity in the region downstream of the reattachment point. Estimated long time growth rates for the turbulent kinetic energy and dissipation rate of homogeneous shear flow are utilized to develop an optimal set of constants for the two equation kappa-epsilon model. The physical implications of the model performance are also discussed.

Rate constants for the thermal decomposition of ethanol and its bimolecular reactions with OH and D : reflected shock tube and theoretical studies.

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

Sivaramakrishnan, R.; Su, M.-C.; Michael, J. V.

2010-09-09

The thermal decomposition of ethanol and its reactions with OH and D have been studied with both shock tube experiments and ab initio transition state theory-based master equation calculations. Dissociation rate constants for ethanol have been measured at high T in reflected shock waves using OH optical absorption and high-sensitivity H-atom ARAS detection. The three dissociation processes that are dominant at high T are: C{sub 2}H{sub 5}OH {yields} C{sub 2}H{sub 4} + H{sub 2}O; C{sub 2}H{sub 5}OH {yields} CH{sub 3} + CH{sub 2}OH; C{sub 2}H{sub 5}OH {yields} C{sub 2}H{sub 5} + OH. The rate coefficient for reaction C was measuredmore » directly with high sensitivity at 308 nm using a multipass optical White cell. Meanwhile, H-atom ARAS measurements yield the overall rate coefficient and that for the sum of reactions B and C, since H-atoms are instantaneously formed from the decompositions of CH{sub 2}OH and C{sub 2}H{sub 5} into CH{sub 2}O + H and C{sub 2}H{sub 4} + H, respectively. By difference, rate constants for reaction 1 could be obtained. One potential complication is the scavenging of OH by unreacted ethanol in the OH experiments, and therefore, rate constants for OH + C{sub 2}H{sub 5}OH {yields} products were measured using tert-butyl hydroperoxide (tBH) as the thermal source for OH. The present experiments can be represented by the Arrhenius expression k = (2.5 {+-} 0.43) x 10{sup -11} exp(- 911 {+-} 191 K/T) cm{sup 3} molecule{sup -1} s{sup -1} over the T range 857-1297 K. For completeness, we have also measured the rate coefficient for the reaction of D atoms with ethanol D + C{sub 2}H{sub 5}OH {yields} products whose H analogue is another key reaction in the combustion of ethanol. Over the T range 1054-1359 K, the rate constants from the present experiments can be represented by the Arrhenius expression, k = (3.98 {+-} 0.76) x 10{sup -10} exp(- 4494 {+-} 235 K/T) cm{sup 3} molecule{sup -1} s{sup -1}. The high-pressure rate coefficients for reactions B and C were studied with variable reaction coordinate transition state theory employing directly determined CASPT2/cc-pvdz interaction energies. Reactions A, D, and E were studied with conventional transition state theory employing QCISD(T)/CBS energies. For the saddle point in reaction A, additional high-level corrections are evaluated. The predicted reaction exo- and endothermicities are in good agreement with the current Active Thermochemical Tables values. The transition state theory predictions for the microcanonical rate coefficients in ethanol decomposition are incorporated in master equation calculations to yield predictions for the temperature and pressure dependences of reactions A-C. With modest adjustments (<1 kcal/mol) to a few key barrier heights, the present experimental and adjusted theoretical results yield a consistent description of both the decomposition (1-3) and abstraction kinetics (4 and 5). The present results are compared with earlier experimental and theoretical work.« less

The costs of living in a thermal fluctuating environment for the tropical haematophagous bug, Rhodnius prolixus.

PubMed

Rolandi, Carmen; Schilman, Pablo E

2018-05-01

Environmental temperature is an abiotic factor with great influence on biological processes of living beings. Jensen's inequality states that for non-lineal processes, such as most biological phenomena, the effects of thermal fluctuations cannot be predicted from mean constant temperatures. We studied the effect of daily temperature fluctuation (DTF) on Rhodnius prolixus, a model organism in insect physiology, and an important vector of Chagas disease. We measured development time from egg to adult, fecundity, fertility, body mass reduction rate (indirect measurement of nutrient consumption rates) and survival after a single blood meal. Insects were reared at constant temperature (24 °C), or with a DTF (17-32 °C; mean = 24 °C). Taking into account Jensen's inequality as well as the species tropical distribution, we predict that living in a variable thermal environment will have higher costs than inhabiting a stable one. Development time and fertility were not affected by DTF. However, fecundity was lower in females reared at DTF than at constant temperature, and males had higher body mass reduction rate and lower survival in the DTF regime, suggesting higher costs associated to fluctuating thermal environments. At a population and epidemiological level, higher energetic costs would imply an increase in nutrient consumption rate, biting frequency, and, consequently increasing disease transmission from infected insects. On the contrary, lower fecundity could be associated with a decrease in population growth. This knowledge will not only provide basic information to the field of insect ecophysiology, but also could be a useful background to develop population and disease transmission models. Copyright © 2018 Elsevier Ltd. All rights reserved.

The Rate Constant for the Reaction H + C2H5 at T = 295 - 150K

NASA Technical Reports Server (NTRS)

Pimentel, Andre S.; Payne, Walter A.; Nesbitt, Fred L.; Cody, Regina J.; Stief, Louis J.

2004-01-01

The reaction between the hydrogen atom and the ethyl (C2H3) radical is predicted by photochemical modeling to be the most important loss process for C2H5 radicals in the atmospheres of Jupiter and Saturn. This reaction is also one of the major sources for the methyl radicals in these atmospheres. These two simplest hydrocarbon radicals are the initial species for the synthesis of larger hydrocarbons. Previous measurements of the rate constant for the H + C2H5 reaction varied by a factor of five at room temperature, and some studies showed a dependence upon temperature while others showed no such dependence. In addition, the previous studies were at higher temperatures and generally higher pressures than that needed for use in planetary atmospheric models. The rate constant for the reaction H + C2H5 has been measured directly at T = 150, 202 and 295 K and at P = 1.0 Torr He for all temperatures and additionally at P = 0.5 and 2.0 Torr He at T = 202 K. The measurements were performed in a discharge - fast flow system. The decay of the C2H5 radical in the presence of excess hydrogen was monitored by low-energy electron impact mass spectrometry under pseudo-first order conditions. H atoms and C2H5 radicals were generated rapidly and simultaneously by the reaction of fluorine atoms with H2 and C2H6, respectively. The total rate constant was found to be temperature and pressure independent. The measured total rate constant at each temperature are: k(sub 1)(295K) = (1.02+/-0.24)x10(exp -10), k(sub 1)(202K) = (1.02+/-0.22)x10(exp -10) and k(sub 1)(150K) = (0.93+/-0.21)x10(exp -10), all in units of cu cm/molecule/s. The total rate constant derived from all the combined measurements is k(sub 1) = (l.03+/-0.17)x10(exp -10) cu cm/molecule/s. At room temperature our results are about a factor of two higher than the recommended rate constant and a factor of three lower than the most recently published study.

Flow and volume dependence of rat airway resistance during constant flow inflation and deflation.

PubMed

Rubini, Alessandro; Carniel, Emanuele Luigi; Parmagnani, Andrea; Natali, Arturo Nicola

2011-12-01

The aim of this study was to measure the flow and volume dependence of both the ohmic and the viscoelastic pressure dissipations of the normal rat respiratory system separately during inflation and deflation. The study was conducted in the Respiratory Physiology Laboratory in our institution. Measurements were obtained for Seven albino Wistar rats of both sexes by using the flow interruption method during constant flow inflations and deflations. Measurements included anesthesia induction, tracheostomy and positioning of a tracheal cannula, positive pressure ventilation, constant flow respiratory system inflations and deflations at two different volumes and flows. The ohmic resistance exhibited volume and flow dependence, decreasing with lung volume and increasing with flow rate, during both inflation and deflation. The stress relaxation-related viscoelastic resistance also exhibited volume and flow dependence. It decreased with the flow rate at a constant lung volume during both inflation and deflation, but exhibited a different behavior with the lung volume at a constant flow rate (i.e., increased during inflations and decreased during deflations). Thus, stress relaxation in the rat lungs exhibited a hysteretic behavior. The observed flow and volume dependence of respiratory system resistance may be predicted by an equation derived from a model of the respiratory system that consists of two distinct compartments. The equation agrees well with the experimental data and indicates that the loading time is the critical parameter on which stress relaxation depends, during both lung inflation and deflation.

Determination of the alpha(s) using jet rates at LEP

NASA Astrophysics Data System (ADS)

Donkers, Michael A.

Jets are produced in any high energy collision of particles in which quarks are produced in the final state. Using the OPAL detector to measure particles produced in e+e- collisions at the LEP accelerator, the rate of jet formation has been measured at 91 GeV as well as each of the LEP2 energies, ranging from 161 GeV to 207 GeV. The jet rate observables, in particular the differential 2-jet rate and the average jet rate can be used to determine a value of the strong coupling constant, alphas, by fitting to various theoretical predictions. The value of alphas has been determined using data at 91 GeV and a combined sample comprising all of the LEP2 energies with a luminosity weighted centre-of-mass energy of 195.8 GeV for 10 theoretical predictions and two jet clustering algorithms. A fit of the 91 GeV and LEP2 values of alphas determined using the ln R matching prediction is also performed on the D2 and distributions to the 3-loop alphas prediction to produce 4 values of alphas(MZ 0).

Diffusion and binding constants for acetylcholine derived from the falling phase of miniature endplate currents.

PubMed Central

Land, B R; Harris, W V; Salpeter, E E; Salpeter, M M

1984-01-01

In previous papers we studied the rising phase of a miniature endplate current (MEPC) to derive diffusion and forward rate constants controlling acetylcholine (AcCho) in the intact neuromuscular junction. The present study derives similar values (but with smaller error ranges) for these constants by including experimental results from the falling phase of the MEPC. We find diffusion to be 4 X 10(-6) cm2 s-1, slightly slower than free diffusion, forward binding to be 3.3 X 10(7) M-1 s-1, and the distance from an average release site to the nearest exit from the cleft to be 1.6 micron. We also estimate the back reaction rates. From our values we can accurately describe the shape of MEPCs under different conditions of receptor and esterase concentration. Since we suggest that unbinding is slower than isomerization, we further predict that there should be several short "closing flickers" during the total open time for an AcCho-ligated receptor channel. PMID:6584895

Calculations of rate constants for the three-body recombination of H2 in the presence of H2

NASA Technical Reports Server (NTRS)

Schwenke, David W.

1988-01-01

A new global potential energy hypersurface for H2 + H2 is constructed and quasiclassical trajectory calculations performed using the resonance complex theory and energy transfer mechanism to estimate the rate of three body recombination over the temperature range 100 to 5000 K. The new potential is a faithful representation of ab initio electron structure calculations, is unchanged under the operation of exchanging H atoms, and reproduces the accurate H3 potential as one H atom is pulled away. Included in the fitting procedure are geometries expected to be important when one H2 is near or above the dissociation limit. The dynamics calculations explicitly include the motion of all four atoms and are performed efficiently using a vectorized variable-stepsize integrator. The predicted rate constants are approximately a factor of two smaller than experimental estimates over a broad temperature range.

Investigating calcite growth rates using a quartz crystal microbalance with dissipation (QCM-D)

NASA Astrophysics Data System (ADS)

Cao, Bo; Stack, Andrew G.; Steefel, Carl I.; DePaolo, Donald J.; Lammers, Laura N.; Hu, Yandi

2018-02-01

Calcite precipitation plays a significant role in processes such as geological carbon sequestration and toxic metal sequestration and, yet, the rates and mechanisms of calcite growth under close to equilibrium conditions are far from well understood. In this study, a quartz crystal microbalance with dissipation (QCM-D) was used for the first time to measure macroscopic calcite growth rates. Calcite seed crystals were first nucleated and grown on sensors, then growth rates of calcite seed crystals were measured in real-time under close to equilibrium conditions (saturation index, SI = log ({Ca2+}/{CO32-}/Ksp) = 0.01-0.7, where {i} represent ion activities and Ksp = 10-8.48 is the calcite thermodynamic solubility constant). At the end of the experiments, total masses of calcite crystals on sensors measured by QCM-D and inductively coupled plasma mass spectrometry (ICP-MS) were consistent, validating the QCM-D measurements. Calcite growth rates measured by QCM-D were compared with reported macroscopic growth rates measured with auto-titration, ICP-MS, and microbalance. Calcite growth rates measured by QCM-D were also compared with microscopic growth rates measured by atomic force microscopy (AFM) and with rates predicted by two process-based crystal growth models. The discrepancies in growth rates among AFM measurements and model predictions appear to mainly arise from differences in step densities, and the step velocities were consistent among the AFM measurements as well as with both model predictions. Using the predicted steady-state step velocity and the measured step densities, both models predict well the growth rates measured using QCM-D and AFM. This study provides valuable insights into the effects of reactive site densities on calcite growth rate, which may help design future growth models to predict transient-state step densities.

A modification of Murray's law for shear-thinning rheology.

PubMed

McGah, Patrick M; Capobianchi, Massimo

2015-05-01

This study reformulates Murray's well-known principle of minimum work as applied to the cardiovascular system to include the effects of the shear-thinning rheology of blood. The viscous behavior is described using the extended modified power law (EMPL), which is a time-independent, but shear-thinning rheological constitutive equation. The resulting minimization problem is solved numerically for typical parameter ranges. The non-Newtonian analysis still predicts the classical cubic diameter dependence of the volume flow rate and the cubic branching law. The current analysis also predicts a constant wall shear stress throughout the vascular tree, albeit with a numerical value about 15-25% higher than the Newtonian analysis. Thus, experimentally observed deviations from the cubic branching law or the predicted constant wall shear stress in the vasculature cannot likely be attributed to blood's shear-thinning behavior. Further differences between the predictions of the non-Newtonian and the Newtonian analyses are highlighted, and the limitations of the Newtonian analysis are discussed. Finally, the range and limits of applicability of the current results as applied to the human arterial tree are also discussed.

Selection on Network Dynamics Drives Differential Rates of Protein Domain Evolution

PubMed Central

Mannakee, Brian K.; Gutenkunst, Ryan N.

2016-01-01

The long-held principle that functionally important proteins evolve slowly has recently been challenged by studies in mice and yeast showing that the severity of a protein knockout only weakly predicts that protein’s rate of evolution. However, the relevance of these studies to evolutionary changes within proteins is unknown, because amino acid substitutions, unlike knockouts, often only slightly perturb protein activity. To quantify the phenotypic effect of small biochemical perturbations, we developed an approach to use computational systems biology models to measure the influence of individual reaction rate constants on network dynamics. We show that this dynamical influence is predictive of protein domain evolutionary rate within networks in vertebrates and yeast, even after controlling for expression level and breadth, network topology, and knockout effect. Thus, our results not only demonstrate the importance of protein domain function in determining evolutionary rate, but also the power of systems biology modeling to uncover unanticipated evolutionary forces. PMID:27380265

Studies of the 4-JET Rate and of Moments of Event Shape Observables Using Jade Data

NASA Astrophysics Data System (ADS)

Kluth, S.

2005-04-01

Data from e+e- annihilation into hadrons collected by the JADE experiment at centre-of-mass energies between 14 and 44 GeV were used to study the 4-jet rate using the Durham algorithm as well as the first five moments of event shape observables. The data were compared with NLO QCD predictions, augmented by resummed NLLA calculations for the 4-jet rate, in order to extract values of the strong coupling constant αS. The preliminary results are αS(MZ0) = 0.1169 ± 0.0026 (4-jet rate) and αS(MZ0) = 0.1286 ± 0.0072 (moments) consistent with the world average value. For some of the higher moments systematic deficiencies of the QCD predictions are observed.

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

Dang, Liem X.; Vo, Quynh N.; Nilsson, Mikael

We report one of the first simulations using a classical rate theory approach to predict the mechanism of the exchange process between water and aqueous uranyl ions. Using our water and ion-water polarizable force fields and molecular dynamics techniques, we computed the potentials of mean force for the uranyl ion-water pair as the function of pressures at ambient temperature. Subsequently, these simulated potentials of mean force were used to calculate rate constants using the transition rate theory; the time dependent transmission coefficients were also examined using the reactive flux method and Grote-Hynes treatments of the dynamic response of the solvent.more » The computed activation volumes using transition rate theory and the corrected rate constants are positive, thus the mechanism of this particular water-exchange is a dissociative process. We discuss our rate theory results and compare them with previously studies in which non-polarizable force fields were used. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.« less

Including Thermal Fluctuations in Actomyosin Stable States Increases the Predicted Force per Motor and Macroscopic Efficiency in Muscle Modelling

PubMed Central

2016-01-01

Muscle contractions are generated by cyclical interactions of myosin heads with actin filaments to form the actomyosin complex. To simulate actomyosin complex stable states, mathematical models usually define an energy landscape with a corresponding number of wells. The jumps between these wells are defined through rate constants. Almost all previous models assign these wells an infinite sharpness by imposing a relatively simple expression for the detailed balance, i.e., the ratio of the rate constants depends exponentially on the sole myosin elastic energy. Physically, this assumption corresponds to neglecting thermal fluctuations in the actomyosin complex stable states. By comparing three mathematical models, we examine the extent to which this hypothesis affects muscle model predictions at the single cross-bridge, single fiber, and organ levels in a ceteris paribus analysis. We show that including fluctuations in stable states allows the lever arm of the myosin to easily and dynamically explore all possible minima in the energy landscape, generating several backward and forward jumps between states during the lifetime of the actomyosin complex, whereas the infinitely sharp minima case is characterized by fewer jumps between states. Moreover, the analysis predicts that thermal fluctuations enable a more efficient contraction mechanism, in which a higher force is sustained by fewer attached cross-bridges. PMID:27626630

Biofiltration of methanol vapor

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

Shareefdeen, Z.; Baltzis, B.C.; Oh, Youngsook

1993-03-05

Biofiltration of solvent and fuel vapors may offer a cost-effective way to comply with increasingly strict air emission standards. An important step in the development of this technology is to derive and validate mathematical models of the biofiltration process for predictive and scaleup calculations. For the study of methanol vapor biofiltration, an 8-membered bacterial consortium was obtained from methanol-exposed soil. The bacteria were immobilized on solid support and packed into a 5-cm diameter, 60-cm-high column provided with appropriate flowmeters and sampling ports. The solid support was prepared by mixing two volumes of peat with three volumes of perlite particles. Twomore » series of experiments were performed. In the first, the inlet methanol concentration was kept constant while the superficial air velocity was varied from run to run. In the second series, the air flow rate (velocity) was kept constant while the inlet methanol concentration was varied. The unit proved effective in removing methanol at rates up to 112.8 g h[sup [minus]1] m[sup [minus]3] packing. A mathematical model has been derived and validated. The model described and predicted experimental results closely. Both experimental data and model predictions suggest that the methanol biofiltration process was limited by oxygen diffusion and methanol degradation kinetics.« less

Hydrogen transfer reactions of interstellar Complex Organic Molecules

NASA Astrophysics Data System (ADS)

Álvarez-Barcia, S.; Russ, P.; Kästner, J.; Lamberts, T.

2018-06-01

Radical recombination has been proposed to lead to the formation of complex organic molecules (COMs) in CO-rich ices in the early stages of star formation. These COMs can then undergo hydrogen addition and abstraction reactions leading to a higher or lower degree of saturation. Here, we have studied 14 hydrogen transfer reactions for the molecules glyoxal, glycoaldehyde, ethylene glycol, and methylformate and an additional three reactions where CHnO fragments are involved. Over-the-barrier reactions are possible only if tunneling is invoked in the description at low temperature. Therefore the rate constants for the studied reactions are calculated using instanton theory that takes quantum effects into account inherently. The reactions were characterized in the gas phase, but this is expected to yield meaningful results for CO-rich ices due to the minimal alteration of reaction landscapes by the CO molecules. We found that rate constants should not be extrapolated based on the height of the barrier alone, since the shape of the barrier plays an increasingly larger role at decreasing temperature. It is neither possible to predict rate constants based only on considering the type of reaction, the specific reactants and functional groups play a crucial role. Within a single molecule, though, hydrogen abstraction from an aldehyde group seems to be always faster than hydrogen addition to the same carbon atom. Reactions that involve heavy-atom tunneling, e.g., breaking or forming a C-C or C-O bond, have rate constants that are much lower than those where H transfer is involved.

Real-time Adaptive Control Using Neural Generalized Predictive Control

NASA Technical Reports Server (NTRS)

Haley, Pam; Soloway, Don; Gold, Brian

1999-01-01

The objective of this paper is to demonstrate the feasibility of a Nonlinear Generalized Predictive Control algorithm by showing real-time adaptive control on a plant with relatively fast time-constants. Generalized Predictive Control has classically been used in process control where linear control laws were formulated for plants with relatively slow time-constants. The plant of interest for this paper is a magnetic levitation device that is nonlinear and open-loop unstable. In this application, the reference model of the plant is a neural network that has an embedded nominal linear model in the network weights. The control based on the linear model provides initial stability at the beginning of network training. In using a neural network the control laws are nonlinear and online adaptation of the model is possible to capture unmodeled or time-varying dynamics. Newton-Raphson is the minimization algorithm. Newton-Raphson requires the calculation of the Hessian, but even with this computational expense the low iteration rate make this a viable algorithm for real-time control.

Prediction of the Creep-Fatigue Lifetime of Alloy 617: An Application of Non-destructive Evaluation and Information Integration

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

Vivek Agarwal; Richard Wright; Timothy Roney

A relatively simple method using the nominal constant average stress information and the creep rupture model is developed to predict the creep-fatigue lifetime of Alloy 617, in terms of time to rupture. The nominal constant average stress is computed using the stress relaxation curve. The predicted time to rupture can be converted to number of cycles to failure using the strain range, the strain rate during each cycle, and the hold time information. The predicted creep-fatigue lifetime is validated against the experimental measurements of the creep-fatigue lifetime collected using conventional laboratory creep-fatigue tests. High temperature creep-fatigue tests of Alloy 617more » were conducted in air at 950°C with a tensile hold period of up to 1800s in a cycle at total strain ranges of 0.3% and 0.6%. It was observed that the proposed method is conservative in that the predicted lifetime is less than the experimentally determined values. The approach would be relevant to calculate the remaining useful life to a component like a steam generator that might fail by the creep-fatigue mechanism.« less

Microtubule Dynamics Scale with Cell Size to Set Spindle Length and Assembly Timing.

PubMed

Lacroix, Benjamin; Letort, Gaëlle; Pitayu, Laras; Sallé, Jérémy; Stefanutti, Marine; Maton, Gilliane; Ladouceur, Anne-Marie; Canman, Julie C; Maddox, Paul S; Maddox, Amy S; Minc, Nicolas; Nédélec, François; Dumont, Julien

2018-05-21

Successive cell divisions during embryonic cleavage create increasingly smaller cells, so intracellular structures must adapt accordingly. Mitotic spindle size correlates with cell size, but the mechanisms for this scaling remain unclear. Using live cell imaging, we analyzed spindle scaling during embryo cleavage in the nematode Caenorhabditis elegans and sea urchin Paracentrotus lividus. We reveal a common scaling mechanism, where the growth rate of spindle microtubules scales with cell volume, which explains spindle shortening. Spindle assembly timing is, however, constant throughout successive divisions. Analyses in silico suggest that controlling the microtubule growth rate is sufficient to scale spindle length and maintain a constant assembly timing. We tested our in silico predictions to demonstrate that modulating cell volume or microtubule growth rate in vivo induces a proportional spindle size change. Our results suggest that scalability of the microtubule growth rate when cell size varies adapts spindle length to cell volume. Copyright © 2018 Elsevier Inc. All rights reserved.

Intermittent Drug Dosing Intervals Guided by the Operational Multiple Dosing Half Lives for Predictable Plasma Accumulation and Fluctuation

PubMed Central

Grover, Anita; Benet, Leslie Z.

2013-01-01

Intermittent drug dosing intervals are usually initially guided by the terminal pharmacokinetic half life and are dependent on drug formulation. For chronic multiple dosing and for extended release dosage forms, the terminal half life often does not predict the plasma drug accumulation or fluctuation observed. We define and advance applications for the operational multiple dosing half lives for drug accumulation and fluctuation after multiple oral dosing at steady-state. Using Monte Carlo simulation, our results predict a way to maximize the operational multiple dosing half lives relative to the terminal half life by using a first-order absorption rate constant close to the terminal elimination rate constant in the design of extended release dosage forms. In this way, drugs that may be eliminated early in the development pipeline due to a relatively short half life can be formulated to be dosed at intervals three times the terminal half life, maximizing compliance, while maintaining tight plasma concentration accumulation and fluctuation ranges. We also present situations in which the operational multiple dosing half lives will be especially relevant in the determination of dosing intervals, including for drugs that follow a direct PKPD model and have a narrow therapeutic index, as the rate of concentration decrease after chronic multiple dosing (that is not the terminal half life) can be determined via simulation. These principles are illustrated with case studies on valproic acid, diazepam, and anti-hypertensives. PMID:21499748

Self-consistent quantum kinetic theory of diatomic molecule formation

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

Forrey, Robert C.

2015-07-14

A quantum kinetic theory of molecule formation is presented which includes three-body recombination and radiative association for a thermodynamically closed system which may or may not exchange energy with its surrounding at a constant temperature. The theory uses a Sturmian representation of a two-body continuum to achieve a steady-state solution of a governing master equation which is self-consistent in the sense that detailed balance between all bound and unbound states is rigorously enforced. The role of quasibound states in catalyzing the molecule formation is analyzed in complete detail. The theory is used to make three predictions which differ from conventionalmore » kinetic models. These predictions suggest significant modifications may be needed to phenomenological rate constants which are currently in wide use. Implications for models of low and high density systems are discussed.« less

Computational chemistry and aeroassisted orbital transfer vehicles

NASA Technical Reports Server (NTRS)

Cooper, D. M.; Jaffe, R. L.; Arnold, J. O.

1985-01-01

An analysis of the radiative heating phenomena encountered during a typical aeroassisted orbital transfer vehicle (AOTV) trajectory was made to determine the potential impact of computational chemistry on AOTV design technology. Both equilibrium and nonequilibrium radiation mechanisms were considered. This analysis showed that computational chemistry can be used to predict (1) radiative intensity factors and spectroscopic data; (2) the excitation rates of both atoms and molecules; (3) high-temperature reaction rate constants for metathesis and charge exchange reactions; (4) particle ionization and neutralization rates and cross sections; and (5) spectral line widths.

A dissolution model that accounts for coverage of mineral surfaces by precipitation in core floods

NASA Astrophysics Data System (ADS)

Pedersen, Janne; Jettestuen, Espen; Madland, Merete V.; Hildebrand-Habel, Tania; Korsnes, Reidar I.; Vinningland, Jan Ludvig; Hiorth, Aksel

2016-01-01

In this paper, we propose a model for evolution of reactive surface area of minerals due to surface coverage by precipitating minerals. The model is used to interpret results from an experiment where a chalk core was flooded with MgCl2 for 1072 days, giving rise to calcite dissolution and magnesite precipitation. The model successfully describes both the long-term behavior of the measured effluent concentrations and the more or less homogeneous distribution of magnesite found in the core after 1072 days. The model also predicts that precipitating magnesite minerals form as larger crystals or aggregates of smaller size crystals, and not as thin flakes or as a monomolecular layer. Using rate constants obtained from literature gave numerical effluent concentrations that diverged from observed values only after a few days of flooding. To match the simulations to the experimental data after approximately 1 year of flooding, a rate constant that is four orders of magnitude lower than reported by powder experiments had to be used. We argue that a static rate constant is not sufficient to describe a chalk core flooding experiment lasting for nearly 3 years. The model is a necessary extension of standard rate equations in order to describe long term core flooding experiments where there is a large degree of textural alteration.

Effects of benthic flora on arsenic transport

USGS Publications Warehouse

Kuwabara, James S.; Chang, Cecily C.Y.; Pasilis, Sofie P.

1990-01-01

Chemical and biological interactions involving arsenic (As) and phosphorus (P) appear to affect significantly As transport and distribution in Whitewood Creek, South Dakota. Data (first‐order uptake rate constants, standing crop, and accumulation factors) that can be used to predict As transport have been determined using algae collected in the creek along a transect from upstream of mine discharge down gradient through a 57‐km impacted reach. Cultures of Achnanthes minutissima (Bacillariophyceae) were isolated from four sites along a longitudinal gradient of dissolved As within the study reach and were maintained at ambient dissolved‐As concentrations. Arsenic sorption‐rate constants for cell surfaces of these isolates were estimated as a function of dissolved arsenate and orthophosphate. All isolates sorbed orthophosphate preferentially over arsenate. Initial sorption of both arsenate and orthophosphate appeared to follow a first‐order equation within media formulations but did not adequately describe other observed effects among formulations or between isolates. Although estimated sorption‐rate constants increased slightly with increased dissolved arsenate concentration, algae isolated from a site with elevated dissolved As had a significantly slower rate of As uptake compared with the same species isolated from an uncontaminated site upstream. Field and laboratory results indicate that the benthic flora represent a significant As pool, which may episodically affect water‐column concentrations. 

Predicting the Rate Constant of Electron Tunneling Reactions at the CdSe-TiO2 Interface.

PubMed

Hines, Douglas A; Forrest, Ryan P; Corcelli, Steven A; Kamat, Prashant V

2015-06-18

Current interest in quantum dot solar cells (QDSCs) motivates an understanding of the electron transfer dynamics at the quantum dot (QD)-metal oxide (MO) interface. Employing transient absorption spectroscopy, we have monitored the electron transfer rate (ket) at this interface as a function of the bridge molecules that link QDs to TiO2. Using mercaptoacetic acid, 3-mercaptopropionic acid, 8-mercaptooctanoic acid, and 16-mercaptohexadecanoic acid, we observe an exponential attenuation of ket with increasing linker length, and attribute this to the tunneling of the electron through the insulating linker molecule. We model the electron transfer reaction using both rectangular and trapezoidal barrier models that have been discussed in the literature. The one-electron reduction potential (equivalent to the lowest unoccupied molecular orbital) of each molecule as determined by cyclic voltammetry (CV) was used to estimate the effective barrier height presented by each ligand at the CdSe-TiO2 interface. The electron transfer rate (ket) calculated for each CdSe-ligand-TiO2 interface using both models showed the results in agreement with the experimentally determined trend. This demonstrates that electron transfer between CdSe and TiO2 can be viewed as electron tunneling through a layer of linking molecules and provides a useful method for predicting electron transfer rate constants.

Mathematical modeling of PDC bit drilling process based on a single-cutter mechanics

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

Wojtanowicz, A.K.; Kuru, E.

1993-12-01

An analytical development of a new mechanistic drilling model for polycrystalline diamond compact (PDC) bits is presented. The derivation accounts for static balance of forces acting on a single PDC cutter and is based on assumed similarity between bit and cutter. The model is fully explicit with physical meanings given to all constants and functions. Three equations constitute the mathematical model: torque, drilling rate, and bit life. The equations comprise cutter`s geometry, rock properties drilling parameters, and four empirical constants. The constants are used to match the model to a PDC drilling process. Also presented are qualitative and predictive verificationsmore » of the model. Qualitative verification shows that the model`s response to drilling process variables is similar to the behavior of full-size PDC bits. However, accuracy of the model`s predictions of PDC bit performance is limited primarily by imprecision of bit-dull evaluation. The verification study is based upon the reported laboratory drilling and field drilling tests as well as field data collected by the authors.« less

Regulation of Catch Bonds by Rate of Force Application*

PubMed Central

Sarangapani, Krishna K.; Qian, Jin; Chen, Wei; Zarnitsyna, Veronika I.; Mehta, Padmaja; Yago, Tadayuki; McEver, Rodger P.; Zhu, Cheng

2011-01-01

The current paradigm for receptor-ligand dissociation kinetics assumes off-rates as functions of instantaneous force without impact from its prior history. This a priori assumption is the foundation for predicting dissociation from a given initial state using kinetic equations. Here we have invalidated this assumption by demonstrating the impact of force history with single-bond kinetic experiments involving selectins and their ligands that mediate leukocyte tethering and rolling on vascular surfaces during inflammation. Dissociation of bonds between L-selectin and P-selectin glycoprotein ligand-1 (PSGL-1) loaded at a constant ramp rate to a constant hold force behaved as catch-slip bonds at low ramp rates that transformed to slip-only bonds at high ramp rates. Strikingly, bonds between L-selectin and 6-sulfo-sialyl Lewis X were impervious to ramp rate changes. This ligand-specific force history effect resembled the effect of a point mutation at the L-selectin surface (L-selectinA108H) predicted to contact the former but not the latter ligand, suggesting that the high ramp rate induced similar structural changes as the mutation. Although the A108H substitution in L-selectin eliminated the ramp rate responsiveness of its dissociation from PSGL-1, the inverse mutation H108A in P-selectin acquired the ramp rate responsiveness. Our data are well explained by the sliding-rebinding model for catch-slip bonds extended to incorporate the additional force history dependence, with Ala-108 playing a pivotal role in this structural mechanism. These results call for a paradigm shift in modeling the mechanical regulation of receptor-ligand bond dissociation, which includes conformational coupling between binding pocket and remote regions of the interacting molecules. PMID:21775439

Thermal degradation of deoxynivalenol during maize bread baking.

PubMed

Numanoglu, E; Gökmen, V; Uygun, U; Koksel, H

2012-01-01

The thermal degradation of deoxynivalenol (DON) was determined at isothermal baking conditions within the temperature range of 100-250°C, using a crust-like model, which was prepared with naturally contaminated maize flour. No degradation was observed at 100°C. For the temperatures of 150, 200 and 250°C, thermal degradation rate constants (k) were calculated and temperature dependence of DON degradation was observed by using Arrhenius equation. The degradation of DON obeyed Arrhenius law with a regression coefficient of 0.95. A classical bread baking operation was also performed at 250°C for 70 min and the rate of DON degradation in the bread was estimated by using the kinetic data derived from the model study. The crust and crumb temperatures recorded during bread baking were used to calculate the thermal degradation rate constants (k) and partial DON degradations at certain time intervals. Using these data, total degradation at the end of the entire baking process was predicted for both crust and crumb. This DON degradation was consistent with the experimental degradation data, confirming the accuracy of kinetic constants determined by means of the crust-like model.

Evolved stars as complex chemical laboratories - the quest for gaseous chemistry

NASA Astrophysics Data System (ADS)

Katrien Els Decin, Leen

2015-08-01

At the end of their life, most stars lose a large fraction of their mass through a stellar wind. The stellar winds of evolved (super)giant stars are the dominant suppliers for the pristine building blocks of the interstellar medium (ISM). Crucial to the understanding of the chemical life cycle of the ISM is hence a profound insight in the chemical and physical structure governing these stellar winds.These winds are really unique chemical laboratories in which currently more than 70 different molecules and 15 different dust species are detected. Several chemical processes such as neutral-neutral and ion-molecule gas-phase reactions, dust nucleation and growth, and photo-processes determine the chemical content of these winds. However, gas-phase and dust-nucleation chemistry for astronomical environments still faces many challenges. One should realize that only ˜15% of the rate coefficients for gas-phase reactions considered to occur in (inter/circum)stellar regions at temperatures (T) below 300K have been subject to direct laboratory determinations and that the temperature dependence of the rate constants is often not known; only ˜2% have rate constants at T<200K and less than 0.5% at T<100 K. For stellar wind models, an important bottleneck occurs among the reactions involving silicon- and sulfur-bearing species, for which only a few have documented reaction rates. Often, researchers are implementing ‘educated guesses’ for these unknown rates, sometimes forcing the network to yield predictions concurring with (astronomical) observations. Large uncertainties are inherent in this type of ‘optimized’ chemical schemes.Thanks to an ERC-CoG grant, we are now in the position to solve some riddles involved in understanding the gas-phase chemistry in evolved stars. In this presentation, I will demonstrate the need for accurate temperature-dependent gas-phase reaction rate constants and will present our new laboratory equipment built to measure the rate constants for species key in stellar wind chemistry. Specifically, we aim to obtain the rate constants of reactions involving silicon- and sulphur bearing species and HCCO for 30

Variational RRKM theory calculation of thermal rate constant for carbon—hydrogen bond fission reaction of nitro benzene

NASA Astrophysics Data System (ADS)

Manesh, Afshin Taghva; Heidarnezhad, Zabi alah; Masnabadi, Nasrin

2013-07-01

The present work provides quantitative results for the rate of unimolecular carbon-hydrogen bond fission reaction of benzene and nitro benzene at elevated temperatures up to 2000 K. The potential energy surface for each C-H (in the ortho, meta, and para sites) bond fission reaction of nitro benzene was investigated by ab initio calculations. The geometry and vibrational frequencies of the species involved in this process were optimized at the MP2 level of theory, using the cc-pvdz basis set. Since C-H bond fission channel is barrier less reaction, we have used variational RRKM theory to predict rate constants. By means of calculated rate constant at the different temperatures, the activation energy and exponential factor were determined. The Arrhenius expression for C-H bond fission reaction of nitro benzene on the ortho, meta and para sites are k( T) = 2.1 × 1017exp(-56575.98/ T), k( T) = 2.1 × 1017exp(-57587.45/ T), and k( T) = 3.3 × 1016exp(-57594.79/ T) respectively. The Arrhenius expression for C-H bond fission reaction of benzene is k( T) = 2 × 1018exp(-59343.48.18/ T). The effect of NO2 group, location of hydrogen atoms on the substituted benzene ring, reaction degeneracy, benzene ring resonance and tunneling effect on the rate expression have been discussed.

Stereoselective Inhibition of CYP2C19 and CYP3A4 by Fluoxetine and Its Metabolite: Implications for Risk Assessment of Multiple Time-Dependent Inhibitor Systems

PubMed Central

Lutz, Justin D.; VandenBrink, Brooke M.; Babu, Katipudi N.; Nelson, Wendel L.; Kunze, Kent L.

2013-01-01

Recent guidance on drug-drug interaction (DDI) testing recommends evaluation of circulating metabolites. However, there is little consensus on how to quantitatively predict and/or assess the risk of in vivo DDIs by multiple time-dependent inhibitors (TDIs) including metabolites from in vitro data. Fluoxetine was chosen as the model drug to evaluate the role of TDI metabolites in DDI prediction because it is a TDI of both CYP3A4 and CYP2C19 with a circulating N-dealkylated inhibitory metabolite, norfluoxetine. In pooled human liver microsomes, both enantiomers of fluoxetine and norfluoxetine were TDIs of CYP2C19, (S)-norfluoxetine was the most potent inhibitor with time-dependent inhibition affinity constant (KI) of 7 μM, and apparent maximum time-dependent inhibition rate (kinact,app) of 0.059 min−1. Only (S)-fluoxetine and (R)-norfluoxetine were TDIs of CYP3A4, with (R)-norfluoxetine being the most potent (KI = 8 μM, and kinact,app = 0.011 min−1). Based on in-vitro-to-in-vivo predictions, (S)-norfluoxetine plays the most important role in in vivo CYP2C19 DDIs, whereas (R)-norfluoxetine is most important in CYP3A4 DDIs. Comparison of two multiple TDI prediction models demonstrated significant differences between them in in-vitro-to-in-vitro predictions but not in in-vitro-to-in-vivo predictions. Inclusion of all four inhibitors predicted an in vivo decrease in CYP2C19 (95%) and CYP3A4 (60–62%) activity. The results of this study suggest that adequate worst-case risk assessment for in vivo DDIs by multiple TDI systems can be achieved by incorporating time-dependent inhibition by both parent and metabolite via simple addition of the in vivo time-dependent inhibition rate/cytochrome P450 degradation rate constant (λ/kdeg) values, but quantitative DDI predictions will require a more thorough understanding of TDI mechanisms. PMID:23785064

Influence of UV dose on the UV/H2O2 process for the degradation of carbamazepine in wastewater.

PubMed

Somathilake, Purnima; Dominic, John Albino; Achari, Gopal; Langford, Cooper H; Tay, Joo-Hwa

2018-05-02

This study evaluates the influence of UV dose on degradation of carbamazepine (CBZ) in wastewater under UV-C (λ = 254 nm) photolysis with and without H 2 O 2 . The rate of degradation of CBZ exhibited a direct dependence on the intensity of incident UV irradiation as the rate of degradation was observed to increase linearly (R 2  = 0.98) with UV intensity between 1.67 and 8.95 × 10 17 photons/s. More than 95% of the CBZ that spiked in wastewater rapidly degraded within 4 min with a first-order rate constant of 1.2 min -1 for an optimum H 2 O 2 dose of 100 mg/L. Bench-scale continuous flow reactor experiments also showed that CBZ degraded with first-order kinetics at a rate constant of 1.02 min -1 . The kinetic parameters obtained for a continuous bench-scale reactor were in good agreement with the relationships developed through batch experiments with only a marginal deviation of ± 6.5%. The relationship between UV intensity and CBZ degradation rate obtained in this study was extrapolated to the UV disinfection unit of a wastewater treatment plant to predict possible degradation of CBZ during UV disinfection. The addition of 100 mg/L of H 2 O 2 to the secondary-treated effluent entering the UV disinfection unit is predicted to achieve over 60% degradation of CBZ.

Simulation of the induction of oxidation of low-density lipoprotein by high copper concentrations: evidence for a nonconstant rate of initiation.

PubMed

Abuja, P M; Albertini, R; Esterbauer, H

1997-06-01

Kinetic simulation can help obtain deeper insight into the molecular mechanisms of complex processes, such as lipid peroxidation (LPO) in low-density lipoprotein (LDL). We have previously set up a single-compartment model of this process, initiating with radicals generated externally at a constant rate to show the interplay of radical scavenging and chain propagation. Here we focus on the initiating events, substituting constant rate of initiation (Ri) by redox cycling of Cu2+ and Cu+. Our simulation reveals that early events in copper-mediated LDL oxidation include (1) the reduction of Cu2+ by tocopherol (TocOH) which generates tocopheroxyl radical (TocO.), (2) the fate of TocO. which either is recycled or recombines with lipid peroxyl radical (LOO.), and (3) the reoxidation of Cu+ by lipid hydroperoxide which results in alkoxyl radical (LO.) formation. So TocO., LOO., and LO. can be regarded as primordial radicals, and the sum of their formation rates is the total rate of initiation, Ri. As experimental information of these initiating events cannot be obtained experimentally, the whole model was validated experimentally by comparison of LDL oxidation in the presence and absence of bathocuproine as predicted by simulation. Simulation predicts that Ri decreases by 2 orders of magnitude during lag time. This has important consequences for the estimation of oxidation resistance in copper-mediated LDL oxidation: after consumption of tocopherol, even small amounts of antioxidants may prolong the lag phase for a considerable time.

STRESS a SN survey at ESO

NASA Astrophysics Data System (ADS)

Botticella, M. T.

We performed the Southern inTermediate Redshift ESO Supernova Search (STRESS), a survey specifically designed to measure the rate of both SNe Ia and CC SNe, in order to obtain a direct comparison of the high redshift and local rates and to investigate the dependence of the rates on specific galaxy properties, most notably their colour. We found that the type Ia SN rate, at mean redshift z = 0.3, is 0.22+0.10+0.16-0.08-0.14 h270 SNu, while the CC SN rate, at z = 0.21, is 0.82+0.31+0.300.24-0.26 h270 SNu. The quoted errors are the statistical and systematic uncertainties. With respect to the local value, the CC SN rate at z = 0.2 is higher by a factor of ˜ 2, whereas the type Ia SN rate remains almost constant. We also measured the SN rates in the red and blue galaxies and found that the SN Ia rate seems to be constant in galaxies of different colour, whereas the CC SN rate seems to peak in blue galaxies, as in the local Universe. Finally we exploited the link between SFH and SN rates to predict the evolutionary behaviour of the SN rates and compare it with the path indicated by observations.

Theoretical Kinetics Analysis for $$\\dot{H}$$ Atom Addition to 1,3-Butadiene and Related Reactions on the $$\\dot{C}$$ 4H 7 Potential Energy Surface

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

Li, Yang; Klippenstein, Stephen J.; Zhou, Chong-Wen

The oxidation chemistry of the simplest conjugated hydrocarbon, 1,3-butadiene, can provide a first step in understanding the role of poly-unsaturated hydrocarbons in combustion and, in particular, an understanding of their contribution towards soot formation. Based on our previous work on propene and the butene isomers (1-, 2- and isobutene), it was found that the reaction kinetics of H-atom addition to the C=C double bond plays a significant role in fuel consumption kinetics and influences the predictions of high-temperature ignition delay times, product species concentrations and flame speed measurements. In this study, the rate constants and thermodynamic properties formore » $$\\dot{H}$$-atom addition to 1,3-butadiene and related reactions on the $$\\dot{C}$$ 4H 7 potential energy surface have been calculated using two different series of quantum chemical methods and two different kinetic codes. Excellent agreement is obtained between the two different kinetics codes. The calculated results including zero point energies, single point energies, rate constants, barrier heights and thermochemistry are systematically compared among the two quantum chemical methods. 1-methylallyl ($$\\dot{C}$$ 4H 71-3) and 3-buten-1- yl ($$\\dot{C}$$ 4H 71-4) radicals and C 2H 4 + $$\\dot{C}$$2H3 are found to be the most important channels and reactivity promoting products, respectively. We calculated that terminal addition is dominant (> 80%) compared to internal $$\\dot{H}$$-atom addition at all temperatures in the range 298 – 2000 K. However, this dominance decreases with increasing temperature. The calculated rate constants for the bimolecular reaction C 4H 6 + $$\\dot{H}$$ → products and C 2H 4 + $$\\dot{C}$$ 2H 3 → products are in excellent agreement with both experimental and theoretical results from the literature. For selected C 4 species the calculated thermochemical values are also in good agreement with literature data. In addition, the rate constants for H-atom abstraction by $$\\dot{H}$$ atoms have also been calculated, and it is found that abstraction from the central carbon atoms is the dominant channel (> 70%) at temperatures in the range 298 – 2000 K. Lastly, by incorporating our calculated rate constants for both H-atom addition and abstraction into our recently developed 1,3-butadiene model, we show that laminar flame speed predictions are significantly improved, emphasizing the value of this study.« less

Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations for solvent-based carbon capture. Part 2: Chemical absorption across a wetted wall column: Original Research Article: Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations

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

Wang, Chao; Xu, Zhijie; Lai, Kevin

The first part of this paper (Part 1) presents a numerical model for non-reactive physical mass transfer across a wetted wall column (WWC). In Part 2, we improved the existing computational fluid dynamics (CFD) model to simulate chemical absorption occurring in a WWC as a bench-scale study of solvent-based carbon dioxide (CO2) capture. To generate data for WWC model validation, CO2 mass transfer across a monoethanolamine (MEA) solvent was first measured on a WWC experimental apparatus. The numerical model developed in this work has the ability to account for both chemical absorption and desorption of CO2 in MEA. In addition,more » the overall mass transfer coefficient predicted using traditional/empirical correlations is conducted and compared with CFD prediction results for both steady and wavy falling films. A Bayesian statistical calibration algorithm is adopted to calibrate the reaction rate constants in chemical absorption/desorption of CO2 across a falling film of MEA. The posterior distributions of the two transport properties, i.e., Henry’s constant and gas diffusivity in the non-reacting nitrous oxide (N2O)/MEA system obtained from Part 1 of this study, serves as priors for the calibration of CO2 reaction rate constants after using the N2O/CO2 analogy method. The calibrated model can be used to predict the CO2 mass transfer in a WWC for a wider range of operating conditions.« less

Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations for solvent-based carbon capture. Part 2: Chemical absorption across a wetted wall column: Original Research Article: Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations

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

Wang, Chao; Xu, Zhijie; Lai, Kevin

Part 1 of this paper presents a numerical model for non-reactive physical mass transfer across a wetted wall column (WWC). In Part 2, we improved the existing computational fluid dynamics (CFD) model to simulate chemical absorption occurring in a WWC as a bench-scale study of solvent-based carbon dioxide (CO 2) capture. In this study, to generate data for WWC model validation, CO 2 mass transfer across a monoethanolamine (MEA) solvent was first measured on a WWC experimental apparatus. The numerical model developed in this work can account for both chemical absorption and desorption of CO 2 in MEA. In addition,more » the overall mass transfer coefficient predicted using traditional/empirical correlations is conducted and compared with CFD prediction results for both steady and wavy falling films. A Bayesian statistical calibration algorithm is adopted to calibrate the reaction rate constants in chemical absorption/desorption of CO 2 across a falling film of MEA. The posterior distributions of the two transport properties, i.e., Henry's constant and gas diffusivity in the non-reacting nitrous oxide (N 2O)/MEA system obtained from Part 1 of this study, serves as priors for the calibration of CO 2 reaction rate constants after using the N 2O/CO 2 analogy method. Finally, the calibrated model can be used to predict the CO 2 mass transfer in a WWC for a wider range of operating conditions.« less

Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations for solvent-based carbon capture. Part 2: Chemical absorption across a wetted wall column: Original Research Article: Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations

DOE PAGES

Wang, Chao; Xu, Zhijie; Lai, Kevin; ...

2017-10-24

Part 1 of this paper presents a numerical model for non-reactive physical mass transfer across a wetted wall column (WWC). In Part 2, we improved the existing computational fluid dynamics (CFD) model to simulate chemical absorption occurring in a WWC as a bench-scale study of solvent-based carbon dioxide (CO 2) capture. In this study, to generate data for WWC model validation, CO 2 mass transfer across a monoethanolamine (MEA) solvent was first measured on a WWC experimental apparatus. The numerical model developed in this work can account for both chemical absorption and desorption of CO 2 in MEA. In addition,more » the overall mass transfer coefficient predicted using traditional/empirical correlations is conducted and compared with CFD prediction results for both steady and wavy falling films. A Bayesian statistical calibration algorithm is adopted to calibrate the reaction rate constants in chemical absorption/desorption of CO 2 across a falling film of MEA. The posterior distributions of the two transport properties, i.e., Henry's constant and gas diffusivity in the non-reacting nitrous oxide (N 2O)/MEA system obtained from Part 1 of this study, serves as priors for the calibration of CO 2 reaction rate constants after using the N 2O/CO 2 analogy method. Finally, the calibrated model can be used to predict the CO 2 mass transfer in a WWC for a wider range of operating conditions.« less

Development of a model to simulate infection dynamics of Mycobacterium bovis in cattle herds in the United States

PubMed Central

Smith, Rebecca L.; Schukken, Ynte H.; Lu, Zhao; Mitchell, Rebecca M.; Grohn, Yrjo T.

2013-01-01

Objective To develop a mathematical model to simulate infection dynamics of Mycobacterium bovis in cattle herds in the United States and predict efficacy of the current national control strategy for tuberculosis in cattle. Design Stochastic simulation model. Sample Theoretical cattle herds in the United States. Procedures A model of within-herd M bovis transmission dynamics following introduction of 1 latently infected cow was developed. Frequency- and density-dependent transmission modes and 3 tuberculin-test based culling strategies (no test-based culling, constant (annual) testing with test-based culling, and the current strategy of slaughterhouse detection-based testing and culling) were investigated. Results were evaluated for 3 herd sizes over a 10-year period and validated via simulation of known outbreaks of M bovis infection. Results On the basis of 1,000 simulations (1000 herds each) at replacement rates typical for dairy cattle (0.33/y), median time to detection of M bovis infection in medium-sized herds (276 adult cattle) via slaughterhouse surveillance was 27 months after introduction, and 58% of these herds would spontaneously clear the infection prior to that time. Sixty-two percent of medium-sized herds without intervention and 99% of those managed with constant test-based culling were predicted to clear infection < 10 years after introduction. The model predicted observed outbreaks best for frequency-dependent transmission, and probability of clearance was most sensitive to replacement rate. Conclusions and Clinical Relevance Although modeling indicated the current national control strategy was sufficient for elimination of M bovis infection from dairy herds after detection, slaughterhouse surveillance was not sufficient to detect M bovis infection in all herds and resulted in subjectively delayed detection, compared with the constant testing method. Further research is required to economically optimize this strategy. PMID:23865885

ZERODUR®: new stress corrosion data improve strength fatigue prediction

NASA Astrophysics Data System (ADS)

Hartmann, Peter; Kleer, Günter; Rist, Tobias

2015-09-01

The extremely low thermal expansion glass ceramic ZERODUR® finds more and more applications as sophisticated light weight structures with thin ribs or as thin shells. Quite often they will be subject to higher mechanical loads such as rocket launches or modulating wobbling vibrations. Designing such structures requires calculation methods and data taking into account their long term fatigue. With brittle materials fatigue is not only given by the material itself but to a high extent also by its surface condition and the environmental media especially humidity. This work extends the latest data and information gathered on the bending strength of ZERODUR® with new results concerning its long term behavior under tensile stress. The parameter needed for prediction calculations which combines the influences of time and environmental media is the stress corrosion constant n. Results of the past differ significantly from each other. In order to obtain consistent data the stress corrosion constant has been measured with the method comparing the breakage statistical distributions at different stress increase rates. For better significance the stress increase rate was varied over four orders of magnitude from 0.004 MPa/s to 40 MPa/s. Experiments were performed under normal humidity for long term earth bound applications and under nitrogen atmosphere as equivalent to dry environment occurring for example with telescopes in deserts and also equivalent to vacuum for space applications. As shown earlier the bending strength of diamond ground surfaces of ZERODUR® can be represented with a three parameter Weibull distribution. Predictions on the long term strength change of ZERODUR® structures under tensile stress are possible with reduced uncertainty if Weibull threshold strength values are considered and more reliable stress corrosion constant data are applied.

Target and Tissue Selectivity Prediction by Integrated Mechanistic Pharmacokinetic-Target Binding and Quantitative Structure Activity Modeling.

PubMed

Vlot, Anna H C; de Witte, Wilhelmus E A; Danhof, Meindert; van der Graaf, Piet H; van Westen, Gerard J P; de Lange, Elizabeth C M

2017-12-04

Selectivity is an important attribute of effective and safe drugs, and prediction of in vivo target and tissue selectivity would likely improve drug development success rates. However, a lack of understanding of the underlying (pharmacological) mechanisms and availability of directly applicable predictive methods complicates the prediction of selectivity. We explore the value of combining physiologically based pharmacokinetic (PBPK) modeling with quantitative structure-activity relationship (QSAR) modeling to predict the influence of the target dissociation constant (K D ) and the target dissociation rate constant on target and tissue selectivity. The K D values of CB1 ligands in the ChEMBL database are predicted by QSAR random forest (RF) modeling for the CB1 receptor and known off-targets (TRPV1, mGlu5, 5-HT1a). Of these CB1 ligands, rimonabant, CP-55940, and Δ 8 -tetrahydrocanabinol, one of the active ingredients of cannabis, were selected for simulations of target occupancy for CB1, TRPV1, mGlu5, and 5-HT1a in three brain regions, to illustrate the principles of the combined PBPK-QSAR modeling. Our combined PBPK and target binding modeling demonstrated that the optimal values of the K D and k off for target and tissue selectivity were dependent on target concentration and tissue distribution kinetics. Interestingly, if the target concentration is high and the perfusion of the target site is low, the optimal K D value is often not the lowest K D value, suggesting that optimization towards high drug-target affinity can decrease the benefit-risk ratio. The presented integrative structure-pharmacokinetic-pharmacodynamic modeling provides an improved understanding of tissue and target selectivity.

An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures

DOE PAGES

Keromnes, Alan; Metcalfe, Wayne K.; Heufer, Karl A.; ...

2013-03-12

The oxidation of syngas mixtures was investigated experimentally and simulated with an updated chemical kinetic model. Ignition delay times for H 2/CO/O 2/N 2/Ar mixtures have been measured using two rapid compression machines and shock tubes at pressures from 1 to 70 bar, over a temperature range of 914–2220 K and at equivalence ratios from 0.1 to 4.0. Results show a strong dependence of ignition times on temperature and pressure at the end of the compression; ignition delays decrease with increasing temperature, pressure, and equivalence ratio. The reactivity of the syngas mixtures was found to be governed by hydrogen chemistrymore » for CO concentrations lower than 50% in the fuel mixture. For higher CO concentrations, an inhibiting effect of CO was observed. Flame speeds were measured in helium for syngas mixtures with a high CO content and at elevated pressures of 5 and 10 atm using the spherically expanding flame method. A detailed chemical kinetic mechanism for hydrogen and H 2/CO (syngas) mixtures has been updated, rate constants have been adjusted to reflect new experimental information obtained at high pressures and new rate constant values recently published in the literature. Experimental results for ignition delay times and flame speeds have been compared with predictions using our newly revised chemical kinetic mechanism, and good agreement was observed. In the mechanism validation, particular emphasis is placed on predicting experimental data at high pressures (up to 70 bar) and intermediate- to high-temperature conditions, particularly important for applications in internal combustion engines and gas turbines. The reaction sequence H 2 + HO˙ 2 ↔ H˙+H 2O 2 followed by H 2O 2(+M) ↔ O˙H+O˙H(+M) was found to play a key role in hydrogen ignition under high-pressure and intermediate-temperature conditions. The rate constant for H 2+HO˙ 2 showed strong sensitivity to high-pressure ignition times and has considerable uncertainty, based on literature values. As a result, a rate constant for this reaction is recommended based on available literature values and on our mechanism validation.« less

Effects of temperature on embryonic development of lake herring (Coregonus artedii)

USGS Publications Warehouse

Colby, Peter J.; Brooke, L.T.

1973-01-01

Embryonic development of lake herring (Coregonus artedii) was observed in the laboratory at 13 constant temperatures from 0.0 to 12.1 C and in Pickerel Lake (Washtenaw County, Michigan) at natural temperature regimes. Rate of development during incubation was based on progression of the embryos through 20 identifiable stages. An equation was derived to predict development stage at constant temperatures, on the general assumption that development stage (DS) is a function of time (days, D) and temperature (T). The equation should also be useful in interpreting estimates from future regressions that include other environmental variables that affect egg development. A second regression model, derived primarily for fluctuating temperatures, related development rate for stage j (DRj), expressed as the reciprocal of time, to temperature (x). The generalized equation for a development stage is: DRj = abx cx2 dx3. In general, time required for embryos to reach each stage of development in Pickerel Lake agreed closely with the time predicted from this equation, derived from our laboratory observations. Hatching time was predicted within 1 day in 1969 and within 2 days in 1970. We used the equations derived with the second model to predict the effect of the superimposition of temperature increases of 1 and 2 C on the measured temperatures in Pickerel Lake. Conceivably, hatching dates could be affected sufficiently to jeopardize the first feeding of lake herring through loss of harmony between hatching date and seasonal food availability.

Predictive modeling of surimi cake shelf life at different storage temperatures

NASA Astrophysics Data System (ADS)

Wang, Yatong; Hou, Yanhua; Wang, Quanfu; Cui, Bingqing; Zhang, Xiangyu; Li, Xuepeng; Li, Yujin; Liu, Yuanping

2017-04-01

The Arrhenius model of the shelf life prediction which based on the TBARS index was established in this study. The results showed that the significant changed of AV, POV, COV and TBARS with temperature increased, and the reaction rate constants k was obtained by the first order reaction kinetics model. Then the secondary model fitting was based on the Arrhenius equation. There was the optimal fitting accuracy of TBARS in the first and the secondary model fitting (R2≥0.95). The verification test indicated that the relative error between the shelf life model prediction value and actual value was within ±10%, suggesting the model could predict the shelf life of surimi cake.

Predicting sample lifetimes in creep fracture of heterogeneous materials

NASA Astrophysics Data System (ADS)

Koivisto, Juha; Ovaska, Markus; Miksic, Amandine; Laurson, Lasse; Alava, Mikko J.

2016-08-01

Materials flow—under creep or constant loads—and, finally, fail. The prediction of sample lifetimes is an important and highly challenging problem because of the inherently heterogeneous nature of most materials that results in large sample-to-sample lifetime fluctuations, even under the same conditions. We study creep deformation of paper sheets as one heterogeneous material and thus show how to predict lifetimes of individual samples by exploiting the "universal" features in the sample-inherent creep curves, particularly the passage to an accelerating creep rate. Using simulations of a viscoelastic fiber bundle model, we illustrate how deformation localization controls the shape of the creep curve and thus the degree of lifetime predictability.

A rational approach to improving productivity in recombinant Pichia pastoris fermentation.

PubMed

d'Anjou, M C; Daugulis, A J

2001-01-05

A Mut(S) Pichia pastoris strain that had been genetically modified to produce and secrete sea raven antifreeze protein was used as a model system to demonstrate the implementation of a rational, model-based approach to improve process productivity. A set of glycerol/methanol mixed-feed continuous stirred-tank reactor (CSTR) experiments was performed at the 5-L scale to characterize the relationship between the specific growth rate and the cell yield on methanol, the specific methanol consumption rate, the specific recombinant protein formation rate, and the productivity based on secreted protein levels. The range of dilution rates studied was 0. 01 to 0.10 h(-1), and the residual methanol concentration was kept constant at approximately 2 g/L (below the inhibitory level). With the assumption that the cell yield on glycerol was constant, the cell yield on methanol increased from approximately 0.5 to 1.5 over the range studied. A maximum specific methanol consumption rate of 20 mg/g. h was achieved at a dilution rate of 0.06 h(-1). The specific product formation rate and the volumetric productivity based on product continued to increase over the range of dilution rates studied, and the maximum values were 0.06 mg/g. h and 1.7 mg/L. h, respectively. Therefore, no evidence of repression by glycerol was observed over this range, and operating at the highest dilution rate studied maximized productivity. Fed-batch mass balance equations, based on Monod-type kinetics and parameters derived from data collected during the CSTR work, were then used to predict cell growth and recombinant protein production and to develop an exponential feeding strategy using two carbon sources. Two exponential fed-batch fermentations were conducted according to the predicted feeding strategy at specific growth rates of 0.03 h(-1) and 0.07 h(-1) to verify the accuracy of the model. Cell growth was accurately predicted in both fed-batch runs; however, the model underestimated recombinant product concentration. The overall volumetric productivity of both runs was approximately 2.2 mg/L. h, representing a tenfold increase in the productivity compared with a heuristic feeding strategy. Copyright 2001 John Wiley & Sons, Inc.

Endochronic theory of transient creep and creep recovery

NASA Technical Reports Server (NTRS)

Wu, H. C.; Chen, L.

1979-01-01

Short time creep and creep recovery were investigated by means of the endochronic theory of viscoplasticity. It is shown that the constitutive equations for constant-strain-rate stress-strain behavior, creep, creep recovery, and stress relaxation can all ber derived from the general constitutive equation by imposing appropriate constraints. In this unified approach, the effect of strain-hardening is naturally accounted for when describing creep and creep recovery. The theory predicts with reasonable accuracy the creep and creep recovery behaviors for Aluminum 1100-0 at 150 C. It was found that the strain-rate history at prestraining stage affects the subsequent creep. A critical stress was also established for creep recovery. The theory predicts a forward creep for creep recovery stress greater than the critical stress. For creep recovery stress less than the critical stress, the theory then predicts a normal strain recovery.

Kinetics of Methane Production from Swine Manure and Buffalo Manure.

PubMed

Sun, Chen; Cao, Weixing; Liu, Ronghou

2015-10-01

The degradation kinetics of swine and buffalo manure for methane production was investigated. Six kinetic models were employed to describe the corresponding experimental data. These models were evaluated by two statistical measurements, which were root mean square prediction error (RMSPE) and Akaike's information criterion (AIC). The results showed that the logistic and Fitzhugh models could predict the experimental data very well for the digestion of swine and buffalo manure, respectively. The predicted methane yield potential for swine and buffalo manure was 487.9 and 340.4 mL CH4/g volatile solid (VS), respectively, which was close to experimental values, when the digestion temperature was 36 ± 1 °C in the biochemical methane potential assays. Besides, the rate constant revealed that swine manure had a much faster methane production rate than buffalo manure.

Rate dependency of delayed rectifier currents during the guinea-pig ventricular action potential

PubMed Central

Rocchetti, Marcella; Besana, Alessandra; Gurrola, Georgina B; Possani, Lourival D; Zaza, Antonio

2001-01-01

The action potential clamp technique was exploited to evaluate the rate dependency of delayed rectifier currents (IKr and IKs) during physiological electrical activity. IKr and IKs were measured in guinea-pig ventricular myocytes at pacing cycle lengths (CL) of 1000 and 250 ms.A shorter CL, with the attendant changes in action potential shape, was associated with earlier activation and increased magnitude of both IKr and IKs. Nonetheless, the relative contributions of IKr and IKs to total transmembrane current were independent of CL.Shortening of diastolic interval only (constant action potential shape) enhanced IKs, but not IKr.IKr was increased by a change in the action potential shape only (constant diastolic interval).In ramp clamp experiments, IKr amplitude was directly proportional to repolarization rate at values within the low physiological range (< 1.0 V s−1); at higher repolarization rates proportionality became shallower and finally reversed.When action potential duration (APD) was modulated by constant current injection (I-clamp), repolarization rates > 1.0 V s−1 were associated with a reduced effect of IKr block on APD. The effect of changes in repolarization rate was independent of CL and occurred in the presence of IKs blockade.In spite of its complexity, the behaviour of IKr was accurately predicted by a numerical model based entirely on known kinetic properties of the current.Both IKr and IKs may be increased at fast heart rates, but this may occur through completely different mechanisms. The mechanisms identified are such as to contribute to abnormal rate dependency of repolarization in prolonged repolarization syndromes. PMID:11483703

False CAM alarms from radon fluctuations.

PubMed

Hayes, Robert

2003-11-01

The root cause of many false continuous air monitor (CAM) alarms is revealed for CAMs that use constant spectral shape assumptions in transuranic (TRU) alpha activity determination algorithms. This paper shows that when atmospheric radon levels continually decrease and bottom out at a minimum level, reduced false TRU count rates are not only expected but measured. Similarly, when the radon levels continually increase to a maximum level, elevated false TRU count rates were measured as predicted. The basis for expecting this dependence on changes in radon levels is discussed.

Approximate convective heating equations for hypersonic flows

NASA Technical Reports Server (NTRS)

Zoby, E. V.; Moss, J. N.; Sutton, K.

1979-01-01

Laminar and turbulent heating-rate equations appropriate for engineering predictions of the convective heating rates about blunt reentry spacecraft at hypersonic conditions are developed. The approximate methods are applicable to both nonreacting and reacting gas mixtures for either constant or variable-entropy edge conditions. A procedure which accounts for variable-entropy effects and is not based on mass balancing is presented. Results of the approximate heating methods are in good agreement with existing experimental results as well as boundary-layer and viscous-shock-layer solutions.

A Coarse-Grained Biophysical Model of E. coli and Its Application to Perturbation of the rRNA Operon Copy Number

PubMed Central

Tadmor, Arbel D.; Tlusty, Tsvi

2008-01-01

We propose a biophysical model of Escherichia coli that predicts growth rate and an effective cellular composition from an effective, coarse-grained representation of its genome. We assume that E. coli is in a state of balanced exponential steady-state growth, growing in a temporally and spatially constant environment, rich in resources. We apply this model to a series of past measurements, where the growth rate and rRNA-to-protein ratio have been measured for seven E. coli strains with an rRNA operon copy number ranging from one to seven (the wild-type copy number). These experiments show that growth rate markedly decreases for strains with fewer than six copies. Using the model, we were able to reproduce these measurements. We show that the model that best fits these data suggests that the volume fraction of macromolecules inside E. coli is not fixed when the rRNA operon copy number is varied. Moreover, the model predicts that increasing the copy number beyond seven results in a cytoplasm densely packed with ribosomes and proteins. Assuming that under such overcrowded conditions prolonged diffusion times tend to weaken binding affinities, the model predicts that growth rate will not increase substantially beyond the wild-type growth rate, as indicated by other experiments. Our model therefore suggests that changing the rRNA operon copy number of wild-type E. coli cells growing in a constant rich environment does not substantially increase their growth rate. Other observations regarding strains with an altered rRNA operon copy number, such as nucleoid compaction and the rRNA operon feedback response, appear to be qualitatively consistent with this model. In addition, we discuss possible design principles suggested by the model and propose further experiments to test its validity. PMID:18437222

A hybrid constructed wetland for organic-material and nutrient removal from sewage: Process performance and multi-kinetic models.

PubMed

Nguyen, X Cuong; Chang, S Woong; Nguyen, Thi Loan; Ngo, H Hao; Kumar, Gopalakrishnan; Banu, J Rajesh; Vu, M Cuong; Le, H Sinh; Nguyen, D Duc

2018-09-15

A pilot-scale hybrid constructed wetland with vertical flow and horizontal flow in series was constructed and used to investigate organic material and nutrient removal rate constants for wastewater treatment and establish a practical predictive model for use. For this purpose, the performance of multiple parameters was statistically evaluated during the process and predictive models were suggested. The measurement of the kinetic rate constant was based on the use of the first-order derivation and Monod kinetic derivation (Monod) paired with a plug flow reactor (PFR) and a continuously stirred tank reactor (CSTR). Both the Lindeman, Merenda, and Gold (LMG) analysis and Bayesian model averaging (BMA) method were employed for identifying the relative importance of variables and their optimal multiple regression (MR). The results showed that the first-order-PFR (M 2 ) model did not fit the data (P > 0.05, and R 2  < 0.5), whereas the first-order-CSTR (M 1 ) model for the chemical oxygen demand (COD Cr ) and Monod-CSTR (M 3 ) model for the COD Cr and ammonium nitrogen (NH 4 -N) showed a high correlation with the experimental data (R 2  > 0.5). The pollutant removal rates in the case of M 1 were 0.19 m/d (COD Cr ) and those for M 3 were 25.2 g/m 2 ∙d for COD Cr and 2.63 g/m 2 ∙d for NH 4 -N. By applying a multi-variable linear regression method, the optimal empirical models were established for predicting the final effluent concentration of five days' biochemical oxygen demand (BOD 5 ) and NH 4 -N. In general, the hydraulic loading rate was considered an important variable having a high value of relative importance, which appeared in all the optimal predictive models. Copyright © 2018 Elsevier Ltd. All rights reserved.

Desorption kinetics of hydrophobic organic chemicals from sediment to water: a review of data and models.

PubMed

Birdwell, Justin; Cook, Robert L; Thibodeaux, Louis J

2007-03-01

Resuspension of contaminated sediment can lead to the release of toxic compounds to surface waters where they are more bioavailable and mobile. Because the timeframe of particle resettling during such events is shorter than that needed to reach equilibrium, a kinetic approach is required for modeling the release process. Due to the current inability of common theoretical approaches to predict site-specific release rates, empirical algorithms incorporating the phenomenological assumption of biphasic, or fast and slow, release dominate the descriptions of nonpolar organic chemical release in the literature. Two first-order rate constants and one fraction are sufficient to characterize practically all of the data sets studied. These rate constants were compared to theoretical model parameters and functionalities, including chemical properties of the contaminants and physical properties of the sorbents, to determine if the trends incorporated into the hindered diffusion model are consistent with the parameters used in curve fitting. The results did not correspond to the parameter dependence of the hindered diffusion model. No trend in desorption rate constants, for either fast or slow release, was observed to be dependent on K(OC) or aqueous solubility for six and seven orders of magnitude, respectively. The same was observed for aqueous diffusivity and sediment fraction organic carbon. The distribution of kinetic rate constant values was approximately log-normal, ranging from 0.1 to 50 d(-1) for the fast release (average approximately 5 d(-1)) and 0.0001 to 0.1 d(-1) for the slow release (average approximately 0.03 d(-1)). The implications of these findings with regard to laboratory studies, theoretical desorption process mechanisms, and water quality modeling needs are presented and discussed.

Metabolic Rate Constants for Hydroquinone in F344 Rat and Human Liver Isolated Hepatocytes: Application to a PBPK model.

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

Poet, Torka S.; Wu, Hong; English, J C.

2004-11-15

Hydroquinone (HQ) is an important industrial chemical that also occurs naturally in foods and in the leaves and bark of a number of plant species. Exposure of laboratory animals to HQ may result in a species-, sex-, and strain-specific nephrotoxicity. The sensitivity of male F344 vs. female F344 and Sprague-Dawley rats or B6C3F1 mice appears to be related to differences in the rates of formation and further metabolism of key nephrotoxic metabolites. Metabolic rate constants for the conversion of HQ through several metabolic steps to the mono-glutathione conjugate and subsequent detoxification via mercapturic acid were measured in suspension cultures ofmore » hepatocytes isolated from male F344 rats and humans. An in vitro mathematic kinetic model was used to analyze each metabolic step by simultaneously fitting the disappearance of each substrate and the appearance of subsequent metabolites. An iterative, nested approach was used whereby downstream metabolites were considered first and the model was constrained by the requirement that rate constants determined during analysis of individual metabolic steps must also satisfy the complete, integrated metabolism scheme, including competitive pathways. The results from this study indicated that the overall capacity for metabolism of HQ and its mono-glutathione conjugate is greater in hepatocytes from humans than those isolated from rats, suggesting a greater capacity for detoxification of the glutathione conjugates. Metabolic rate constants were applied to an existing physiologically based pharmacokinetic model and the model was used to predict total glutathione metabolites produced in the liver. The results showed that body burdens of these metabolites will be much higher in rats than humans.« less

Electrostatic Potential Energy within a Protein Monitored by Metal Charge-Dependent Hydrogen Exchange

PubMed Central

Anderson, Janet S.; LeMaster, David M.; Hernández, Griselda

2006-01-01

Hydrogen exchange measurements on Zn(II)-, Ga(III)-, and Ge(IV)-substituted Pyrococcus furiosus rubredoxin demonstrate that the log ratio of the base-catalyzed rate constants (Δ log kex) varies inversely with the distance out to at least 12 Å from the metal. This pattern is consistent with the variation of the amide nitrogen pK values with the metal charge-dependent changes in the electrostatic potential. Fifteen monitored amides lie within this range, providing an opportunity to assess the strength of electrostatic interactions simultaneously at numerous positions within the structure. Poisson-Boltzmann calculations predict an optimal effective internal dielectric constant of 6. The largest deviations between the experimentally estimated and the predicted ΔpK values appear to result from the conformationally mobile charged side chains of Lys-7 and Glu-48 and from differential shielding of the peptide units arising from their orientation relative to the metal site. PMID:17012322

Treatment of uncertainties in atmospheric chemical systems: A combined modeling and experimental approach

NASA Astrophysics Data System (ADS)

Pun, Betty Kong-Ling

1998-12-01

Uncertainty is endemic in modeling. This thesis is a two- phase program to understand the uncertainties in urban air pollution model predictions and in field data used to validate them. Part I demonstrates how to improve atmospheric models by analyzing the uncertainties in these models and using the results to guide new experimentation endeavors. Part II presents an experiment designed to characterize atmospheric fluctuations, which have significant implications towards the model validation process. A systematic study was undertaken to investigate the effects of uncertainties in the SAPRC mechanism for gas- phase chemistry in polluted atmospheres. The uncertainties of more than 500 parameters were compiled, including reaction rate constants, product coefficients, organic composition, and initial conditions. Uncertainty propagation using the Deterministic Equivalent Modeling Method (DEMM) revealed that the uncertainties in ozone predictions can be up to 45% based on these parametric uncertainties. The key parameters found to dominate the uncertainties of the predictions include photolysis rates of NO2, O3, and formaldehyde; the rate constant for nitric acid formation; and initial amounts of NOx and VOC. Similar uncertainty analysis procedures applied to two other mechanisms used in regional air quality models led to the conclusion that in the presence of parametric uncertainties, the mechanisms cannot be discriminated. Research efforts should focus on reducing parametric uncertainties in photolysis rates, reaction rate constants, and source terms. A new tunable diode laser (TDL) infrared spectrometer was designed and constructed to measure multiple pollutants simultaneously in the same ambient air parcels. The sensitivities of the one hertz measurements were 2 ppb for ozone, 1 ppb for NO, and 0.5 ppb for NO2. Meteorological data were also collected for wind, temperature, and UV intensity. The field data showed clear correlations between ozone, NO, and NO2 in the one-second time scale. Fluctuations in pollutant concentrations were found to be extremely dependent on meteorological conditions. Deposition fluxes calculated using the Eddy Correlation technique were found to be small on concrete surfaces. These high time-resolution measurements were used to develop an understanding of the variability in atmospheric measurements, which would be useful in determining the acceptable discrepancy of model and observations. (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617-253-5668; Fax 617-253-1690.)

A Predictive Model Has Identified Tick-Borne Encephalitis High-Risk Areas in Regions Where No Cases Were Reported Previously, Poland, 1999–2012

PubMed Central

Rubikowska, Barbara; Bratkowski, Jakub; Ustrnul, Zbigniew; Vanwambeke, Sophie O.

2018-01-01

During 1999–2012, 77% of the cases of tick-borne encephalitis (TBE) were recorded in two out of 16 Polish provinces. However, historical data, mostly from national serosurveys, suggest that the disease could be undetected in many areas. The aim of this study was to identify which routinely-measured meteorological, environmental, and socio-economic factors are associated to TBE human risk across Poland, with a particular focus on areas reporting few cases, but where serosurveys suggest higher incidence. We fitted a zero-inflated Poisson model using data on TBE incidence recorded in 108 NUTS-5 administrative units in high-risk areas over the period 1999–2012. Subsequently we applied the best fitting model to all Polish municipalities. Keeping the remaining variables constant, the predicted rate increased with the increase of air temperature over the previous 10–20 days, precipitation over the previous 20–30 days, in forestation, forest edge density, forest road density, and unemployment. The predicted rate decreased with increasing distance from forests. The map of predicted rates was consistent with the established risk areas. It predicted, however, high rates in provinces considered TBE-free. We recommend raising awareness among physicians working in the predicted high-risk areas and considering routine use of household animal surveys for risk mapping. PMID:29617333

A Predictive Model Has Identified Tick-Borne Encephalitis High-Risk Areas in Regions Where No Cases Were Reported Previously, Poland, 1999-2012.

PubMed

Stefanoff, Pawel; Rubikowska, Barbara; Bratkowski, Jakub; Ustrnul, Zbigniew; Vanwambeke, Sophie O; Rosinska, Magdalena

2018-04-04

During 1999–2012, 77% of the cases of tick-borne encephalitis (TBE) were recorded in two out of 16 Polish provinces. However, historical data, mostly from national serosurveys, suggest that the disease could be undetected in many areas. The aim of this study was to identify which routinely-measured meteorological, environmental, and socio-economic factors are associated to TBE human risk across Poland, with a particular focus on areas reporting few cases, but where serosurveys suggest higher incidence. We fitted a zero-inflated Poisson model using data on TBE incidence recorded in 108 NUTS-5 administrative units in high-risk areas over the period 1999–2012. Subsequently we applied the best fitting model to all Polish municipalities. Keeping the remaining variables constant, the predicted rate increased with the increase of air temperature over the previous 10–20 days, precipitation over the previous 20–30 days, in forestation, forest edge density, forest road density, and unemployment. The predicted rate decreased with increasing distance from forests. The map of predicted rates was consistent with the established risk areas. It predicted, however, high rates in provinces considered TBE-free. We recommend raising awareness among physicians working in the predicted high-risk areas and considering routine use of household animal surveys for risk mapping.

Experimental study of brucite dissolution and precipitation in aqueous solutions: surface speciation and chemical affinity control

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques

2004-01-01

Dissolution and precipitation rates of brucite (Mg(OH) 2) were measured at 25°C in a mixed-flow reactor as a function of pH (2.5 to 12), ionic strength (10 -4 to 3 M), saturation index (-12 < log Ω < 0.4) and aqueous magnesium concentrations (10 -6 to 5·10 -4 M). Brucite surface charge and isoelectric point (pH IEP) were determined by surface titrations in a limited residence time reactor and electrophoretic measurements, respectively. The pH of zero charge and pH IEP were close to 11. A two-pK, one site surface speciation model which assumes a constant capacitance of the electric double layer (5 F/m 2) and lack of dependence on ionic strength predicts the dominance of >MgOH 2+ species at pH < 8 and their progressive replacement by >MgOH° and >MgO - as pH increases to 10-12. Rates are proportional to the square of >MgOH 2+ surface concentration at pH from 2.5 to 12. In accord with surface speciation predictions, dissolution rates do not depend on ionic strength at pH 6.5 to 11. Brucite dissolution and precipitation rates at close to equilibrium conditions obeyed TST-derived rate laws. At constant saturation indices, brucite precipitation rates were proportional to the square of >MgOH 2+ concentration. The following rate equation, consistent with transition state theory, describes brucite dissolution and precipitation kinetics over a wide range of solution composition and chemical affinity: R=k Mg+ · {>MgOH 2+} 2 · (1-Ω 2) where kMg+ is the dissolution rate constant, {> i} is surface species concentration (mol/m 2), and Ω is the solution saturation index with respect to brucite. Measurements of nonsteady state brucite dissolution rates, in response to cycling the pH from 12 to 2 (pH-jump experiments), indicate the important role of surface hydroxylation — that leads to the formation of Mg oxo or -hydroxo complexes — in the formation of dissolution-active sites. Replacement of water molecules by these oxygen donor complexes in the Mg coordination sphere has a labilizing effect on the dynamics of the remaining water molecules and thus increases reaction rates.

Theoretical study of the reaction mechanism and kinetics of low-molecular-weight atmospheric aldehydes (C1-C4) with NO2

NASA Astrophysics Data System (ADS)

Ji, Yuemeng; Gao, Yanpeng; Li, Guiying; An, Taicheng

2012-07-01

Accurate description of atmospheric reactions of a series of low-molecular-weight (LMW) aldehydes (C1-C4) with NO2 has been modeled using a direct dynamic approach. The profiles of the potential energy surface were constructed at the BMC-CCSD//MPWB1K/6-311G(d,p) level of theory, and two different pathways have been found: H-abstraction and NO2-addition. The modeling results found that the contribution of NO2-addition reaction pathway to the total rate constant is very small and thus this kind of pathway is insignificant in atmospheric conditions. The predicted H-abstraction products are mainly reactive acyl radical and nitrous acid (HONO) which is very mutagenic and carcinogenic pollutant as well as the precursor of acid deposition. The rate constants of both pathways were also deduced by using canonical variational transition state theory incorporating with the small curvature tunneling correction within 200-360 and 360-2000 K. Theoretical overall rate constants are in good agreement with the available experimental values, whose increase in the order of kformaldehyde < kacetaldehyde < kpropanal < kbutanal, implying that relative long-chain LMW aldehydes are more reactive toward NO2 than those short-chain LMW aldehydes in the atmospheric condition. At 298 K, the total rate constants of LMW aldehydes (C1-C4) with NO2 are obtained as 1.65 × 10-25, 1.43 × 10-24, 3.39 × 10-24 and 1.83 × 10-23 cm3 molecule-1 s-1, respectively.

Modeling of thermal degradation kinetics of the C-glucosyl xanthone mangiferin in an aqueous model solution as a function of pH and temperature and protective effect of honeybush extract matrix.

PubMed

Beelders, Theresa; de Beer, Dalene; Kidd, Martin; Joubert, Elizabeth

2018-01-01

Mangiferin, a C-glucosyl xanthone, abundant in mango and honeybush, is increasingly targeted for its bioactive properties and thus to enhance functional properties of food. The thermal degradation kinetics of mangiferin at pH3, 4, 5, 6 and 7 were each modeled at five temperatures ranging between 60 and 140°C. First-order reaction models were fitted to the data using non-linear regression to determine the reaction rate constant at each pH-temperature combination. The reaction rate constant increased with increasing temperature and pH. Comparison of the reaction rate constants at 100°C revealed an exponential relationship between the reaction rate constant and pH. The data for each pH were also modeled with the Arrhenius equation using non-linear and linear regression to determine the activation energy and pre-exponential factor. Activation energies decreased slightly with increasing pH. Finally, a multi-linear model taking into account both temperature and pH was developed for mangiferin degradation. Sterilization (121°C for 4min) of honeybush extracts dissolved at pH4, 5 and 7 did not cause noticeable degradation of mangiferin, although the multi-linear model predicted 34% degradation at pH7. The extract matrix is postulated to exert a protective effect as changes in potential precursor content could not fully explain the stability of mangiferin. Copyright © 2017 Elsevier Ltd. All rights reserved.

Modelling bioaccumulation of semi-volatile organic compounds (SOCs) from air in plants based on allometric principles.

PubMed

Steyaert, Nils L L; Hauck, Mara; Van Hulle, Stijn W H; Hendriks, A Jan

2009-10-01

A model was developed for gaseous plant-air exchange of semi-volatile organic compounds. Based on previous soil-plant modelling, uptake and elimination kinetics were scaled as a function of plant mass and octanol-air partition ratios. Exchange of chemicals was assumed to be limited by resistances encountered during diffusion through a laminar boundary layer of air and permeation through the cuticle of the leaf. The uptake rate constant increased and the elimination rate constant decreased with the octanol-air partition ratio both apparently levelling off at high values. Differences in kinetics between species could be explained by their masses. Validation on independent data showed that bio-concentration factors of PCBs, chlorobenzenes and other chemicals were predicted well by the model. For pesticides, polycyclic aromatic hydrocarbons and dioxins deviations occurred.

Glucose predictability, blood capillary permeability, and glucose utilization rate in subcutaneous, skeletal muscle, and visceral fat tissues.

PubMed

Koutny, Tomas

2013-11-01

This study suggests an approach for the comparison and evaluation of particular compartments with modest experimental setup costs. A glucose level prediction model was used to evaluate the compartment's glucose transport rate across the blood capillary membrane and the glucose utilization rate by the cells. The glucose levels of the blood, subcutaneous tissue, skeletal muscle tissue, and visceral fat were obtained in experiments conducted on hereditary hypertriglyceridemic rats. After the blood glucose level had undergone a rapid change, the experimenter attempted to reach a steady blood glucose level by manually correcting the glucose infusion rate and maintaining a constant insulin infusion rate. The interstitial fluid glucose levels of subcutaneous tissue, skeletal muscle tissue, and visceral fat were evaluated to determine the reaction delay compared with the change in the blood glucose level, the interstitial fluid glucose level predictability, the blood capillary permeability, the effect of the concentration gradient, and the glucose utilization rate. Based on these data, the glucose transport rate across the capillary membrane and the utilization rate in a particular tissue were determined. The rates obtained were successfully verified against positron emission tomography experiments. The subcutaneous tissue exhibits the lowest and the most predictable glucose utilization rate, whereas the skeletal muscle tissue has the greatest glucose utilization rate. In contrast, the visceral fat is the least predictable and has the shortest reaction delay compared with the change in the blood glucose level. The reaction delays obtained for the subcutaneous tissue and skeletal muscle tissue were found to be approximately equal using a metric based on the time required to reach half of the increase in the interstitial fluid glucose level. © 2013 Published by Elsevier Ltd.

Association rate constants for reactions between resonance-stabilized radicals: C 3H 3 + C 3H 3, C 3H 3 + C 3H 5, and C 3H 5 + C 3H 5

DOE PAGES

Georgievskii, Yuri; Miller, James A.; Klippenstein, Stephen J.

2007-05-18

Reactions between resonance-stabilized radicals play an important role in combustion chemistry. The theoretical prediction of rate coefficients and product distributions for such reactions is complicated by the fact that the initial complex-formation steps and some dissociation steps are barrierless. In this work, direct variable reaction coordinate transition state theory (VRC-TST) is used to predict accurately the association rate constants for the self and cross reactions of propargyl and allyl radicals. For each reaction, a set of multifaceted dividing surfaces is used to account for the multiple possible addition channels. Because of their resonant nature the geometric relaxation of the radicalsmore » is important. Here, the effect of this relaxation is explicitly calculated with the UB3LYP/cc-pvdz method for each mutual orientation encountered in the configurational integrals over the transition state dividing surfaces. The final energies are obtained from CASPT2/cc-pvdz calculations with all π-orbitals in the active space. Evaluations along the minimum energy path suggest that basis set corrections are negligible. The VRC-TST approach was also used to calculate the association rate constant and the corresponding number of states for the C 6H 5 + H → C 6H 6 exit channel of the C 3H 3 + C 3H 3 reaction, which is also barrierless. For this reaction, the interaction energies were evaluated with the CASPT2(2e,2o)/cc-pvdz method and a 1-D correction is included on the basis of CAS+1+2+QC/aug-cc-pvtz calculations for the CH 3 + H reference system. For the C 3H 3 + C 3H 3 reaction, the VRC-TST results for the energy and angular momentum resolved numbers of states in the entrance channels and in the C 6H 5 + H exit channel are incorporated in a master equation simulation to determine the temperature and pressure dependence of the phenomenological rate coefficients. The rate constants for the C 3H 3 + C 3H 3 and C 3H 5 + C 3H 5 self-reactions compare favorably with the available experimental data. Finally, to our knowledge there are no experimental rate data for the C 3H 3 + C 3H 5 reaction.« less

Method to predict relative hydriding within a group of zirconium alloys under nuclear irradiation

DOEpatents

Johnson, Jr., A. Burtron; Levy, Ira S.; Trimble, Dennis J.; Lanning, Donald D.; Gerber, Franna S.

1990-01-01

An out-of-reactor method for screening to predict relative in-reactor hydriding behavior of zirconium-bsed materials is disclosed. Samples of zirconium-based materials having different composition and/or fabrication are autoclaved in a relatively concentrated (0.3 to 1.0M) aqueous lithium hydroxide solution at constant temperatures within the water reactor coolant temperature range (280.degree. to 316.degree. C.). Samples tested by this out-of-reactor procedure, when compared on the basis of the ratio of hydrogen weight gain to oxide weight gain, accurately predict the relative rate of hyriding for the same materials when subject to in-reactor (irradiated) corrision.

An initial-abstraction, constant-loss model for unit hydrograph modeling for applicable watersheds in Texas

USGS Publications Warehouse

Asquith, William H.; Roussel, Meghan C.

2007-01-01

Estimation of representative hydrographs from design storms, which are known as design hydrographs, provides for cost-effective, riskmitigated design of drainage structures such as bridges, culverts, roadways, and other infrastructure. During 2001?07, the U.S. Geological Survey (USGS), in cooperation with the Texas Department of Transportation, investigated runoff hydrographs, design storms, unit hydrographs,and watershed-loss models to enhance design hydrograph estimation in Texas. Design hydrographs ideally should mimic the general volume, peak, and shape of observed runoff hydrographs. Design hydrographs commonly are estimated in part by unit hydrographs. A unit hydrograph is defined as the runoff hydrograph that results from a unit pulse of excess rainfall uniformly distributed over the watershed at a constant rate for a specific duration. A time-distributed, watershed-loss model is required for modeling by unit hydrographs. This report develops a specific time-distributed, watershed-loss model known as an initial-abstraction, constant-loss model. For this watershed-loss model, a watershed is conceptualized to have the capacity to store or abstract an absolute depth of rainfall at and near the beginning of a storm. Depths of total rainfall less than this initial abstraction do not produce runoff. The watershed also is conceptualized to have the capacity to remove rainfall at a constant rate (loss) after the initial abstraction is satisfied. Additional rainfall inputs after the initial abstraction is satisfied contribute to runoff if the rainfall rate (intensity) is larger than the constant loss. The initial abstraction, constant-loss model thus is a two-parameter model. The initial-abstraction, constant-loss model is investigated through detailed computational and statistical analysis of observed rainfall and runoff data for 92 USGS streamflow-gaging stations (watersheds) in Texas with contributing drainage areas from 0.26 to 166 square miles. The analysis is limited to a previously described, watershed-specific, gamma distribution model of the unit hydrograph. In particular, the initial-abstraction, constant-loss model is tuned to the gamma distribution model of the unit hydrograph. A complex computational analysis of observed rainfall and runoff for the 92 watersheds was done to determine, by storm, optimal values of initial abstraction and constant loss. Optimal parameter values for a given storm were defined as those values that produced a modeled runoff hydrograph with volume equal to the observed runoff hydrograph and also minimized the residual sum of squares of the two hydrographs. Subsequently, the means of the optimal parameters were computed on a watershed-specific basis. These means for each watershed are considered the most representative, are tabulated, and are used in further statistical analyses. Statistical analyses of watershed-specific, initial abstraction and constant loss include documentation of the distribution of each parameter using the generalized lambda distribution. The analyses show that watershed development has substantial influence on initial abstraction and limited influence on constant loss. The means and medians of the 92 watershed-specific parameters are tabulated with respect to watershed development; although they have considerable uncertainty, these parameters can be used for parameter prediction for ungaged watersheds. The statistical analyses of watershed-specific, initial abstraction and constant loss also include development of predictive procedures for estimation of each parameter for ungaged watersheds. Both regression equations and regression trees for estimation of initial abstraction and constant loss are provided. The watershed characteristics included in the regression analyses are (1) main-channel length, (2) a binary factor representing watershed development, (3) a binary factor representing watersheds with an abundance of rocky and thin-soiled terrain, and (4) curve numb

Modeling and validation of autoinducer-mediated bacterial gene expression in microfluidic environments

PubMed Central

Austin, Caitlin M.; Stoy, William; Su, Peter; Harber, Marie C.; Bardill, J. Patrick; Hammer, Brian K.; Forest, Craig R.

2014-01-01

Biosensors exploiting communication within genetically engineered bacteria are becoming increasingly important for monitoring environmental changes. Currently, there are a variety of mathematical models for understanding and predicting how genetically engineered bacteria respond to molecular stimuli in these environments, but as sensors have miniaturized towards microfluidics and are subjected to complex time-varying inputs, the shortcomings of these models have become apparent. The effects of microfluidic environments such as low oxygen concentration, increased biofilm encapsulation, diffusion limited molecular distribution, and higher population densities strongly affect rate constants for gene expression not accounted for in previous models. We report a mathematical model that accurately predicts the biological response of the autoinducer N-acyl homoserine lactone-mediated green fluorescent protein expression in reporter bacteria in microfluidic environments by accommodating these rate constants. This generalized mass action model considers a chain of biomolecular events from input autoinducer chemical to fluorescent protein expression through a series of six chemical species. We have validated this model against experimental data from our own apparatus as well as prior published experimental results. Results indicate accurate prediction of dynamics (e.g., 14% peak time error from a pulse input) and with reduced mean-squared error with pulse or step inputs for a range of concentrations (10 μM–30 μM). This model can help advance the design of genetically engineered bacteria sensors and molecular communication devices. PMID:25379076

Temperature-dependent electrochemical heat generation in a commercial lithium-ion battery

NASA Astrophysics Data System (ADS)

Bandhauer, Todd M.; Garimella, Srinivas; Fuller, Thomas F.

2014-02-01

Lithium-ion batteries suffer from inherent thermal limitations (i.e., capacity fade and thermal runaway); thus, it is critical to understand heat generation experienced in the batteries under normal operation. In the current study, reversible and irreversible electrochemical heat generation rates were measured experimentally on a small commercially available C/LiFePO4 lithium-ion battery designed for high-rate applications. The battery was tested over a wide range of temperatures (10-60 °C) and discharge and charge rates (∼C/4-5C) to elucidate their effects. Two samples were tested in a specially designed wind tunnel to maintain constant battery surface temperature within a maximum variation of ±0.88 °C. A data normalization technique was employed to account for the observed capacity fade, which was largest at the highest rates. The heat rate was shown to increase with both increasing rate and decreasing temperature, and the reversible heat rate was shown to be significant even at the highest rate and temperature (7.4% at 5C and 55 °C). Results from cycling the battery using a dynamic power profile also showed that constant-current data predict the dynamic performance data well. In addition, the reversible heat rate in the dynamic simulation was shown to be significant, especially for charge-depleting HEV applications.

Creep fatigue life prediction for engine hot section materials (isotropic)

NASA Technical Reports Server (NTRS)

Moreno, Vito; Nissley, David; Lin, Li-Sen Jim

1985-01-01

The first two years of a two-phase program aimed at improving the high temperature crack initiation life prediction technology for gas turbine hot section components are discussed. In Phase 1 (baseline) effort, low cycle fatigue (LCF) models, using a data base generated for a cast nickel base gas turbine hot section alloy (B1900+Hf), were evaluated for their ability to predict the crack initiation life for relevant creep-fatigue loading conditions and to define data required for determination of model constants. The variables included strain range and rate, mean strain, strain hold times and temperature. None of the models predicted all of the life trends within reasonable data requirements. A Cycle Damage Accumulation (CDA) was therefore developed which follows an exhaustion of material ductility approach. Material ductility is estimated based on observed similarities of deformation structure between fatigue, tensile and creep tests. The cycle damage function is based on total strain range, maximum stress and stress amplitude and includes both time independent and time dependent components. The CDA model accurately predicts all of the trends in creep-fatigue life with loading conditions. In addition, all of the CDA model constants are determinable from rapid cycle, fully reversed fatigue tests and monotonic tensile and/or creep data.

Integration of Harvest and Time-to-Event Data Used to Estimate Demographic Parameters for White-tailed Deer

NASA Astrophysics Data System (ADS)

Norton, Andrew S.

An integral component of managing game species is an understanding of population dynamics and relative abundance. Harvest data are frequently used to estimate abundance of white-tailed deer. Unless harvest age-structure is representative of the population age-structure and harvest vulnerability remains constant from year to year, these data alone are of limited value. Additional model structure and auxiliary information has accommodated this shortcoming. Specifically, integrated age-at-harvest (AAH) state-space population models can formally combine multiple sources of data, and regularization via hierarchical model structure can increase flexibility of model parameters. I collected known fates data, which I evaluated and used to inform trends in survival parameters for an integrated AAH model. I used temperature and snow depth covariates to predict survival outside of the hunting season, and opening weekend temperature and percent of corn harvest covariates to predict hunting season survival. When auxiliary empirical data were unavailable for the AAH model, moderately informative priors provided sufficient information for convergence and parameter estimates. The AAH model was most sensitive to errors in initial abundance, but this error was calibrated after 3 years. Among vital rates, the AAH model was most sensitive to reporting rates (percentage of mortality during the hunting season related to harvest). The AAH model, using only harvest data, was able to track changing abundance trends due to changes in survival rates even when prior models did not inform these changes (i.e. prior models were constant when truth varied). I also compared AAH model results with estimates from the Wisconsin Department of Natural Resources (WIDNR). Trends in abundance estimates from both models were similar, although AAH model predictions were systematically higher than WIDNR estimates in the East study area. When I incorporated auxiliary information (i.e. integrated AAH model) about survival outside the hunting season from known fates data, predicted trends appeared more closely related to what was expected. Disagreements between the AAH model and WIDNR estimates in the East were likely related to biased predictions for reporting and survival rates from the AAH model.

A new method of estimating thermal performance of embryonic development rate yields accurate prediction of embryonic age in wild reptile nests.

PubMed

Rollinson, Njal; Holt, Sarah M; Massey, Melanie D; Holt, Richard C; Nancekivell, E Graham; Brooks, Ronald J

2018-05-01

Temperature has a strong effect on ectotherm development rate. It is therefore possible to construct predictive models of development that rely solely on temperature, which have applications in a range of biological fields. Here, we leverage a reference series of development stages for embryos of the turtle Chelydra serpentina, which was described at a constant temperature of 20 °C. The reference series acts to map each distinct developmental stage onto embryonic age (in days) at 20 °C. By extension, an embryo taken from any given incubation environment, once staged, can be assigned an equivalent age at 20 °C. We call this concept "Equivalent Development", as it maps the development stage of an embryo incubated at a given temperature to its equivalent age at a reference temperature. In the laboratory, we used the concept of Equivalent Development to estimate development rate of embryos of C. serpentina across a series of constant temperatures. Using these estimates of development rate, we created a thermal performance curve measured in units of Equivalent Development (TPC ED ). We then used the TPC ED to predict developmental stage of embryos in several natural turtle nests across six years. We found that 85% of the variation of development stage in natural nests could be explained. Further, we compared the predictive accuracy of the model based on the TPC ED to the predictive accuracy of a degree-day model, where development is assumed to be linearly related to temperature and the amount of accumulated heat is summed over time. Information theory suggested that the model based on the TPC ED better describes variation in developmental stage in wild nests than the degree-day model. We suggest the concept of Equivalent Development has several strengths and can be broadly applied. In particular, studies on temperature-dependent sex determination may be facilitated by the concept of Equivalent Development, as development age maps directly onto the developmental series of the organism, allowing critical periods of sex determination to be delineated without invasive sampling, even under fluctuating temperature. Copyright © 2018 Elsevier Ltd. All rights reserved.

Laboratory measurements and methane photochemistry modeling

NASA Technical Reports Server (NTRS)

Romani, P. N.

1990-01-01

Methane is photolyzed by the solar UV in the stratosphere of Saturn. Subsequent photochemistry leads to the production of acetylene (C2H2) and diacetylene (C4H2). These species are produced where it is relatively warm (T is greater than or equal to 140 K), but the tropopause temperature of Saturn (approximately 80 K) is low enough that these two species may freeze out to their respective ices. Numerical models which include both photochemistry and condensation loss make predictions about the mixing ratios of these species and haze production rates. These models are dependent upon knowing reaction pathways and their associated kinetic reaction rate constants and vapor pressures. How uncertainties in the chemistry and improvements in the vapor pressures affect model predictions for Saturn are discussed.

Kinetics studies of the reactions of main fourth-period monocations (Ga+, Ge+, As+, and Se+) with methyl fluoride.

PubMed

Barrientos, Carmen; Rayón, Víctor Manuel; Largo, Antonio; Sordo, José Ángel; Redondo, Pilar

2013-08-22

Thermodynamics and kinetics theoretical studies on the gas-phase reactions of fluoromethane with main fourth-period monocations (Ga(+), Ge(+), As(+), and Se(+)) have been carried out. Density functional theory (in particular mPW1K functional) was employed in the description of the potential energy surfaces, and refinement of the energies were done at the CCSD(T) level. The reaction rate constants were estimated using variational/conventional microcanonical transition state theory. From a thermodynamic viewpoint, the fluorine abstraction product is predicted for Ga(+) and Ge(+), whereas for As(+) and Se(+) the elimination product, MCH2(+) (M = As, Se) + HF, is the preferred one. Nevertheless, the most favorable channel for the reactions of CH3F with Ga(+) and Se(+) cations present a net activation barrier. In the case of Ga(+), the reaction proceeds via an addition channel forming the adduct complex, CH3FGa(+), whereas for Se(+) no reaction is found, in agreement with the experiments. The predicted reaction rate constants are in reasonable good agreement with the experimental values available. Apart from the harpoon-like mechanism, our results suggest that an oxidative addition mechanism seems to play a relevant role.

Multimedia modeling of engineered nanoparticles with SimpleBox4nano: model definition and evaluation.

PubMed

Meesters, Johannes A J; Koelmans, Albert A; Quik, Joris T K; Hendriks, A Jan; van de Meent, Dik

2014-05-20

Screening level models for environmental assessment of engineered nanoparticles (ENP) are not generally available. Here, we present SimpleBox4Nano (SB4N) as the first model of this type, assess its validity, and evaluate it by comparisons with a known material flow model. SB4N expresses ENP transport and concentrations in and across air, rain, surface waters, soil, and sediment, accounting for nanospecific processes such as aggregation, attachment, and dissolution. The model solves simultaneous mass balance equations (MBE) using simple matrix algebra. The MBEs link all concentrations and transfer processes using first-order rate constants for all processes known to be relevant for ENPs. The first-order rate constants are obtained from the literature. The output of SB4N is mass concentrations of ENPs as free dispersive species, heteroaggregates with natural colloids, and larger natural particles in each compartment in time and at steady state. Known scenario studies for Switzerland were used to demonstrate the impact of the transport processes included in SB4N on the prediction of environmental concentrations. We argue that SB4N-predicted environmental concentrations are useful as background concentrations in environmental risk assessment.

Kinetics of Diffusional Droplet Growth in a Liquid/Liquid Two-Phase System

NASA Technical Reports Server (NTRS)

Glicksman, M. E.; Fradkov, V. E.

1996-01-01

We address the problem of diffusional interactions in a finite sized cluster of spherical particles for volume fractions, V(sub v) in the range 0-0.01. We determined the quasi-static monopole diffusion solution for n particles distributed at random in a continuous matrix. A global mass conservation condition is employed, obviating the need for any external boundary condition. The numerical results provide the instantaneous (snapshot) growth or shrinkage rate of each particle, precluding the need for extensive time-dependent computations. The close connection between these snapshot results and the coarsegrained kinetic constants are discussed. A square-root dependence of the deviations of the rate constants from their zero volume fraction value is found for the higher V(sub v) investigated. This behavior is consistent with predictions from diffusion Debye-Huckel screening theory. By contrast, a cube-root dependence, reported in earlier numerical studies, is found for the lower V(sub v) investigated. The roll-over region of the volume fraction where the two asymptotics merge depends on the number of particles, n, alone. A theoretical estimate for the roll-over point predicts that the corresponding V(sub v) varies as n(sup -2), in good agreement with the numerical results.

A quasi-QSPR modelling for the photocatalytic decolourization rate constants and cellular viability (CV%) of nanoparticles by CORAL.

PubMed

Toropova, A P; Toropov, A A; Benfenati, E

2015-01-01

Most quantitative structure-property/activity relationships (QSPRs/QSARs) predict various endpoints related to organic compounds. Gradually, the variety of organic compounds has been extended to inorganic, organometallic compounds and polymers. However, the so-called molecular descriptors cannot be defined for super-complex substances such as different nanomaterials and peptides, since there is no simple and clear representation of their molecular structure. Some possible ways to define approaches for a predictive model in the case of super-complex substances are discussed. The basic idea of the approach is to change the traditionally used paradigm 'the endpoint is a mathematical function of the molecular structure' with another paradigm 'the endpoint is a mathematical function of available eclectic information'. The eclectic data can be (i) conditions of a synthesis, (ii) technological attributes, (iii) size of nanoparticles, (iv) concentration, (v) attributes related to cell membranes, and so on. Two examples of quasi-QSPR/QSAR analyses are presented and discussed. These are (i) photocatalytic decolourization rate constants (DRC) (10(-5)/s) of different nanopowders; and (ii) the cellular viability under the effect of nano-SiO(2).

Additive effects on the energy barrier for synaptic vesicle fusion cause supralinear effects on the vesicle fusion rate.

PubMed

Schotten, Sebastiaan; Meijer, Marieke; Walter, Alexander Matthias; Huson, Vincent; Mamer, Lauren; Kalogreades, Lawrence; ter Veer, Mirelle; Ruiter, Marvin; Brose, Nils; Rosenmund, Christian; Sørensen, Jakob Balslev; Verhage, Matthijs; Cornelisse, Lennart Niels

2015-04-14

The energy required to fuse synaptic vesicles with the plasma membrane ('activation energy') is considered a major determinant in synaptic efficacy. From reaction rate theory, we predict that a class of modulations exists, which utilize linear modulation of the energy barrier for fusion to achieve supralinear effects on the fusion rate. To test this prediction experimentally, we developed a method to assess the number of releasable vesicles, rate constants for vesicle priming, unpriming, and fusion, and the activation energy for fusion by fitting a vesicle state model to synaptic responses induced by hypertonic solutions. We show that complexinI/II deficiency or phorbol ester stimulation indeed affects responses to hypertonic solution in a supralinear manner. An additive vs multiplicative relationship between activation energy and fusion rate provides a novel explanation for previously observed non-linear effects of genetic/pharmacological perturbations on synaptic transmission and a novel interpretation of the cooperative nature of Ca(2+)-dependent release.

Kinetic modeling of lactic acid production from batch submerged fermentation of cheese whey

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

Tango, M.S.A.; Ghaly, A.E.

1999-12-01

A kinetic model for the production of lactic acid through batch submerged fermentation of cheese whey using Lactobacillus helveticus was developed. The model accounts for the effect of substrate limitation, substrate inhibition, lactic acid inhibition, maintenance energy and cell death on the cell growth, substrate utilization, and lactic acid production during the fermentation process. The model was evaluated using experimental data from Tango and Ghaly (1999). The predicted results obtained from the model compared well with experimental (R{sup 2} = 0.92--0.98). The model was also used to investigate the effect of the initial substrate concentration on the lag period, fermentationmore » time, specific growth rate, and cell productivity during batch fermentation. The maximum specific growth rate ({micro}{sub m}), the saturation constant (K{sub S}), the substrate inhibition constant (K{sub IS}), and the lactic acid inhibition constant (K{sub IP}) were found to be 0.25h{sup {minus}1}, 0.9 g/L, 250.0 g/L, and 60.0 g/L, respectively. High initial lactose concentration in cheese whey reduced both the specific growth rate and substrate utilization rate due to the substrate inhibition phenomenon. The maximum lactic acid production occurred at about 100 g/L initial lactose concentration after 40 h of fermentation. The maximum lactic acid concentration above which Lactobacillus helveticus did not grow was found to be 80.0 g/L.« less

Landfill gas generation after mechanical biological treatment of municipal solid waste. Estimation of gas generation rate constants.

PubMed

Gioannis, G De; Muntoni, A; Cappai, G; Milia, S

2009-03-01

Mechanical biological treatment (MBT) of residual municipal solid waste (RMSW) was investigated with respect to landfill gas generation. Mechanically treated RMSW was sampled at a full-scale plant and aerobically stabilized for 8 and 15 weeks. Anaerobic tests were performed on the aerobically treated waste (MBTW) in order to estimate the gas generation rate constants (k,y(-1)), the potential gas generation capacity (L(o), Nl/kg) and the amount of gasifiable organic carbon. Experimental results show how MBT allowed for a reduction of the non-methanogenic phase and of the landfill gas generation potential by, respectively, 67% and 83% (8 weeks treatment), 82% and 91% (15 weeks treatment), compared to the raw waste. The amount of gasified organic carbon after 8 weeks and 15 weeks of treatment was equal to 11.01+/-1.25kgC/t(MBTW) and 4.54+/-0.87kgC/t(MBTW), respectively, that is 81% and 93% less than the amount gasified from the raw waste. The values of gas generation rate constants obtained for MBTW anaerobic degradation (0.0347-0.0803y(-1)) resemble those usually reported for the slowly and moderately degradable fractions of raw MSW. Simulations performed using a prediction model support the hypothesis that due to the low production rate, gas production from MBTW landfills is well-suited to a passive management strategy.

Reduction of Fe(III) colloids by Shewanella putrefaciens: A kinetic model

NASA Astrophysics Data System (ADS)

Bonneville, Steeve; Behrends, Thilo; van Cappellen, Philippe; Hyacinthe, Christelle; Röling, Wilfred F. M.

2006-12-01

A kinetic model for the microbial reduction of Fe(III) oxyhydroxide colloids in the presence of excess electron donor is presented. The model assumes a two-step mechanism: (1) attachment of Fe(III) colloids to the cell surface and (2) reduction of Fe(III) centers at the surface of attached colloids. The validity of the model is tested using Shewanella putrefaciens and nanohematite as model dissimilatory iron reducing bacteria and Fe(III) colloidal particles, respectively. Attachment of nanohematite to the bacteria is formally described by a Langmuir isotherm. Initial iron reduction rates are shown to correlate linearly with the relative coverage of the cell surface by nanohematite particles, hence supporting a direct electron transfer from membrane-bound reductases to mineral particles attached to the cells. Using internally consistent parameter values for the maximum attachment capacity of Fe(III) colloids to the cells, Mmax, the attachment constant, KP, and the first-order Fe(III) reduction rate constant, k, the model reproduces the initial reduction rates of a variety of fine-grained Fe(III) oxyhydroxides by S. putrefaciens. The model explains the observed dependency of the apparent Fe(III) half-saturation constant, Km∗, on the solid to cell ratio, and it predicts that initial iron reduction rates exhibit saturation with respect to both the cell density and the abundance of the Fe(III) oxyhydroxide substrate.

Stochastic theory of large-scale enzyme-reaction networks: Finite copy number corrections to rate equation models

NASA Astrophysics Data System (ADS)

Thomas, Philipp; Straube, Arthur V.; Grima, Ramon

2010-11-01

Chemical reactions inside cells occur in compartment volumes in the range of atto- to femtoliters. Physiological concentrations realized in such small volumes imply low copy numbers of interacting molecules with the consequence of considerable fluctuations in the concentrations. In contrast, rate equation models are based on the implicit assumption of infinitely large numbers of interacting molecules, or equivalently, that reactions occur in infinite volumes at constant macroscopic concentrations. In this article we compute the finite-volume corrections (or equivalently the finite copy number corrections) to the solutions of the rate equations for chemical reaction networks composed of arbitrarily large numbers of enzyme-catalyzed reactions which are confined inside a small subcellular compartment. This is achieved by applying a mesoscopic version of the quasisteady-state assumption to the exact Fokker-Planck equation associated with the Poisson representation of the chemical master equation. The procedure yields impressively simple and compact expressions for the finite-volume corrections. We prove that the predictions of the rate equations will always underestimate the actual steady-state substrate concentrations for an enzyme-reaction network confined in a small volume. In particular we show that the finite-volume corrections increase with decreasing subcellular volume, decreasing Michaelis-Menten constants, and increasing enzyme saturation. The magnitude of the corrections depends sensitively on the topology of the network. The predictions of the theory are shown to be in excellent agreement with stochastic simulations for two types of networks typically associated with protein methylation and metabolism.

A root-mean-square approach for predicting fatigue crack growth under random loading

NASA Technical Reports Server (NTRS)

Hudson, C. M.

1981-01-01

A method for predicting fatigue crack growth under random loading which employs the concept of Barsom (1976) is presented. In accordance with this method, the loading history for each specimen is analyzed to determine the root-mean-square maximum and minimum stresses, and the predictions are made by assuming the tests have been conducted under constant-amplitude loading at the root-mean-square maximum and minimum levels. The procedure requires a simple computer program and a desk-top computer. For the eleven predictions made, the ratios of the predicted lives to the test lives ranged from 2.13 to 0.82, which is a good result, considering that the normal scatter in the fatigue-crack-growth rates may range from a factor of two to four under identical loading conditions.

Role of Excited Nitrogen In The Ionosphere

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.; Cartwright, D. C.; Bolorizadeh, M. A.

2006-12-01

Sunlight photoionises atoms and molecules in the Earth's upper atmosphere, producing ions and photoelectrons. The photoelectrons then produce further ionisation by electron impact. These processes produce the ionosphere, which contains various positive ions, such as NO+, N+, and O+, and an equal density of free electrons. O+(4S) ions are long-lived and so the electron density is determined mainly by the density of O+(4S). This density is dependent on ambipolar diffusion and on loss processes, which are principally reactions with O2 and N2. The reaction with N2 is known to be strongly dependent on the vibrational state of N2 but the rate constants are not well determined for the ionosphere. Vibrational excitation of N2 is produced by direct excitation by thermal electrons and photoelectrons and by cascade from the excited states of N2 that are produced by photoelectron impact. It can also be produced by a chemical reaction and by vibrational-translational transitions. The vibrational excitation is lost by deexcitation by electron impact, by step-wise quenching in collisions with O atoms, and in the reaction with O+(4S). The distribution of vibrational levels is rearranged by vibrational-vibrational transitions, and by molecular diffusion vertically in the atmosphere. A computational model that includes these processes and predicts the electron density as a function of height in the ionosphere is described. This model is a combination of a "statistical equilibrium" calculation, which is used to predict the populations of the excited states of N2, and a time-step calculation of the atmospheric reactions and processes. The latter includes a calculation of photoionisation down through the atmosphere as a function of time of day and solar activity, and calculations at 0.1 s intervals of the changing densities of positive ions, electrons and N2 in the different vibrational levels. The validity of the model is tested by comparison of the predicted electron densities with the International Reference Ionosphere (IRI) of electron density measurements. The contribution of various input parameters can be investigated by their effect on the accuracy of the calculated electron densities. Here the effects of two different sets of rate constants for the reaction of vibrationally excited N2 with O+(4S) are investigated. For reference, predictions using the different sets are compared with laboratory measurements. Then the effect of using the different sets in the computational model of the ionosphere is investigated. It is shown that one set gives predictions of electron densities that are in reasonable agreement with the IRI, while the other set does not. Both sets result in underestimation of the electron density at the height of the peak electron density in the atmosphere, suggesting that either the amount of vibrational excitation or the rate constants may be overestimated. Our comparison is made for two cases with different conditions, to give an indication of the limitations of the atmospheric modeling and also insight into ways in which the sets of rate constants may be deficient.

Theory of long binding events in single-molecule–controlled rotation experiments on F1-ATPase

PubMed Central

Volkán-Kacsó, Sándor; Marcus, Rudolph A.

2017-01-01

The theory of elastic group transfer for the binding and release rate constants for nucleotides in F1-ATPase as a function of the rotor angle is further extended in several respects. (i) A method is described for predicting the experimentally observed lifetime distribution of long binding events in the controlled rotation experiments by taking into account the hydrolysis and synthesis reactions occurring during these events. (ii) A method is also given for treating the long binding events in the experiments and obtaining the rate constants for the hydrolysis and synthesis reactions occurring during these events. (iii) The theory in the previous paper is given in a symmetric form, an extension that simplifies the application of the theory to experiments. It also includes a theory-based correction of the reported “on” and “off” rates by calculating the missed events. A near symmetry of the data about the angle of −40° and a “turnover” in the binding rate data vs. rotor angle for angles greater than ∼40° is also discussed. PMID:28652332

The Rate of Seasonal Changes in Temperature Alters Acclimation of Performance under Climate Change.

PubMed

Nilsson-Örtman, Viktor; Johansson, Frank

2017-12-01

How the ability to acclimate will impact individual performance and ecological interactions under climate change remains poorly understood. Theory predicts that the benefit an organism can gain from acclimating depends on the rate at which temperatures change relative to the time it takes to induce beneficial acclimation. Here, we present a conceptual model showing how slower seasonal changes under climate change can alter species' relative performance when they differ in acclimation rate and magnitude. To test predictions from theory, we performed a microcosm experiment where we reared a mid- and a high-latitude damselfly species alone or together under the rapid seasonality currently experienced at 62°N and the slower seasonality predicted for this latitude under climate change and measured larval growth and survival. To separate acclimation effects from fixed thermal responses, we simulated growth trajectories based on species' growth rates at constant temperatures and quantified how much and how fast species needed to acclimate to match the observed growth trajectories. Consistent with our predictions, the results showed that the midlatitude species had a greater capacity for acclimation than the high-latitude species. Furthermore, since acclimation occurred at a slower rate than seasonal temperature changes, the midlatitude species had a small growth advantage over the high-latitude species under the current seasonality but a greater growth advantage under the slower seasonality predicted for this latitude under climate change. In addition, the two species did not differ in survival under the current seasonality, but the midlatitude species had higher survival under the predicted climate change scenario, possibly because rates of cannibalism were lower when smaller heterospecifics were present. These findings highlight the need to incorporate acclimation rates in ecological models.

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

NASA Technical Reports Server (NTRS)

Hsu, K.-J.; Demore, W. B.

1994-01-01

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

Determination of a Degradation Constant for CYP3A4 by Direct Suppression of mRNA in a Novel Human Hepatocyte Model, HepatoPac.

PubMed

Ramsden, Diane; Zhou, Jin; Tweedie, Donald J

2015-09-01

Accurate determination of rates of de novo synthesis and degradation of cytochrome P450s (P450s) has been challenging. There is a high degree of variability in the multiple published values of turnover for specific P450s that is likely exacerbated by differences in methodologies. For CYP3A4, reported half-life values range from 10 to 140 hours. An accurate value for kdeg has been identified as a major limitation for prediction of drug interactions involving mechanism-based inhibition and/or induction. Estimation of P450 half-life from in vitro test systems, such as human hepatocytes, is complicated by differential decreased enzyme function over culture time, attenuation of the impact of enzyme loss through inclusion of glucocorticoids in media, and viability limitations over long-term culture times. HepatoPac overcomes some of these challenges by providing extended stability of enzymes (2.5 weeks in our hands). As such it is a unique tool for studying rates of enzyme degradation achieved through modulation of enzyme levels. CYP3A4 mRNA levels were rapidly depleted by >90% using either small interfering RNA or addition of interleukin-6, which allowed an estimation of the degradation rate constant for CYP3A protein over an incubation time of 96 hours. The degradation rate constant of 0.0240 ± 0.005 hour(-1) was reproducible in hepatocytes from five different human donors. These donors also reflected the overall population with respect to CYP3A5 genotype. This methodology can be applied to additional enzymes and may provide a more accurate in vitro derived kdeg value for predicting clinical drug-drug interaction outcomes. Copyright © 2015 by The American Society for Pharmacology and Experimental Therapeutics.

Chemical Kinetics of Hydrogen Atom Abstraction from Allylic Sites by 3O2; Implications for Combustion Modeling and Simulation.

PubMed

Zhou, Chong-Wen; Simmie, John M; Somers, Kieran P; Goldsmith, C Franklin; Curran, Henry J

2017-03-09

Hydrogen atom abstraction from allylic C-H bonds by molecular oxygen plays a very important role in determining the reactivity of fuel molecules having allylic hydrogen atoms. Rate constants for hydrogen atom abstraction by molecular oxygen from molecules with allylic sites have been calculated. A series of molecules with primary, secondary, tertiary, and super secondary allylic hydrogen atoms of alkene, furan, and alkylbenzene families are taken into consideration. Those molecules include propene, 2-butene, isobutene, 2-methylfuran, and toluene containing the primary allylic hydrogen atom; 1-butene, 1-pentene, 2-ethylfuran, ethylbenzene, and n-propylbenzene containing the secondary allylic hydrogen atom; 3-methyl-1-butene, 2-isopropylfuran, and isopropylbenzene containing tertiary allylic hydrogen atom; and 1-4-pentadiene containing super allylic secondary hydrogen atoms. The M06-2X/6-311++G(d,p) level of theory was used to optimize the geometries of all of the reactants, transition states, products and also the hinder rotation treatments for lower frequency modes. The G4 level of theory was used to calculate the electronic single point energies for those species to determine the 0 K barriers to reaction. Conventional transition state theory with Eckart tunnelling corrections was used to calculate the rate constants. The comparison between our calculated rate constants with the available experimental results from the literature shows good agreement for the reactions of propene and isobutene with molecular oxygen. The rate constant for toluene with O 2 is about an order magnitude slower than that experimentally derived from a comprehensive model proposed by Oehlschlaeger and coauthors. The results clearly indicate the need for a more detailed investigation of the combustion kinetics of toluene oxidation and its key pyrolysis and oxidation intermediates. Despite this, our computed barriers and rate constants retain an important internal consistency. Rate constants calculated in this work have also been used in predicting the reactivity of the target fuels of 1-butene, 2-butene, isobutene, 2-methylfuran, 2,5-dimethylfuran, and toluene, and the results show that the ignition delay times for those fuels have been increased by a factor of 1.5-3. This work provides a first systematic study of one of the key initiation reaction for compounds containing allylic hydrogen atoms.

Utilizing Diffusion Theory to predict carbon dioxide concentration in an indoor environment

NASA Astrophysics Data System (ADS)

Kramer, Andrew R.

This research details a new method of relating sources of carbon dioxide to carbon dioxide concentration in a room operating in a reduced ventilation mode by utilizing Diffusion Theory. The theoretical basis of this research involved solving Fick's Second Law of Diffusion in spherical coordinates for a source of carbon dioxide flowing at a constant rate and located in the center of an impermeable spherical boundary. The solution was developed using a Laplace Transformation. A spherical diffusion test chamber was constructed and used to validate and benchmark the developed theory. The method was benchmarked by using Dispersion Coefficients for large carbon dioxide flow rates due to diffusion induced convection. The theoretical model was adapted to model a room operating with restricted ventilation in the presence of a known, constant source of carbon dioxide. The room was modeled as a sphere of volume equal to the room and utilized a Dispersion Coefficient that is consistent with published values. The developed Diffusion Model successfully predicted the spatial concentration of carbon dioxide in a room operating in a reduced ventilation mode in the presence of a source of carbon dioxide. The flow rates of carbon dioxide that were used in the room are comparable to the average flow rate of carbon dioxide from a person during quiet breathing, also known as the Tidal Breathing. This indicates the Diffusion Model developed from this research has the potential to correlate carbon dioxide concentration with static occupancy levels which can lead to energy savings through a reduction in air exchange rates when low occupancy is detected.

The Henry's constant of monochloramine.

PubMed

Garcia, Miguel A; Anderson, Michael A

2018-02-01

Monochloramine is a secondary disinfectant used in drinking water and is also formed in chlorinated wastewater. While known to hydrolyze over time and react with dissolved organic matter, its partitioning between the aqueous and gas phase has not been extensively studied. Preliminary experiments demonstrated that monochloramine concentrations in solutions open to the atmosphere or actively aerated decreased more rapidly than in sealed solutions, indicating significant losses to the atmosphere. For example, a monochloramine solution open to the atmosphere yielded a loss rate constant of 0.08 d -1 , a value twice that for sealed samples without headspace (0.04 d -1 ) where loss occurs exclusively as a result of hydrolysis. A solution aerated at 10 mL s -1 had a loss rate constant nearly 10× greater than that for hydrolysis alone (0.35 d -1 ). To better understand partitioning of monochloramine to the gas phase and potential for volatilization, the dimensionless Henry's law constants of monochloramine (K H ) were determined using an equilibrium headspace technique at five different temperatures (11, 16, 21, 27, and 32 °C). The resulting values ranged from 8 × 10 -3 to 4 × 10 -2 , indicating a semi-volatile compound, and were found to be consistent with quantitative structure activity relationship predictions. At 20 °C, monochloramine exhibits a dimensionless Henry's constant of about 1.7 × 10 -2 which is 35 times greater than ammonia but comparable to the Henry's constant of inorganic semi-volatile compounds such sulfur dioxide. The Henry's constant values for monochloramine suggests that volatilization could be a relevant loss process in open systems such as rivers receiving chlorinated wastewater effluent, swimming pools and cooling towers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Simulated transport and biodegradation of chlorinated ethenes in a fractured dolomite aquifer near Niagara Falls, New York

USGS Publications Warehouse

Yager, Richard M.

2002-01-01

Leakage of trichloroethene (TCE) from a neutralization pond at a former manufacturing facility near Niagara Falls, N.Y. during 1950-87 into the Guelph Formation of the Lockport Group, a fractured dolomite aquifer, created a plume of TCE and its metabolites that, by 1990, extended about 4,300 feet south of the facility. A smaller plume of dense, nonaqueous-phase liquids (DNAPL) probably serves as a continuing source of TCE. The presence of the TCE metabolites cis-1,2-dichloroethene (DCE), vinyl chloride (VC), and ethene in the plume, and the results of previous laboratory microcosm studies, indicate that the TCE is being degraded by naturally occurring microorganisms. Biodegradation rates of TCE and its metabolites were estimated through simulation with BIOMOC, a solute-transport model that represents multispecies reactions through Monod kinetics. A fracture zone in the Guelph Formation was represented as a porous medium containing an extensive, 3-foot thick layer with several interconnected fractures; this layer is bounded above and below by subhorizontal stratigraphic contacts. The Monod reaction constants were estimated through nonlinear regression to minimize the difference between computed concentrations of TCE and its metabolites, and the concentrations measured before and during 5 years of pump-and-treat remediation.Transport simulations indicated that, by April 1998, the chlorinated ethene plume had reached a dynamic equilibrium between the rate of TCE dissolution and the rate of removal through pumping and biodegradation. Biodegradation of chlorinated ethenes at the site can be simulated as first-order reactions because the concentrations are generally less than the half-saturation constants estimated for Monod kinetics (320 mg/L for TCE, 10 mg/L for DCE, and 1 mg/L for VC). Computed degradation rates are proportional to the estimated ground-water velocity, which could vary by more than an order magnitude at the site, as indicated by the estimated range of fracture porosity--3 to 0.3 percent. Half-lives corresponding to first-order rate constants estimated for the lower velocity (5 to 15 feet per day) ranged from 21 to 25 days for TCE, 170 to 230 days for DCE, and 18 to 23 days for VC.Chlorinated ethene concentrations of April 1998 were better reproduced when the TCE source was represented as a constant concentration than as a constant flux, because the latter predicted that the plume would dissipate after 5 years of pump-and-treat remediation. This result indicates that the rate of TCE dissolution is not limited by the mass of TCE in the DNAPL plume. Simulation of diffusion by the transport model MOC3D indicated that concentrations of these contaminants within the rock matrix surrounding the fracture zone were relatively unchanged after 5 years of pump-and-treat remediation. The principal sources of uncertainty in the prediction of biodegradation rates and of the fate of chlorinated ethenes at the site are the fracture porosity and DNAPL mass in the aquifer.

Control of the Protein Turnover Rates in Lemna minor

PubMed Central

Trewavas, A.

1972-01-01

The control of protein turnover in Lemna minor has been examined using a method described in the previous paper for determining the rate constants of synthesis and degradation of protein. If Lemna is placed on water, there is a reduction in the rate constants of synthesis of protein and an increase (3- to 6-fold) in the rate constant of degradation. The net effect is a loss of protein from the tissue. Omission of nitrate, phosphate, sulfate, magnesium, or calcium results in increases in the rate constant of degradation of protein. An unusual dual effect of benzyladenine on the turnover constants has been observed. Treatment of Lemna grown on sucrose-mineral salts with benzyladenine results in alterations only in the rate constant of synthesis. Treatment of Lemna grown on water with benzyladenine alters only the rate constant of degradation. Abscisic acid on the other hand alters both rate constants of synthesis and degradation of protein together. Inclusion of growth-inhibiting amino acids in the medium results in a reduction in the rate constants of synthesis and increases in the rate constant of degradation of protein. It is concluded that the rate of turnover of protein in Lemna is very dependent on the composition of the growth medium. Conditions which reduce growth rates also reduce the rates of synthesis of protein and increase those of degradation. PMID:16657895

Use of polynomial expressions to describe the bioconcentration of hydrophobic chemicals by fish

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

Connell, D.W.; Hawker, D.W.

1988-12-01

For the bioconcentration of hydrophobic chemicals by fish, relationships have been previously established between uptake rate constants (k1) and the octanol/water partition coefficient (Kow), and also between the clearance rate constant (k2) and Kow. These have been refined and extended on the basis of data for chlorinated hydrocarbons, and closely related compounds including polychlorinated dibenzodioxins, that covered a wider range of hydrophobicity (2.5 less than log Kow less than 9.5). This has allowed the development of new relationships between log Kow and various factors, including the bioconcentration factor (as log KB), equilibrium time (as log teq), and maximum biotic concentrationmore » (as log CB), which include extremely hydrophobic compounds previously not taken into account. The shape of the curves generated by these equations are in qualitative agreement with theoretical prediction and are described by polynomial expressions which are generally approximately linear over the more limited range of log Kow values used to develop previous relationships. The influences of factors such as hydrophobicity, aqueous solubility, molecular weight, lipid solubility, and also exposure time were considered. Decreasing lipid solubilities of extremely hydrophobic chemicals were found to result in increasing clearance rate constants, as well decreasing equilibrium times and bioconcentration factors.« less

Thermal degradation kinetics of anthocyanins from blood orange, blackberry, and roselle using the arrhenius, eyring, and ball models.

PubMed

Cisse, Mady; Vaillant, Fabrice; Acosta, Oscar; Dhuique-Mayer, Claudie; Dornier, Manuel

2009-07-22

Anthocyanin stability was assessed over temperatures ranging from 30 to 90 degrees C for seven products: blood orange juice [Citrus sinensis (L.) Osbeck]; two tropical highland blackberry juices (Rubus adenotrichus Schlech.), one with high content and the other with low content of suspended insoluble solids (SIS); and four roselle extracts (Hibiscus sabdariffa L.). The blackberry juice showed the highest content of anthocyanins with 1.2 g/L (two times less in the roselle extracts and 12 times less in the blood orange juice). The rate constant for anthocyanin degradation and isothermal kinetic parameters were calculated according to three models: Arrhenius, Eyring, and Ball. Anthocyanins in blood orange juice presented the highest rate constant for degradation, followed by the blackberry juices and roselle extracts. Values of activation energies were 66 and 37 kJ/mol, respectively, for blood orange and blackberry and 47-61 kJ/mol for roselle extracts. For the blackberry juices, a high SIS content provided only slight protection for the anthocyanins. The increasing content of dissolved oxygen, from 0.5 to 8.5 g/L, did not significantly increase the rate constant. For both isothermal and nonisothermal treatments, all three models accurately predicted anthocyanin losses from different food matrices.

Estimation of rate constants of PCB dechlorination reactions using an anaerobic dehalogenation model.

PubMed

Karakas, Filiz; Imamoglu, Ipek

2017-02-15

This study aims to estimate anaerobic dechlorination rate constants (k m ) of reactions of individual PCB congeners using data from four laboratory microcosms set up using sediment from Baltimore Harbor. Pathway k m values are estimated by modifying a previously developed model as Anaerobic Dehalogenation Model (ADM) which can be applied to any halogenated hydrophobic organic (HOC). Improvements such as handling multiple dechlorination activities (DAs) and co-elution of congeners, incorporating constraints, using new goodness of fit evaluation led to an increase in accuracy, speed and flexibility of ADM. DAs published in the literature in terms of chlorine substitutions as well as specific microorganisms and their combinations are used for identification of pathways. The best fit explaining the congener pattern changes was found for pathways of Phylotype DEH10, which has the ability to remove doubly flanked chlorines in meta and para positions, para flanked chlorines in meta position. The range of estimated k m values is between 0.0001-0.133d -1 , the median of which is found to be comparable to the few available published biologically confirmed rate constants. Compound specific modelling studies such as that performed by ADM can enable monitoring and prediction of concentration changes as well as toxicity during bioremediation. Copyright © 2016 Elsevier B.V. All rights reserved.

Enzymatic mechanisms of biological magnetic sensitivity.

PubMed

Letuta, Ulyana G; Berdinskiy, Vitaly L; Udagawa, Chikako; Tanimoto, Yoshifumi

2017-10-01

Primary biological magnetoreceptors in living organisms is one of the main research problems in magnetobiology. Intracellular enzymatic reactions accompanied by electron transfer have been shown to be receptors of magnetic fields, and spin-dependent ion-radical processes can be a universal mechanism of biological magnetosensitivity. Magnetic interactions in intermediate ion-radical pairs, such as Zeeman and hyperfine (HFI) interactions, in accordance with proposed strict quantum mechanical theory, can determine magnetic-field dependencies of reactions that produce biologically important molecules needed for cell growth. Hyperfine interactions of electrons with nuclear magnetic moments of magnetic isotopes can explain the most important part of biomagnetic sensitivities in a weak magnetic field comparable to the Earth's magnetic field. The theoretical results mean that magnetic-field dependencies of enzymatic reaction rates in a weak magnetic field that can be independent of HFI constant a, if H < a, and are determined by the rate constant of chemical transformations in the enzyme active site. Both Zeeman and HFI interactions predict strong magnetic-field dependence in weak magnetic fields and magnetic-field independence of enzymatic reaction rate constants in strong magnetic fields. The theoretical results can explain the magnetic sensitivity of E. coli cell and demonstrate that intracellular enzymatic reactions are primary magnetoreceptors in living organisms. Bioelectromagnetics. 38:511-521, 2017. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Finite-Temperature Behavior of PdH x Elastic Constants Computed by Direct Molecular Dynamics

DOE PAGES

Zhou, X. W.; Heo, T. W.; Wood, B. C.; ...

2017-05-30

In this paper, robust time-averaged molecular dynamics has been developed to calculate finite-temperature elastic constants of a single crystal. We find that when the averaging time exceeds a certain threshold, the statistical errors in the calculated elastic constants become very small. We applied this method to compare the elastic constants of Pd and PdH 0.6 at representative low (10 K) and high (500 K) temperatures. The values predicted for Pd match reasonably well with ultrasonic experimental data at both temperatures. In contrast, the predicted elastic constants for PdH 0.6 only match well with ultrasonic data at 10 K; whereas, atmore » 500 K, the predicted values are significantly lower. We hypothesize that at 500 K, the facile hydrogen diffusion in PdH 0.6 alters the speed of sound, resulting in significantly reduced values of predicted elastic constants as compared to the ultrasonic experimental data. Finally, literature mechanical testing experiments seem to support this hypothesis.« less

Modelling and analysis of creep deformation and fracture in a 1 Cr 1/2 Mo ferritic steel

NASA Astrophysics Data System (ADS)

Dyson, B. F.; Osgerby, D.

A quantitative model, based upon a proposed new mechanism of creep deformation in particle-hardened alloys, has been validated by analysis of creep data from a 13CrMo 4 4 (1Cr 1/2 Mo) material tested under a range of stresses and temperatures. The methodology that has been used to extract the model parameters quantifies, as a first approximation, only the main degradation (damage) processes - in the case of the 1CR 1/2 Mo steel, these are considered to be the parallel operation of particle-coarsening and a progressively increasing stress due to a constant-load boundary condition. These 'global' model parameters can then be modified (only slightly) as required to obtain a detailed description and 'fit' to the rupture lifetime and strain/time trajectory of any individual test. The global model parameter approach may be thought of as predicting average behavior and the detailed fits as taking account of uncertainties (scatter) due to variability in the material. Using the global parameter dataset, predictions have also been made of behavior under biaxial stressing; constant straining rate; constant total strain (stress relaxation) and the likely success or otherwise of metallographic and mechanical remanent lifetime procedures.

Accuracy of 1D microvascular flow models in the limit of low Reynolds numbers.

PubMed

Pindera, Maciej Z; Ding, Hui; Athavale, Mahesh M; Chen, Zhijian

2009-05-01

We describe results of numerical simulations of steady flows in tubes with branch bifurcations using fully 3D and reduced 1D geometries. The intent is to delineate the range of validity of reduced models used for simulations of flows in microcapillary networks, as a function of the flow Reynolds number Re. Results from model problems indicate that for Re less than 1 and possibly as high as 10, vasculatures may be represented by strictly 1D Poiseuille flow geometries with flow variation in the axial dimensions only. In that range flow rate predictions in the different branches generated by 1D and 3D models differ by a constant factor, independent of Re. When the cross-sectional areas of the branches are constant these differences are generally small and appear to stem from an uncertainty of how the individual branch lengths are defined. This uncertainty can be accounted for by a simple geometrical correction. For non-constant cross-sections the differences can be much more significant. If additional corrections for the presence of branch junctions and flow area variations are not taken into account in 1D models of complex vasculatures, the resultant flow predictions should be interpreted with caution.

Hydrothermal atomic force microscopy observations of barite step growth rates as a function of the aqueous barium-to-sulfate ratio

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

Bracco, Jacquelyn N.; Gooijer, Yiscka; Higgins, Steven R.

The rate of growth of ionic minerals from solutions with varying aqueous cation:anion ratios may result in significant errors in mineralization rates predicted by commonly-used affinity-based rate equations. To assess the potential influence of solute stoichiometry on barite growth, step velocities on the barite (001) surface have been measured at 108 °C using hydrothermal atomic force microscopy (HAFM) at moderate supersaturation and as a function of the aqueous barium:sulfate ratio (r). Barite growth hillocks at r ~ 1 were bounded bymore » $$\\langle$$120$$\\rangle$$ steps, however at r < 1, kink site densities increased, steps followed a direction vicinal to $$\\langle$$120$$\\rangle$$, and the [010] steps developed. At r > 1, steps roughened and rounded as the kink site density increased. Step velocities peaked at r = 1 and decreased roughly symmetrically as a function of r, indicating the attachment rates of barium and sulfate ions are similar under these conditions. We hypothesize that the differences in our observations at high and low r arise from differences in the attachment rate constants for the obtuse and acute $$\\langle$$120$$\\rangle$$ steps. Based on results at low r, the data suggests the attachment rate constant for barium ions is similar for obtuse and acute steps. Based on results at high r, the data suggests the attachment rate constant for sulfate is greater for obtuse steps than acute steps. In conclusion, utilizing a step growth model developed by Stack and Grantham (2010) the experimental step velocities as a function of r were readily fit while attempts to fit the data using a model developed by Zhang and Nancollas (1998) were less successful.« less

Hydrothermal atomic force microscopy observations of barite step growth rates as a function of the aqueous barium-to-sulfate ratio

DOE PAGES

Bracco, Jacquelyn N.; Gooijer, Yiscka; Higgins, Steven R.

2016-03-19

The rate of growth of ionic minerals from solutions with varying aqueous cation:anion ratios may result in significant errors in mineralization rates predicted by commonly-used affinity-based rate equations. To assess the potential influence of solute stoichiometry on barite growth, step velocities on the barite (001) surface have been measured at 108 °C using hydrothermal atomic force microscopy (HAFM) at moderate supersaturation and as a function of the aqueous barium:sulfate ratio (r). Barite growth hillocks at r ~ 1 were bounded bymore » $$\\langle$$120$$\\rangle$$ steps, however at r < 1, kink site densities increased, steps followed a direction vicinal to $$\\langle$$120$$\\rangle$$, and the [010] steps developed. At r > 1, steps roughened and rounded as the kink site density increased. Step velocities peaked at r = 1 and decreased roughly symmetrically as a function of r, indicating the attachment rates of barium and sulfate ions are similar under these conditions. We hypothesize that the differences in our observations at high and low r arise from differences in the attachment rate constants for the obtuse and acute $$\\langle$$120$$\\rangle$$ steps. Based on results at low r, the data suggests the attachment rate constant for barium ions is similar for obtuse and acute steps. Based on results at high r, the data suggests the attachment rate constant for sulfate is greater for obtuse steps than acute steps. In conclusion, utilizing a step growth model developed by Stack and Grantham (2010) the experimental step velocities as a function of r were readily fit while attempts to fit the data using a model developed by Zhang and Nancollas (1998) were less successful.« less

Temperature-Dependent Kinetic Model for Nitrogen-Limited Wine Fermentations▿

PubMed Central

Coleman, Matthew C.; Fish, Russell; Block, David E.

2007-01-01

A physical and mathematical model for wine fermentation kinetics was adapted to include the influence of temperature, perhaps the most critical factor influencing fermentation kinetics. The model was based on flask-scale white wine fermentations at different temperatures (11 to 35°C) and different initial concentrations of sugar (265 to 300 g/liter) and nitrogen (70 to 350 mg N/liter). The results show that fermentation temperature and inadequate levels of nitrogen will cause stuck or sluggish fermentations. Model parameters representing cell growth rate, sugar utilization rate, and the inactivation rate of cells in the presence of ethanol are highly temperature dependent. All other variables (yield coefficient of cell mass to utilized nitrogen, yield coefficient of ethanol to utilized sugar, Monod constant for nitrogen-limited growth, and Michaelis-Menten-type constant for sugar transport) were determined to vary insignificantly with temperature. The resulting mathematical model accurately predicts the observed wine fermentation kinetics with respect to different temperatures and different initial conditions, including data from fermentations not used for model development. This is the first wine fermentation model that accurately predicts a transition from sluggish to normal to stuck fermentations as temperature increases from 11 to 35°C. Furthermore, this comprehensive model provides insight into combined effects of time, temperature, and ethanol concentration on yeast (Saccharomyces cerevisiae) activity and physiology. PMID:17616615

Comparing 2-nt 3' overhangs against blunt-ended siRNAs: a systems biology based study.

PubMed

Ghosh, Preetam; Dullea, Robert; Fischer, James E; Turi, Tom G; Sarver, Ronald W; Zhang, Chaoyang; Basu, Kalyan; Das, Sajal K; Poland, Bradley W

2009-07-07

In this study, we formulate a computational reaction model following a chemical kinetic theory approach to predict the binding rate constant for the siRNA-RISC complex formation reaction. The model allowed us to study the potency difference between 2-nt 3' overhangs against blunt-ended siRNA molecules in an RNA interference (RNAi) system. The rate constant predicted by this model was fed into a stochastic simulation of the RNAi system (using the Gillespie stochastic simulator) to study the overall potency effect. We observed that the stochasticity in the transcription/translation machinery has no observable effects in the RNAi pathway. Sustained gene silencing using siRNAs can be achieved only if there is a way to replenish the dsRNA molecules in the cell. Initial findings show about 1.5 times more blunt-ended molecules will be required to keep the mRNA at the same reduced level compared to the 2-nt overhang siRNAs. However, the mRNA levels jump back to saturation after a longer time when blunt-ended siRNAs are used. We found that the siRNA-RISC complex formation reaction rate was 2 times slower when blunt-ended molecules were used pointing to the fact that the presence of the 2-nt overhangs has a greater effect on the reaction in which the bound RISC complex cleaves the mRNA.

Comparing 2-nt 3' overhangs against blunt-ended siRNAs: a systems biology based study

PubMed Central

Ghosh, Preetam; Dullea, Robert; Fischer, James E; Turi, Tom G; Sarver, Ronald W; Zhang, Chaoyang; Basu, Kalyan; Das, Sajal K; Poland, Bradley W

2009-01-01

In this study, we formulate a computational reaction model following a chemical kinetic theory approach to predict the binding rate constant for the siRNA-RISC complex formation reaction. The model allowed us to study the potency difference between 2-nt 3' overhangs against blunt-ended siRNA molecules in an RNA interference (RNAi) system. The rate constant predicted by this model was fed into a stochastic simulation of the RNAi system (using the Gillespie stochastic simulator) to study the overall potency effect. We observed that the stochasticity in the transcription/translation machinery has no observable effects in the RNAi pathway. Sustained gene silencing using siRNAs can be achieved only if there is a way to replenish the dsRNA molecules in the cell. Initial findings show about 1.5 times more blunt-ended molecules will be required to keep the mRNA at the same reduced level compared to the 2-nt overhang siRNAs. However, the mRNA levels jump back to saturation after a longer time when blunt-ended siRNAs are used. We found that the siRNA-RISC complex formation reaction rate was 2 times slower when blunt-ended molecules were used pointing to the fact that the presence of the 2-nt overhangs has a greater effect on the reaction in which the bound RISC complex cleaves the mRNA. PMID:19594876

A screening model to predict microalgae biomass growth in photobioreactors and raceway ponds.

PubMed

Huesemann, M H; Van Wagenen, J; Miller, T; Chavis, A; Hobbs, S; Crowe, B

2013-06-01

A microalgae biomass growth model was developed for screening novel strains for their potential to exhibit high biomass productivities under nutrient-replete conditions in photobioreactors or outdoor ponds. Growth is modeled by first estimating the light attenuation by biomass according to Beer-Lambert's Law, and then calculating the specific growth rate in discretized culture volume slices that receive declining light intensities due to attenuation. The model uses only two physical and two species-specific biological input parameters, all of which are relatively easy to determine: incident light intensity, culture depth, as well as the biomass light absorption coefficient and the specific growth rate as a function of light intensity. Roux bottle culture experiments were performed with Nannochloropsis salina at constant temperature (23°C) at six different incident light intensities (10, 25, 50, 100, 250, and 850 µmol/m(2)  s) to determine both the specific growth rate under non-shading conditions and the biomass light absorption coefficient as a function of light intensity. The model was successful in predicting the biomass growth rate in these Roux bottle batch cultures during the light-limited linear phase at different incident light intensities. Model predictions were moderately sensitive to minor variations in the values of input parameters. The model was also successful in predicting the growth performance of Chlorella sp. cultured in LED-lighted 800 L raceway ponds operated in batch mode at constant temperature (30°C) and constant light intensity (1,650 µmol/m(2)  s). Measurements of oxygen concentrations as a function of time demonstrated that following exposure to darkness, it takes at least 5 s for cells to initiate dark respiration. As a result, biomass loss due to dark respiration in the aphotic zone of a culture is unlikely to occur in highly mixed small-scale photobioreactors where cells move rapidly in and out of the light. By contrast, as supported also by the growth model, biomass loss due to dark respiration occurs in the dark zones of the relatively less well-mixed pond cultures. In addition to screening novel microalgae strains for high biomass productivities, the model can also be used for optimizing the pond design and operation. Additional research is needed to validate the biomass growth model for other microalgae species and for the more realistic case of fluctuating temperatures and light intensities observed in outdoor pond cultures. Copyright © 2012 Wiley Periodicals, Inc.

Accumulation of 2,3,7,8-tetrachlorodibenzo-p-dioxin by rainbow trout (Onchorhynchus mykiss) at environmentally relevant dietary concentrations

USGS Publications Warehouse

Jones, Paul D.; Kannan, Kurunthachalam; Newsted, John L.; Tillitt, Donald E.; Williams, Lisa L.; Giesy, John P.

2001-01-01

Rainbow trout were fed a diet containing 1.8, 18, or 90 pg/g 3H-2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) for up to 320 d. Concentrations of TCDD were determined in muscle, liver, and ovaries at 100, 150, 200, and 250 d. Concentrations of TCDD reached an apparent steady-state concentration in liver after 100 d of exposure, whereas concentrations in other tissues continued to increase until 150 d of exposure. The greatest portion of the total mass of TCDD was present in the muscle tissue with lesser proportions in other organs. As the ovaries developed before spawning, an increase occurred in the total mass of TCDD present in this tissue. The assimilation rate of TCDD during the initial 100 d of the exposure was determined to be between 10 and 30%. This is somewhat less than estimates derived based on both uptake and elimination constants determined during shorter exposures. Biomagnification factors (BMFs) were estimated for all tissues and exposure concentrations, and at all exposure periods. Lipid-normalized BMFs for muscle ranged from 0.38 to 1.51, which is consistent with the value of 1.0 predicted from fugacity theory. Uptake and depuration rate constants were determined and used to predict individual organ TCDD concentrations. Comparison with observed values indicated that the model could be used to predict tissue concentrations from the known concentrations of TCDD in food. This model will allow more refined risk assessments by predicting TCDD concentrations in sensitive tissues such as developing eggs.

Theoretical study of chain transfer to solvent reactions of alkyl acrylates.

PubMed

Moghadam, Nazanin; Srinivasan, Sriraj; Grady, Michael C; Rappe, Andrew M; Soroush, Masoud

2014-07-24

This computational and theoretical study deals with chain transfer to solvent (CTS) reactions of methyl acrylate (MA), ethyl acrylate (EA), and n-butyl acrylate (n-BA) self-initiated homopolymerization in solvents such as butanol (polar, protic), methyl ethyl ketone (MEK) (polar, aprotic), and p-xylene (nonpolar). The results indicate that abstraction of a hydrogen atom from the methylene group next to the oxygen atom in n-butanol, from the methylene group in MEK, and from a methyl group in p-xylene by a live polymer chain are the most likely mechanisms of CTS reactions in MA, EA, and n-BA. Energy barriers and molecular geometries of reactants, products, and transition states are predicted. The sensitivity of the predictions to three hybrid functionals (B3LYP, X3LYP, and M06-2X) and three different basis sets (6-31G(d,p), 6-311G(d), and 6-311G(d,p)) is investigated. Among n-butanol, sec-butanol, and tert-butanol, tert-butanol has the highest CTS energy barrier and the lowest rate constant. Although the application of the conductor-like screening model (COSMO) does not affect the predicted CTS kinetic parameter values, the application of the polarizable continuum model (PCM) results in higher CTS energy barriers. This increase in the predicted CTS energy barriers is larger for butanol and MEK than for p-xylene. The higher rate constants of chain transfer to n-butanol reactions compared to those of chain transfer to MEK and p-xylene reactions suggest the higher CTS reactivity of n-butanol.

Population Dynamics of a Salmonella Lytic Phage and Its Host: Implications of the Host Bacterial Growth Rate in Modelling

PubMed Central

Santos, Sílvio B.; Carvalho, Carla; Azeredo, Joana; Ferreira, Eugénio C.

2014-01-01

The prevalence and impact of bacteriophages in the ecology of bacterial communities coupled with their ability to control pathogens turn essential to understand and predict the dynamics between phage and bacteria populations. To achieve this knowledge it is essential to develop mathematical models able to explain and simulate the population dynamics of phage and bacteria. We have developed an unstructured mathematical model using delay-differential equations to predict the interactions between a broad-host-range Salmonella phage and its pathogenic host. The model takes into consideration the main biological parameters that rule phage-bacteria interactions likewise the adsorption rate, latent period, burst size, bacterial growth rate, and substrate uptake rate, among others. The experimental validation of the model was performed with data from phage-interaction studies in a 5 L bioreactor. The key and innovative aspect of the model was the introduction of variations in the latent period and adsorption rate values that are considered as constants in previous developed models. By modelling the latent period as a normal distribution of values and the adsorption rate as a function of the bacterial growth rate it was possible to accurately predict the behaviour of the phage-bacteria population. The model was shown to predict simulated data with a good agreement with the experimental observations and explains how a lytic phage and its host bacteria are able to coexist. PMID:25051248

Pharmacokinetics of topically applied pilocarpine in the albino rabbit eye.

PubMed

Makoid, M C; Robinson, J R

1979-04-01

The temporal and spatial pattern of [3H]-pilocarpine nitrate distribution in the albino rabbit eye following topical administration was determined. A four-compartment caternary chain model describing this disposition corresponds to the precorneal area, the cornea, the aqueous humor, and the lens and vitreous. Simultaneous computer fitting of data from tissue corresponding to some compartments in the model supported the proposed model. Additional support was provided by the excellent correlation between predicted and observed values in multiple-dosing studies. Several important aspects of ocular drug disposition are evident from the model. The extensive parallel elimination at the absorption site gives rise to an apparent absorption rate constant that is one to two orders of magnitude larger than the true absorption rate constant. In addition, aqueous flow accounts for most of the drug removal. Thus, major effects on absorption and elimination, independent of the drug structure, suggest the possibility of similar pharmacokinetics for vastly different drugs.

A novel modeling approach to the mixing process in twin-screw extruders

NASA Astrophysics Data System (ADS)

Kennedy, Amedu Osaighe; Penlington, Roger; Busawon, Krishna; Morgan, Andy

2014-05-01

In this paper, a theoretical model for the mixing process in a self-wiping co-rotating twin screw extruder by combination of statistical techniques and mechanistic modelling has been proposed. The approach was to examine the mixing process in the local zones via residence time distribution and the flow dynamics, from which predictive models of the mean residence time and mean time delay were determined. Increase in feed rate at constant screw speed was found to narrow the shape of the residence time distribution curve, reduction in the mean residence time and time delay and increase in the degree of fill. Increase in screw speed at constant feed rate was found to narrow the shape of the residence time distribution curve, decrease in the degree of fill in the extruder and thus an increase in the time delay. Experimental investigation was also done to validate the modeling approach.

Critique of Macro Flow/Damage Surface Representations for Metal Matrix Composites Using Micromechanics

NASA Technical Reports Server (NTRS)

Lissenden, Cliff J.; Arnold, Steven M.

1996-01-01

Guidance for the formulation of robust, multiaxial, constitutive models for advanced materials is provided by addressing theoretical and experimental issues using micromechanics. The multiaxial response of metal matrix composites, depicted in terms of macro flow/damage surfaces, is predicted at room and elevated temperatures using an analytical micromechanical model that includes viscoplastic matrix response as well as fiber-matrix debonding. Macro flow/damage surfaces (i.e., debonding envelopes, matrix threshold surfaces, macro 'yield' surfaces, surfaces of constant inelastic strain rate, and surfaces of constant dissipation rate) are determined for silicon carbide/titanium in three stress spaces. Residual stresses are shown to offset the centers of the flow/damage surfaces from the origin and their shape is significantly altered by debonding. The results indicate which type of flow/damage surfaces should be characterized and what loadings applied to provide the most meaningful experimental data for guiding theoretical model development and verification.

Prediction of fire growth on furniture using CFD

NASA Astrophysics Data System (ADS)

Pehrson, Richard David

A fire growth calculation method has been developed that couples a computational fluid dynamics (CFD) model with bench scale cone calorimeter test data for predicting the rate of flame spread on compartment contents such as furniture. The commercial CFD code TASCflow has been applied to solve time averaged conservation equations using an algebraic multigrid solver with mass weighted skewed upstream differencing for advection. Closure models include k-e for turbulence, eddy breakup for combustion following a single step irreversible reaction with Arrhenius rate constant, finite difference radiation transfer, and conjugate heat transfer. Radiation properties are determined from concentrations of soot, CO2 and H2O using the narrow band model of Grosshandler and exponential wide band curve fit model of Modak. The growth in pyrolyzing area is predicted by treating flame spread as a series of piloted ignitions based on coupled gas-fluid boundary conditions. The mass loss rate from a given surface element follows the bench scale test data for input to the combustion prediction. The fire growth model has been tested against foam-fabric mattresses and chairs burned in the furniture calorimeter. In general, agreement between model and experiment for peak heat release rate (HRR), time to peak HRR, and total energy lost is within +/-20%. Used as a proxy for the flame spread velocity, the slope of the HRR curve predicted by model agreed with experiment within +/-20% for all but one case.

Process viscometry in flows of non-Newtonian fluids using an anchor agitator

NASA Astrophysics Data System (ADS)

Jo, Hae Jin; Jang, Hye Kyeong; Kim, Young Ju; Hwang, Wook Ryol

2017-11-01

In this work, we present a viscosity measurement technique for inelastic non-Newtonian fluids directly in flows of anchor agitators that are commonly used in highly viscous fluid mixing particularly with yield stress. A two-blade anchor impeller is chosen as a model flow system and Carbopol 940 solutions and Xanthan gum solutions with various concentrations are investigated as test materials. Following the Metzner-Otto correlation, the effective shear rate constant and the energy dissipation rate constant have been estimated experimentally by establishing (i) the relationship between the power number and the Reynolds number using a reference Newtonian fluid and (ii) the proportionality between the effective shear rate and the impeller speed with a reference non-Newtonian fluid. The effective viscosity that reproduces the same amount of the energy dissipation rate, corresponding to that of Newtonian fluid, has been obtained by measuring torques for various impeller speeds and the accuracy in the viscosity prediction as a function of the shear rate has been compared with the rheological measurement. We report that the process viscometry with the anchor impeller yields viscosity estimation within the relative error of 20% with highly shear-thinning fluids.

Isometric Arm Strength and Subjective Rating of Upper Limb Fatigue in Two-Handed Carrying Tasks

PubMed Central

Li, Kai Way; Chiu, Wen-Sheng

2015-01-01

Sustained carrying could result in muscular fatigue of the upper limb. Ten male and ten female subjects were recruited for measurements of isometric arm strength before and during carrying a load for a period of 4 minutes. Two levels of load of carrying were tested for each of the male and female subjects. Exponential function based predictive equations for the isometric arm strength were established. The mean absolute deviations of these models in predicting the isometric arm strength were in the range of 3.24 to 17.34 N. Regression analyses between the subjective ratings of upper limb fatigue and force change index (FCI) for the carrying were also performed. The results indicated that the subjective rating of muscular fatigue may be estimated by multiplying the FCI with a constant. The FCI may, therefore, be adopted as an index to assess muscular fatigue for two-handed carrying tasks. PMID:25794159

Isometric arm strength and subjective rating of upper limb fatigue in two-handed carrying tasks.

PubMed

Li, Kai Way; Chiu, Wen-Sheng

2015-01-01

Sustained carrying could result in muscular fatigue of the upper limb. Ten male and ten female subjects were recruited for measurements of isometric arm strength before and during carrying a load for a period of 4 minutes. Two levels of load of carrying were tested for each of the male and female subjects. Exponential function based predictive equations for the isometric arm strength were established. The mean absolute deviations of these models in predicting the isometric arm strength were in the range of 3.24 to 17.34 N. Regression analyses between the subjective ratings of upper limb fatigue and force change index (FCI) for the carrying were also performed. The results indicated that the subjective rating of muscular fatigue may be estimated by multiplying the FCI with a constant. The FCI may, therefore, be adopted as an index to assess muscular fatigue for two-handed carrying tasks.

Host shifts and evolutionary radiations of butterflies

PubMed Central

Fordyce, James A.

2010-01-01

Ehrlich and Raven proposed a model of coevolution where major host plant shifts of butterflies facilitate a burst of diversification driven by their arrival to a new adaptive zone. One prediction of this model is that reconstructions of historical diversification of butterflies should indicate an increase in diversification rate following major host shifts. Using reconstructed histories of 15 butterfly groups, I tested this prediction and found general agreement with Ehrlich and Raven's model. Butterfly lineages with an inferred major historical host shift showed evidence of diversification rate variation, with a significant acceleration following the host shift. Lineages without an inferred major host shift generally agreed with a constant-rate model of diversification. These results are consistent with the view that host plant associations have played a profound role in the evolutionary history of butterflies, and show that major shifts to chemically distinct plant groups leave a historical footprint that remains detectable today. PMID:20610430

Rapid sea level rise in the aftermath of a Neoproterozoic snowball Earth

NASA Astrophysics Data System (ADS)

Myrow, P. M.; Lamb, M. P.; Ewing, R. C.

2018-05-01

Earth’s most severe climate changes occurred during global-scale “snowball Earth” glaciations, which profoundly altered the planet’s atmosphere, oceans, and biosphere. Extreme rates of glacioeustatic sea level rise are predicted by the snowball Earth hypothesis, but supporting geologic evidence has been lacking. We use paleohydraulic analysis of wave ripples and tidal laminae in the Elatina Formation, Australia—deposited after the Marinoan glaciation ~635 million years ago—to show that water depths of 9 to 16 meters remained nearly constant for ~100 years throughout 27 meters of sediment accumulation. This accumulation rate was too great to have been accommodated by subsidence and instead indicates an extraordinarily rapid rate of sea level rise (0.2 to 0.27 meters per year). Our results substantiate a fundamental prediction of snowball Earth models of rapid deglaciation during the early transition to a supergreenhouse climate.

Constitutive law for seismicity rate based on rate and state friction: Dieterich 1994 revisited.

NASA Astrophysics Data System (ADS)

Heimisson, E. R.; Segall, P.

2017-12-01

Dieterich [1994] derived a constitutive law for seismicity rate based on rate and state friction, which has been applied widely to aftershocks, earthquake triggering, and induced seismicity in various geological settings. Here, this influential work is revisited, and re-derived in a more straightforward manner. By virtue of this new derivation the model is generalized to include changes in effective normal stress associated with background seismicity. Furthermore, the general case when seismicity rate is not constant under constant stressing rate is formulated. The new derivation provides directly practical integral expressions for the cumulative number of events and rate of seismicity for arbitrary stressing history. Arguably, the most prominent limitation of Dieterich's 1994 theory is the assumption that seismic sources do not interact. Here we derive a constitutive relationship that considers source interactions between sub-volumes of the crust, where the stress in each sub-volume is assumed constant. Interactions are considered both under constant stressing rate conditions and for arbitrary stressing history. This theory can be used to model seismicity rate due to stress changes or to estimate stress changes using observed seismicity from triggered earthquake swarms where earthquake interactions and magnitudes are take into account. We identify special conditions under which influence of interactions cancel and the predictions reduces to those of Dieterich 1994. This remarkable result may explain the apparent success of the model when applied to observations of triggered seismicity. This approach has application to understanding and modeling induced and triggered seismicity, and the quantitative interpretation of geodetic and seismic data. It enables simultaneous modeling of geodetic and seismic data in a self-consistent framework. To date physics-based modeling of seismicity with or without geodetic data has been found to give insight into various processes related to aftershocks, VT and injection-induced seismicity. However, the role of various processes such as earthquake interactions and magnitudes and effective normal stress has been unclear. The new theory presented resolves some of the pertinent issues raised in the literature with application of the Dieterich 1994 model.

The vibrational dependence of dissociative recombination: Rate constants for N{sub 2}{sup +}

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

Guberman, Steven L., E-mail: slg@sci.org

Dissociative recombination rate constants are reported with electron temperature dependent uncertainties for the lowest 5 vibrational levels of the N{sub 2}{sup +} ground state. The rate constants are determined from ab initio calculations of potential curves, electronic widths, quantum defects, and cross sections. At 100 K electron temperature, the rate constants overlap with the exception of the third vibrational level. At and above 300 K, the rate constants for excited vibrational levels are significantly smaller than that for the ground level. It is shown that any experimentally determined total rate constant at 300 K electron temperature that is smaller thanmore » 2.0 × 10{sup −7} cm{sup 3}/s is likely to be for ions that have a substantially excited vibrational population. Using the vibrational level specific rate constants, the total rate constant is in very good agreement with that for an excited vibrational distribution found in a storage ring experiment. It is also shown that a prior analysis of a laser induced fluorescence experiment is quantitatively flawed due to the need to account for reactions with unknown rate constants. Two prior calculations of the dissociative recombination rate constant are shown to be inconsistent with the cross sections upon which they are based. The rate constants calculated here contribute to the resolution of a 30 year old disagreement between modeled and observed N{sub 2}{sup +} ionospheric densities.« less

Prediction of trivalent actinide amino(poly)carboxylate complex stability constants using linear free energy relationships with the lanthanide series

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

Uhnak, Nic E.

Prediction of Trivalent Actinide Amino(poly)carboxylate Complex Stability Constants Using Linear Free Energy Relationships with the Lanthanide Series Alternative title: LFER Based Prediction of An(III) APC Stability Constants There is a gap in the literature regarding the complexation of amino(poly)carboxylate (APC) ligands with trivalent actinides (An(III))). The chemistry of the An(III) is nearly identical to that of the trivalent lanthanides Lns, but the An(III) express a slight enhancement when binding APC ligands. Presented in this report is a simple method of predicting the stability constants of the An(III), Pu, Am, Cm, Bk and Cf by using linear free energy relationships (LFER)more » of the An and the lanthanide (Ln) series for 91 APCs. This method produced An stability constants within uncertainty to available literature values for most ligands.« less

The metabolic equivalents of one-mile walking by older adults; implications for health promotion

PubMed Central

Gault, Mandy Lucinda; Willems, Mark Elisabeth Theodorus

2017-01-01

Background: Instructions for older adults regarding the intensity of walking may not elicit an intensity to infer health gains. We recorded the metabolic equivalents (METs) during a 1-mile walk using constant and predicted values of resting MET in older adults to establish walking guidelines for health promotion and participation. Methods: In a cross-sectional design study, participants (15 men, 10 women) walked 1-mile overground, in a wooden floored gymnasium, wearing the Cosmed K4b2 for measurement of energy expenditure. Constant or predicted values for resting MET were used to calculate the number of 1-mile walks to meet 450-750 MET∙min∙wk-1. Results: Participants had MET values higher than 3 for both methods, with 29% and 64% of the participants higher than 6 for a constant and predicted MET value, respectively. The METs of the1-mile walk were (mean ± SD) 6 ± 1 and 7 ± 1 METs using constant and predicted resting MET,and similar for men (constant: 6 ± 1 METs; predicted: 7 ± 1 METs) and women (constant: 5±1METs; predicted: 6 ± 1 METs) (P > 0.05). Conclusion: Older adults that are instructed to walk 1-mile at a fast and constant pace meet the minimum required intensity for physical activity, and public health guidelines. Health professionals, that administer exercise, could encourage older adults to accumulate between six and nine 1-mile walks per week for health gains. PMID:29085799

The metabolic equivalents of one-mile walking by older adults; implications for health promotion.

PubMed

Gault, Mandy Lucinda; Willems, Mark Elisabeth Theodorus

2017-01-01

Background: Instructions for older adults regarding the intensity of walking may not elicit an intensity to infer health gains. We recorded the metabolic equivalents (METs) during a 1-mile walk using constant and predicted values of resting MET in older adults to establish walking guidelines for health promotion and participation. Methods: In a cross-sectional design study, participants (15 men, 10 women) walked 1-mile overground, in a wooden floored gymnasium, wearing the Cosmed K4b 2 for measurement of energy expenditure. Constant or predicted values for resting MET were used to calculate the number of 1-mile walks to meet 450-750 MET∙min∙wk -1 . Results: Participants had MET values higher than 3 for both methods, with 29% and 64% of the participants higher than 6 for a constant and predicted MET value, respectively. The METs of the1-mile walk were (mean ± SD) 6 ± 1 and 7 ± 1 METs using constant and predicted resting MET,and similar for men (constant: 6 ± 1 METs; predicted: 7 ± 1 METs) and women (constant: 5±1METs; predicted: 6 ± 1 METs) (P > 0.05). Conclusion: Older adults that are instructed to walk 1-mile at a fast and constant pace meet the minimum required intensity for physical activity, and public health guidelines. Health professionals, that administer exercise, could encourage older adults to accumulate between six and nine 1-mile walks per week for health gains.

Electron attachment to C{sub 2} fluorocarbon radicals at high temperature

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

Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, Albert A., E-mail: afrl.rvborgmailbox@kirtland.af.mil

Thermal electron attachment to the radical species C{sub 2}F{sub 3} and C{sub 2}F{sub 5} has been studied over the temperature range 300–890 K using the Variable Electron and Neutral Density Attachment Mass Spectrometry technique. Both radicals exclusively undergo dissociative attachment to yield F{sup −}. The rate constant for C{sub 2}F{sub 5} shows little dependence over the temperature range, remaining ∼4 × 10{sup −9} cm{sup 3} s{sup −1}. The rate constant for C{sub 2}F{sub 3} attachment rises steeply with temperature from 3 × 10{sup −11} cm{sup 3} s{sup −1} at 300 K to 1 × 10{sup −9} cm{sup 3} s{sup −1} at 890 K.more » The behaviors of both species at high temperature are in agreement with extrapolations previously made from data below 600 K using a recently developed kinetic modeling approach. Measurements were also made on C{sub 2}F{sub 3}Br and C{sub 2}F{sub 5}Br (used in this work as precursors to the radicals) over the same temperature range, and, for C{sub 2}F{sub 5}Br as a function of electron temperature. The attachment rate constants to both species rise with temperature following Arrhenius behavior. The attachment rate constant to C{sub 2}F{sub 5}Br falls with increasing electron temperature, in agreement with the kinetic modeling. The current data fall in line with past predictions of the kinetic modeling approach, again showing the utility of this simplified approach.« less

Combustion of Interacting Droplet Arrays in a Microgravity Environment

NASA Technical Reports Server (NTRS)

Dietrich, D. L.; Struk, P. M.; Kitano, K.; Ikegami, M.

1999-01-01

Investigations into droplet interactions date back to Rex et al. Recently, Annamalai and Ryan and Annamalai published extensive reviews of droplet array and cloud combustion studies. The authors studied the change in the burning rate constant, k, (relative to that of the single droplet) that results from interactions. Under certain conditions, there exists a separation distance where the droplet lifetime reaches a minimum, or average burning rate constant is a maximum . Additionally, since inter-droplet separation distance, L, increases relative to the droplet size, D, as the burning proceeds, the burning rate is not constant throughout the burn, but changes continuously with time. Only Law and co-workers and Mikami et al. studied interactions under conditions where buoyant forces were negligible. Comparing their results with existing theory, Law and co-workers found that theory over predicted the persistency and intensity of droplet interactions. The droplet interactions also depended on the initial array configuration as well as the instantaneous array configuration. They also concluded that droplet heating was retarded due to interactions and that the burning process did not follow the "D-squared" law. Mikami et al. studied the combustion of a two-droplet array of heptane burning in air at one atm pressure in microgravity. They showed that the instantaneous burning rate constant increases throughout the droplet lifetime, even for a single droplet. Also, the burn time of the array reached a minimum at a critical inter-droplet spacing. In this article, we examine droplet interactions in normal and microgravity environments. The microgravity experiments were in the NASA GRC 2.2 and 5.2 second drop towers, and the JAMIC (Japan Microgravity Center) 10 second drop tower. Special emphasis is directed to combustion under conditions that yield finite extinction diameters, and to determine how droplet interactions affect the extinction process.

Theoretical study of the gas-phase reactions of iodine atoms ((2)P(3/2)) with H(2), H(2)O, HI, and OH.

PubMed

Canneaux, Sébastien; Xerri, Bertrand; Louis, Florent; Cantrel, Laurent

2010-09-02

The rate constants of the reactions of iodine atoms with H(2), H(2)O, HI, and OH have been estimated using 39, 21, 13, and 39 different levels of theory, respectively, and have been compared to the available literature values over the temperature range of 250-2500 K. The aim of this methodological work is to demonstrate that standard theoretical methods are adequate to obtain quantitative rate constants for the reactions involving iodine-containing species. Geometry optimizations and vibrational frequency calculations are performed using three methods (MP2, MPW1K, and BHandHLYP) combined with three basis sets (cc-pVTZ, cc-pVQZ, and 6-311G(d,p)). Single-point energy calculations are performed with the highly correlated ab initio coupled cluster method in the space of single, double, and triple (pertubatively) electron excitations CCSD(T) using the cc-pVnZ (n = T, Q, and 5), aug-cc-pVnZ (n = T, Q, and 5), 6-311G(d,p), 6-311+G(3df,2p), and 6-311++G(3df,3pd) basis sets. Canonical transition state theory with a simple Wigner tunneling correction is used to predict the rate constants as a function of temperature. CCSD(T)/cc-pVnZ//MP2/cc-pVTZ (n = T and Q), CCSD(T)/6-311+G(3df,2p)//MP2/6-311G(d,p), and CCSD(T)/6-311++G(3df,3pd)//MP2/6-311G(d,p) levels of theory provide accurate kinetic rate constants when compared to available literature data. The use of the CCSD(T)/cc-pVQZ//MP2/cc-pVTZ and CCSD(T)/6-311++G(3df,3pd) levels of theory allows one to obtain a better agreement with the literature data for all reactions with the exception of the I + H(2) reaction R(1) . This computational procedure has been also used to predict rate constants for some reactions where no available experimental data exist. The use of quantum chemistry tools could be therefore extended to other elements and next applied to develop kinetic networks involving various fission products, steam, and hydrogen in the absence of literature data. The final objective is to implement the kinetics of gaseous reactions in the ASTEC (Accident Source Term Evaluation Code) code to improve speciation of fission transport, which can be transported along the Reactor Coolant System (RCS) of a Pressurized Water Reactor (PWR) in case of a severe accident.

The Original Michaelis Constant: Translation of the 1913 Michaelis-Menten Paper

PubMed Central

Johnson, Kenneth A.; Goody, Roger S.

2011-01-01

Nearly 100 years ago Michaelis and Menten published their now classic paper (Michaelis, L., and Menten, M. L. (1913) Die Kinetik der Invertinwirkung, Biochemische Zeitschrift 49, 333–369), in which they show that the rate of an enzyme-catalyzed reaction is proportional to the concentration of enzyme-substrate complex predicted by the Michaelis-Menten equation. Because the original text was written in German, yet is often quoted by English speaking authors, we undertook a complete translation of the 1913 publication, which we provide as an online supplement (http://pubs.acs.org). Here we introduce the translation, describe the historical context of the work, and show a new analysis of the original data. In doing so, we uncovered several surprises that reveal an interesting glimpse into the early history of enzymology. In particular, our re-analysis of Michaelis and Menten’s data using modern computational methods revealed an unanticipated rigor and precision in the original publication and uncovered a sophisticated, comprehensive analysis that has been overlooked in the century since their work was published. Michaelis and Menten not only analyzed initial velocity measurements, but they also fit their full time course data to the integrated form of the rate equations, including product inhibition, and derived a single global constant to represent all of their data. That constant was not the Michaelis constant, but rather, Vmax/Km, the specificity constant times the enzyme concentration (kcat/Km*E0). PMID:21888353

A novel model to predict gas-phase hydroxyl radical oxidation kinetics of polychlorinated compounds.

PubMed

Luo, Shuang; Wei, Zongsu; Spinney, Richard; Yang, Zhihui; Chai, Liyuan; Xiao, Ruiyang

2017-04-01

In this study, a novel model based on aromatic meta-substituent grouping was presented to predict the second-order rate constants (k) for OH oxidation of PCBs in gas-phase. Since the oxidation kinetics are dependent on the chlorination degree and position, we hypothesized that it may be more accurate for k value prediction if we group PCB congeners based on substitution positions (i.e., ortho (o), meta (m), and para (p)). To test this hypothesis, we examined the correlation of polarizability (α), a quantum chemical based descriptor for k values, with an empirical Hammett constant (σ + ) on each substitution position. Our result shows that α is highly linearly correlated to ∑σ o,m,p + based on aromatic meta-substituents leading to the grouping based predictive model. With the new model, the calculated k values exhibited an excellent agreement with experimental measurements, and greater predictive power than the quantum chemical based quantitative structure activity relationship (QSAR) model. Further, the relationship of α and ∑σ o,m,p + for PCDDs congeners, together with highest occupied molecular orbital (HOMO) distribution, were used to validate the aromatic meta-substituent grouping method. This newly developed model features a combination of good predictability of quantum chemical based QSAR model and simplicity of Hammett relationship, showing a great potential for fast and computational tractable prediction of k values for gas-phase OH oxidation of polychlorinated compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

Microplastic bases for constitutive characterization of aluminum alloys and their correlation to sheet formability

NASA Astrophysics Data System (ADS)

Diak, Bradley James

Forming limit predictions that incorporate crystal plasticity models still cannot adequately predict the deformation performance of polycrystalline materials. The reason for the limitation in predictive power is that the constitutive equations used to connect to the atomic scale assume an affine deformation which do not have a physical basis, but give general trends. This study was undertaken to better elucidate the microplastic process and how it manifests itself phenomenologically. In this endeavour, the strain rate sensitivity of the flow stress was identified as one parameter that greatly affects the forming limit. Hence, an attempt was made to properly define and measure the strain rate sensitivity according to the dictates of thermodynamics. The thermodynamics of systems can delineate the evolution of the state of a material if the state variables can be characterized and measured. Inevitably, these variables must be determined at constant structure. Using the theory of thermally activated flow, where the movement of dislocations past obstacles is the rate controlling step, the mechanical testing techniques have been designed to statistically assess the dynamic evolution of the microstructure by controlling the temperature, T, and strain rate, dotvarepsilon, and measuring the stress, sigma, mean slip distance, lambda, and mean slip velocity, dotlambda, to define sigma=f(lambda,dotlambda, T). The apparent activation volume, which characterizes the obstacle resistance of strain centres, is determined at constant structure by applying the strain rate change technique. Strain rate sensitivity data are compared to the Cottrell-Stokes relation, and the Haasen plot is used to separate the different contributions to the flow stress. Using these precise measurements at interrupted segments of strain, the evolution of a microstructure during plastic flow can be monitored. By this examination of different rate controlling obstacles, the microstructural parameters which correlate to formability were assessed. Detailed experimental evidence is given for different aluminum alloys containing mainly fast or slow diffusing solute species, transition precipitates, dispersed particles, and/or dislocation debris. These systems of Al-Fe, Al-Cr, Al-Cu, Al-Mg, and Al-Mg-Si, all displayed unique dislocation-defect interactions which could be elucidated by the current theory of thermally activated flow.

Calculation of kinetic rate constants from thermodynamic data

NASA Technical Reports Server (NTRS)

Marek, C. John

1995-01-01

A new scheme for relating the absolute value for the kinetic rate constant k to the thermodynamic constant Kp is developed for gases. In this report the forward and reverse rate constants are individually related to the thermodynamic data. The kinetic rate constants computed from thermodynamics compare well with the current kinetic rate constants. This method is self consistent and does not have extensive rules. It is first demonstrated and calibrated by computing the HBr reaction from H2 and Br2. This method then is used on other reactions.

Long-time dynamic compatibility of elastomeric materials with hydrazine

NASA Technical Reports Server (NTRS)

Coulbert, C. D.; Cuddihy, E. F.; Fedors, R. F.

1973-01-01

The tensile property surfaces for two elastomeric materials, EPT-10 and AF-E-332, were generated in air and in liquid hydrazine environments using constant strain rate tensile tests over a range of temperatures and elongation rates. These results were used to predict the time-to-rupture for these materials in hydrazine as a function of temperature and amount of strain covering a span of operating times from less than a minute to twenty years. The results of limited sheet-folding tests and their relationship to the tensile failure boundary are presented and discussed.

Examination of the wind speed limit function in the Rothermel surface fire spread model

Treesearch

Patricia L. Andrews; Miguel G. Cruz; Richard C. Rothermel

2013-01-01

The Rothermel surface fire spread model includes a wind speed limit, above which predicted rate of spread is constant. Complete derivation of the wind limit as a function of reaction intensity is given, along with an alternate result based on a changed assumption. Evidence indicates that both the original and the revised wind limits are too restrictive. Wind limit is...

Computational Prediction of Kinetic Rate Constants

DTIC Science & Technology

2006-11-30

without requiring additional data. Zero-point energy ( ZPE ) anharmonicity has a large effect on the accuracy of approximate partition function estimates. If...the accurate ZPE is taken into account, separable approximation partition functions using the most accurate torsion treatment and harmonic treatments...for the remaining degrees of freedom agree with accurate QM partition functions to within a mean accuracy of 9%. If no ZPE anharmonicity correction

Method to predict relative hydriding within a group of zirconium alloys under nuclear irradiation

DOEpatents

Johnson, A.B. Jr.; Levy, I.S.; Trimble, D.J.; Lanning, D.D.; Gerber, F.S.

1990-04-10

An out-of-reactor method for screening to predict relative in-reactor hydriding behavior of zirconium-based materials is disclosed. Samples of zirconium-based materials having different compositions and/or fabrication methods are autoclaved in a relatively concentrated (0.3 to 1.0M) aqueous lithium hydroxide solution at constant temperatures within the water reactor coolant temperature range (280 to 316 C). Samples tested by this out-of-reactor procedure, when compared on the basis of the ratio of hydrogen weight gain to oxide weight gain, accurately predict the relative rate of hydriding for the same materials when subject to in-reactor (irradiated) corrosion. 1 figure.

Age-Dependent and Lineage-Dependent Speciation and Extinction in the Imbalance of Phylogenetic Trees.

PubMed

Holman, Eric W

2017-11-01

It is known that phylogenetic trees are more imbalanced than expected from a birth-death model with constant rates of speciation and extinction, and also that imbalance can be better fit by allowing the rate of speciation to decrease as the age of the parent species increases. If imbalance is measured in more detail, at nodes within trees as a function of the number of species descended from the nodes, age-dependent models predict levels of imbalance comparable to real trees for small numbers of descendent species, but predicted imbalance approaches an asymptote not found in real trees as the number of descendent species becomes large. Age-dependence must therefore be complemented by another process such as inheritance of different rates along different lineages, which is known to predict insufficient imbalance at nodes with few descendent species, but can predict increasing imbalance with increasing numbers of descendent species. [Crump-Mode-Jagers process; diversification; macroevolution; taxon sampling; tree of life.]. © The Author(s) 2017. Published by Oxford University Press, on behalf of the Society of Systematic Biologists. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Predicting fractional bed load transport rates: Application of the Wilcock‐Crowe equations to a regulated gravel bed river

USGS Publications Warehouse

Gaeuman, David; Andrews, E.D.; Krause, Andreas; Smith, Wes

2009-01-01

Bed load samples from four locations in the Trinity River of northern California are analyzed to evaluate the performance of the Wilcock‐Crowe bed load transport equations for predicting fractional bed load transport rates. Bed surface particles become smaller and the fraction of sand on the bed increases with distance downstream from Lewiston Dam. The dimensionless reference shear stress for the mean bed particle size (τ*rm) is largest near the dam, but varies relatively little between the more downstream locations. The relation between τ*rm and the reference shear stresses for other size fractions is constant across all locations. Total bed load transport rates predicted with the Wilcock‐Crowe equations are within a factor of 2 of sampled transport rates for 68% of all samples. The Wilcock‐Crowe equations nonetheless consistently under‐predict the transport of particles larger than 128 mm, frequently by more than an order of magnitude. Accurate prediction of the transport rates of the largest particles is important for models in which the evolution of the surface grain size distribution determines subsequent bed load transport rates. Values of τ*rm estimated from bed load samples are up to 50% larger than those predicted with the Wilcock‐Crowe equations, and sampled bed load transport approximates equal mobility across a wider range of grain sizes than is implied by the equations. Modifications to the Wilcock‐Crowe equation for determining τ*rm and the hiding function used to scale τ*rm to other grain size fractions are proposed to achieve the best fit to observed bed load transport in the Trinity River.

Earthquake triggering by transient and static deformations

USGS Publications Warehouse

Gomberg, J.; Beeler, N.M.; Blanpied, M.L.; Bodin, P.

1998-01-01

Observational evidence for both static and transient near-field and far-field triggered seismicity are explained in terms of a frictional instability model, based on a single degree of freedom spring-slider system and rate- and state-dependent frictional constitutive equations. In this study a triggered earthquake is one whose failure time has been advanced by ??t (clock advance) due to a stress perturbation. Triggering stress perturbations considered include square-wave transients and step functions, analogous to seismic waves and coseismic static stress changes, respectively. Perturbations are superimposed on a constant background stressing rate which represents the tectonic stressing rate. The normal stress is assumed to be constant. Approximate, closed-form solutions of the rate-and-state equations are derived for these triggering and background loads, building on the work of Dieterich [1992, 1994]. These solutions can be used to simulate the effects of static and transient stresses as a function of amplitude, onset time t0, and in the case of square waves, duration. The accuracies of the approximate closed-form solutions are also evaluated with respect to the full numerical solution and t0. The approximate solutions underpredict the full solutions, although the difference decreases as t0, approaches the end of the earthquake cycle. The relationship between ??t and t0 differs for transient and static loads: a static stress step imposed late in the cycle causes less clock advance than an equal step imposed earlier, whereas a later applied transient causes greater clock advance than an equal one imposed earlier. For equal ??t, transient amplitudes must be greater than static loads by factors of several tens to hundreds depending on t0. We show that the rate-and-state model requires that the total slip at failure is a constant, regardless of the loading history. Thus a static load applied early in the cycle, or a transient applied at any time, reduces the stress at the initiation of failure, whereas static loads that are applied sufficiently late raise it. Rate-and-state friction predictions differ markedly from those based on Coulomb failure stress changes (??CFS) in which ??t equals the amplitude of the static stress change divided by the background stressing rate. The ??CFS model assumes a stress failure threshold, while the rate-and-state equations require a slip failure threshold. The complete rale-and-state equations predict larger ??t than the ??CFS model does for static stress steps at small t0, and smaller ??t than the ??CFS model for stress steps at large t0. The ??CFS model predicts nonzero ??t only for transient loads that raise the stress to failure stress levels during the transient. In contrast, the rate-and-state model predicts nonzero ??t for smaller loads, and triggered failure may occur well after the transient is finished. We consider heuristically the effects of triggering on a population of faults, as these effects might be evident in seismicity data. Triggering is manifest as an initial increase in seismicity rate that may be followed by a quiescence or by a return to the background rate. Available seismicity data are insufficient to discriminate whether triggered earthquakes are "new" or clock advanced. However, if triggering indeed results from advancing the failure time of inevitable earthquakes, then our modeling suggests that a quiescence always follows transient triggering and that the duration of increased seismicity also cannot exceed the duration of a triggering transient load. Quiescence follows static triggering only if the population of available faults is finite.

Micellar modification of drug stability: analysis of the effect of hexadecyltrimethylammonium halides on the rate of degradation of cephaclor.

PubMed

Oliveira, A G; Cuccovia, I M; Chaimovich, H

1990-01-01

The intra- and intermolecular rates of degradation of cephaclor were determined with and without hexadecyltrimethylammonium bromide (CTABr). Micellar-derived spectral shifts were used to measure the association of the ionic forms as well as to determine the effect of CTABr on the apparent acid dissociation constant of the antibiotic. The rate of degradation of cephaclor increased with detergent and was salt sensitive. Micellar effects were analyzed quantitatively within the framework of the pseudophase ion exchange model. All experimental data were fitted to this model which was used to predict the combined effects of pH and detergent concentration. Micelles increased the rate of OH- attack on cephaclor; most of the effect was due to the concentration of reagents in the micellar pseudophase. The intramolecular degradation was catalyzed 25-fold by micelles, and a working hypothesis to rationalize this effect is proposed. The results demonstrate that quantitative analysis can be utilized to assess and predict effects of detergents on drug stability.

Development of a program to fit data to a new logistic model for microbial growth.

PubMed

Fujikawa, Hiroshi; Kano, Yoshihiro

2009-06-01

Recently we developed a mathematical model for microbial growth in food. The model successfully predicted microbial growth at various patterns of temperature. In this study, we developed a program to fit data to the model with a spread sheet program, Microsoft Excel. Users can instantly get curves fitted to the model by inputting growth data and choosing the slope portion of a curve. The program also could estimate growth parameters including the rate constant of growth and the lag period. This program would be a useful tool for analyzing growth data and further predicting microbial growth.

Escherichia coli promoter sequences predict in vitro RNA polymerase selectivity.

PubMed

Mulligan, M E; Hawley, D K; Entriken, R; McClure, W R

1984-01-11

We describe a simple algorithm for computing a homology score for Escherichia coli promoters based on DNA sequence alone. The homology score was related to 31 values, measured in vitro, of RNA polymerase selectivity, which we define as the product KBk2, the apparent second order rate constant for open complex formation. We found that promoter strength could be predicted to within a factor of +/-4.1 in KBk2 over a range of 10(4) in the same parameter. The quantitative evaluation was linked to an automated (Apple II) procedure for searching and evaluating possible promoters in DNA sequence files.

Predicting chemical degradation during storage from two successive concentration ratios: Theoretical investigation.

PubMed

Peleg, Micha; Normand, Mark D

2015-09-01

When a vitamin's, pigment's or other food component's chemical degradation follows a known fixed order kinetics, and its rate constant's temperature-dependence follows a two parameter model, then, at least theoretically, it is possible to extract these two parameters from two successive experimental concentration ratios determined during the food's non-isothermal storage. This requires numerical solution of two simultaneous equations, themselves the numerical solutions of two differential rate equations, with a program especially developed for the purpose. Once calculated, these parameters can be used to reconstruct the entire degradation curve for the particular temperature history and predict the degradation curves for other temperature histories. The concept and computation method were tested with simulated degradation under rising and/or falling oscillating temperature conditions, employing the exponential model to characterize the rate constant's temperature-dependence. In computer simulations, the method's predictions were robust against minor errors in the two concentration ratios. The program to do the calculations was posted as freeware on the Internet. The temperature profile can be entered as an algebraic expression that can include 'If' statements, or as an imported digitized time-temperature data file, to be converted into an Interpolating Function by the program. The numerical solution of the two simultaneous equations requires close initial guesses of the exponential model's parameters. Programs were devised to obtain these initial values by matching the two experimental concentration ratios with a generated degradation curve whose parameters can be varied manually with sliders on the screen. These programs too were made available as freeware on the Internet and were tested with published data on vitamin A. Copyright © 2015 Elsevier Ltd. All rights reserved.

Communication — Modeling polymer-electrolyte fuel-cell agglomerates with double-trap kinetics

DOE PAGES

Pant, Lalit M.; Weber, Adam Z.

2017-04-14

A new semi-analytical agglomerate model is presented for polymer-electrolyte fuel-cell cathodes. The model uses double-trap kinetics for the oxygen-reduction reaction, which can capture the observed potential-dependent coverage and Tafel-slope changes. An iterative semi-analytical approach is used to obtain reaction rate constants from the double-trap kinetics, oxygen concentration at the agglomerate surface, and overall agglomerate reaction rate. The analytical method can predict reaction rates within 2% of the numerically simulated values for a wide range of oxygen concentrations, overpotentials, and agglomerate sizes, while saving simulation time compared to a fully numerical approach.

Improved resolution of single channel dwell times reveals mechanisms of binding, priming, and gating in muscle AChR

PubMed Central

Mukhtasimova, Nuriya; daCosta, Corrie J.B.

2016-01-01

The acetylcholine receptor (AChR) from vertebrate skeletal muscle initiates voluntary movement, and its kinetics of activation are crucial for maintaining the safety margin for neuromuscular transmission. Furthermore, the kinetic mechanism of the muscle AChR serves as an archetype for understanding activation mechanisms of related receptors from the Cys-loop superfamily. Here we record currents through single muscle AChR channels with improved temporal resolution approaching half an order of magnitude over our previous best. A range of concentrations of full and partial agonists are used to elicit currents from human wild-type and gain-of-function mutant AChRs. For each agonist–receptor combination, rate constants are estimated from maximum likelihood analysis using a kinetic scheme comprised of agonist binding, priming, and channel gating steps. The kinetic scheme and rate constants are tested by stochastic simulation, followed by incorporation of the experimental step response, sampling rate, background noise, and filter bandwidth. Analyses of the simulated data confirm all rate constants except those for channel gating, which are overestimated because of the established effect of noise on the briefest dwell times. Estimates of the gating rate constants were obtained through iterative simulation followed by kinetic fitting. The results reveal that the agonist association rate constants are independent of agonist occupancy but depend on receptor state, whereas those for agonist dissociation depend on occupancy but not on state. The priming rate and equilibrium constants increase with successive agonist occupancy, and for a full agonist, the forward rate constant increases more than the equilibrium constant; for a partial agonist, the forward rate and equilibrium constants increase equally. The gating rate and equilibrium constants also increase with successive agonist occupancy, but unlike priming, the equilibrium constants increase more than the forward rate constants. As observed for a full and a partial agonist, the gain-of-function mutation affects the relationship between rate and equilibrium constants for priming but not for channel gating. Thus, resolving brief single channel currents distinguishes priming from gating steps and reveals how the corresponding rate and equilibrium constants depend on agonist occupancy. PMID:27353445

Inverse method to estimate kinetic degradation parameters of grape anthocyanins in wheat flour under simultaneously changing temperature and moisture.

PubMed

Lai, K P K; Dolan, K D; Ng, P K W

2009-06-01

Thermal and moisture effects on grape anthocyanin degradation were investigated using solid media to simulate processing at temperatures above 100 degrees C. Grape pomace (anthocyanin source) mixed with wheat pastry flour (1: 3, w/w dry basis) was used in both isothermal and nonisothermal experiments by heating the same mixture at 43% (db) initial moisture in steel cells in an oil bath at 80, 105, and 145 degrees C. To determine the effect of moisture on anthocyanin degradation, the grape pomace-wheat flour mixture was heated isothermally at 80 degrees C at constant moisture contents of 10%, 20%, and 43% (db). Anthocyanin degradation followed a pseudo first-order reaction with moisture. Anthocyanins degraded more rapidly with increasing temperature and moisture. The effects of temperature and moisture on the rate constant were modeled according to the Arrhenius and an exponential relationship, respectively. The nonisothermal reaction rate constant and activation energy (mean +/- standard error) were k(80 degrees C, 43% (db) moisture) = 2.81 x 10(-4)+/- 1.1 x 10(-6) s(-1) and DeltaE = 75273 +/- 197 J/g mol, respectively. The moisture parameter for the exponential model was 4.28 (dry basis moisture content)(-1). One possible application of this study is as a tool to predict the loss of anthocyanins in nutraceutical products containing grape pomace. For example, if the process temperature history and moisture history in an extruded snack fortified with grape pomace is known, the percentage anthocyanin loss can be predicted.

On the Appearance of Thresholds in the Dynamical Model of Star Formation

NASA Astrophysics Data System (ADS)

Elmegreen, Bruce G.

2018-02-01

The Kennicutt–Schmidt (KS) relationship between the surface density of the star formation rate (SFR) and the gas surface density has three distinct power laws that may result from one model in which gas collapses at a fixed fraction of the dynamical rate. The power-law slope is 1 when the observed gas has a characteristic density for detection, 1.5 for total gas when the thickness is about constant as in the main disks of galaxies, and 2 for total gas when the thickness is regulated by self-gravity and the velocity dispersion is about constant, as in the outer parts of spirals, dwarf irregulars, and giant molecular clouds. The observed scaling of the star formation efficiency (SFR per unit CO) with the dense gas fraction (HCN/CO) is derived from the KS relationship when one tracer (HCN) is on the linear part and the other (CO) is on the 1.5 part. Observations of a threshold density or column density with a constant SFR per unit gas mass above the threshold are proposed to be selection effects, as are observations of star formation in only the dense parts of clouds. The model allows a derivation of all three KS relations using the probability distribution function of density with no thresholds for star formation. Failed galaxies and systems with sub-KS SFRs are predicted to have gas that is dominated by an equilibrium warm phase where the thermal Jeans length exceeds the Toomre length. A squared relation is predicted for molecular gas-dominated young galaxies.

Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations for solvent-based carbon capture. Part 2: Chemical absorption across a wetted wall column: Original Research Article: Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations

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

Wang, Chao; Xu, Zhijie; Lai, Kevin

Part 1 of this paper presents a numerical model for non-reactive physical mass transfer across a wetted wall column (WWC). In Part 2, we improved the existing computational fluid dynamics (CFD) model to simulate chemical absorption occurring in a WWC as a bench-scale study of solvent-based carbon dioxide (CO2) capture. To generate data for WWC model validation, CO2 mass transfer across a monoethanolamine (MEA) solvent was first measured on a WWC experimental apparatus. The numerical model developed in this work can account for both chemical absorption and desorption of CO2 in MEA. In addition, the overall mass transfer coefficient predictedmore » using traditional/empirical correlations is conducted and compared with CFD prediction results for both steady and wavy falling films. A Bayesian statistical calibration algorithm is adopted to calibrate the reaction rate constants in chemical absorption/desorption of CO2 across a falling film of MEA. The posterior distributions of the two transport properties, i.e., Henry's constant and gas diffusivity in the non-reacting nitrous oxide (N2O)/MEA system obtained from Part 1 of this study, serves as priors for the calibration of CO2 reaction rate constants after using the N2O/CO2 analogy method. The calibrated model can be used to predict the CO2 mass transfer in a WWC for a wider range of operating conditions.« less

Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations for solvent-based carbon capture. Part 2: Chemical absorption across a wetted wall column: Original Research Article: Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations

DOE PAGES

Wang, Chao; Xu, Zhijie; Lai, Kevin; ...

2017-10-24

Part 1 of this paper presents a numerical model for non-reactive physical mass transfer across a wetted wall column (WWC). In Part 2, we improved the existing computational fluid dynamics (CFD) model to simulate chemical absorption occurring in a WWC as a bench-scale study of solvent-based carbon dioxide (CO2) capture. To generate data for WWC model validation, CO2 mass transfer across a monoethanolamine (MEA) solvent was first measured on a WWC experimental apparatus. The numerical model developed in this work can account for both chemical absorption and desorption of CO2 in MEA. In addition, the overall mass transfer coefficient predictedmore » using traditional/empirical correlations is conducted and compared with CFD prediction results for both steady and wavy falling films. A Bayesian statistical calibration algorithm is adopted to calibrate the reaction rate constants in chemical absorption/desorption of CO2 across a falling film of MEA. The posterior distributions of the two transport properties, i.e., Henry's constant and gas diffusivity in the non-reacting nitrous oxide (N2O)/MEA system obtained from Part 1 of this study, serves as priors for the calibration of CO2 reaction rate constants after using the N2O/CO2 analogy method. The calibrated model can be used to predict the CO2 mass transfer in a WWC for a wider range of operating conditions.« less

Modeling Surface Growth of Escherichia coli on Agar Plates

PubMed Central

Fujikawa, Hiroshi; Morozumi, Satoshi

2005-01-01

Surface growth of Escherichia coli cells on a membrane filter placed on a nutrient agar plate under various conditions was studied with a mathematical model. The surface growth of bacterial cells showed a sigmoidal curve with time on a semilogarithmic plot. To describe it, a new logistic model that we presented earlier (H. Fujikawa et al., Food Microbiol. 21:501-509, 2004) was modified. Growth curves at various constant temperatures (10 to 34°C) were successfully described with the modified model (model III). Model III gave better predictions of the rate constant of growth and the lag period than a modified Gompertz model and the Baranyi model. Using the parameter values of model III at the constant temperatures, surface growth at various temperatures was successfully predicted. Surface growth curves at various initial cell numbers were also sigmoidal and converged to the same maximum cell numbers at the stationary phase. Surface growth curves at various nutrient levels were also sigmoidal. The maximum cell number and the rate of growth were lower as the nutrient level decreased. The surface growth curve was the same as that in a liquid, except for the large curvature at the deceleration period. These curves were also well described with model III. The pattern of increase in the ATP content of cells grown on a surface was sigmoidal, similar to that for cell growth. We discovered several characteristics of the surface growth of bacterial cells under various growth conditions and examined the applicability of our model to describe these growth curves. PMID:16332768

Precision control of eluted activity from a Sr/Rb generator for cardiac positron emission tomography.

PubMed

Klein, R; Adler, A; Beanlands, R S; deKemp, R A

2004-01-01

A rubidium-82 (/sup 82/Rb) elution system is described for use with clinical positron emission tomography. The system is self-calibrating with 1.4% repeatability, independent of generator activity and elution flow rate. Saline flow is switched between a /sup 82/Sr//sup 82/Rb generator and a bypass line to achieve a constant activity elution of /sup 82/Rb. In the present study, pulse width modulation (PWM) of a solenoid valve is compared to simple threshold control as a means to simulate a proportional valve. A predictive-corrective control algorithm is developed which produces a constant activity elution within the constraints of long feedback delay and short elution time. Accurate constant-activity elutions of 10-70% of the total generator activity were demonstrated using the threshold comparison control. The adaptive-corrective control of the PWM valve provided a substantial improvement in precision of the steady-state output.

Thermal decomposition of ethanol. II. A computational study of the kinetics and mechanism for the H+C2H5OH reaction

NASA Astrophysics Data System (ADS)

Park, J.; Xu, Z. F.; Lin, M. C.

2003-06-01

The kinetics and mechanism for the H+C2H5OH reaction, a key chain-propagation step in the high temperature decomposition and combustion of ethanol, have been investigated with the modified GAUSSIAN -2 (G2M) method using the structures of the reactants, transition states and products optimized at the B3LYP/6-311+G(d,p) level of theory. Four transition states have been identified for the production of H2+CH3CHOH (TS1), H2+CH2CH2OH (TS2), H2+C2H5O (TS3), and H2O+C2H5 (TS4) with the corresponding barriers, 7.18, 13.30, 14.95, and 27.10 kcal/mol. The predicted rate constants and branching ratios for the three H-abstraction reactions have been calculated over the temperature range 300-3000 K using the conventional and variational transition state theory with quantum-mechanical tunneling corrections. The predicted total rate constant, kt=3.15×103T3.12 exp(-1508/T) cm3 mol-1 s-1, agrees reasonably with existing experimental data; in particular, the result at 423 K was found to agree quantitatively with an available experimental value. The small deviation between the predicted kt and another set of experimental data measured at 295-700 K has been examined by kinetic modeling; the deviation is attributable to insufficient corrections for contributions from secondary reactions.

Interfacial Reaction Studies Using ONIOM

NASA Technical Reports Server (NTRS)

Cardelino, Beatriz H.

2003-01-01

In this report, we focus on the calculations of the energetics and chemical kinetics of heterogeneous reactions for Organometallic vapor phase epitaxy (OMVPE). The work described in this report builds upon our own previous thermochemical and chemical kinetics studies. The first of these articles refers to the prediction of thermochemical properties, and the latter one deals with the prediction of rate constants for gaseous homolytic dissociation reactions. The calculations of this investigation are at the microscopic level. The systems chosen consisted of a gallium nitride (GaN) substrate, and molecular nitrogen (N2) and ammonia (NH3) as adsorbants. The energetics for the adsorption and the adsorbant dissociation processes were estimated, and reaction rate constants for the dissociation reactions of free and adsorbed molecules were predicted. The energetics for substrate decomposition was also computed. The ONIOM method, implemented in the Gaussian98 program, was used to perform the calculations. This approach has been selected since it allows dividing the system into two layers that can be treated at different levels of accuracy. The atoms of the substrate were modeled using molecular mechanics6 with universal force fields, whereas the adsorbed molecules were approximated using quantum mechanics, based on density functional theory methods with B3LYP functionals and 6-311G(d,p) basis sets. Calculations for the substrate were performed in slabs of several unit cells in each direction. The N2 and NH3 adsorbates were attached to a central location at the Ga-lined surface.

Relationship of compressive stress-strain response of engineering materials obtained at constant engineering and true strain rates

DOE PAGES

Song, Bo; Sanborn, Brett

2018-05-07

In this paper, a Johnson–Cook model was used as an example to analyze the relationship of compressive stress-strain response of engineering materials experimentally obtained at constant engineering and true strain rates. There was a minimal deviation between the stress-strain curves obtained at the same constant engineering and true strain rates. The stress-strain curves obtained at either constant engineering or true strain rates could be converted from one to the other, which both represented the intrinsic material response. There is no need to specify the testing requirement of constant engineering or true strain rates for material property characterization, provided that eithermore » constant engineering or constant true strain rate is attained during the experiment.« less

Relationship of compressive stress-strain response of engineering materials obtained at constant engineering and true strain rates

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

Song, Bo; Sanborn, Brett

In this paper, a Johnson–Cook model was used as an example to analyze the relationship of compressive stress-strain response of engineering materials experimentally obtained at constant engineering and true strain rates. There was a minimal deviation between the stress-strain curves obtained at the same constant engineering and true strain rates. The stress-strain curves obtained at either constant engineering or true strain rates could be converted from one to the other, which both represented the intrinsic material response. There is no need to specify the testing requirement of constant engineering or true strain rates for material property characterization, provided that eithermore » constant engineering or constant true strain rate is attained during the experiment.« less

Excited heavy baryons and their symmetries III: Phenomenology

NASA Astrophysics Data System (ADS)

Baccouche, Z. Aziza; Chow, Chi-Keung; Cohen, Thomas D.; Gelman, Boris A.

2001-12-01

Phenomenological applications of an effective theory of low-lying excited states of charm and bottom isoscalar baryons are discussed at leading and next-to-leading order in the combined heavy-quark and large- Nc expansion. The combined expansion is formulated in terms of the counting parameter λ˜1/ mQ,1/ Nc; the combined expansion is in powers of λ1/2. We work up to next-to-leading order. We obtain model-independent predictions for the excitation energies, the semileptonic form factors and electromagnetic decay rates. At leading order in the combined expansion these observables are given in terms of one phenomenological constant which can be determined from the excitation energy of the first excited state of Λc baryon. At next-to-leading order an additional phenomenological constant is required. The spin-averaged mass of the doublet of the first orbitally excited state of Λb is predicted to be approximately 5920 MeV. It is shown that in the combined limit at leading and next-to-leading order there is only one independent form factor describing Λ b→Λ cℓ ν¯; similarly, Λ b→Λ c∗ℓ ν¯ and Λ b→Λ c1ℓ ν¯ decays are described by a single independent form factor. These form factors are calculated at leading and next-to-leading order in the combined expansion. The value of the Λ b→Λ cℓ ν¯ form factor at zero recoil is predicted to be 0.998 at leading order which is very close to HQET value of unity. The electromagnetic decay rates of the first excited states of Λc and Λb are determined at leading and next-to-leading order. The ratio of radiative decay rates Γ(Λ c∗→Λ cγ)/Γ(Λ b1→Λ bγ) is predicted to be approximately 0.2, greatly different from the heavy-quark effective theory value of unity.

Heat and mass transport during microwave heating of mashed potato in domestic oven--model development, validation, and sensitivity analysis.

PubMed

Chen, Jiajia; Pitchai, Krishnamoorthy; Birla, Sohan; Negahban, Mehrdad; Jones, David; Subbiah, Jeyamkondan

2014-10-01

A 3-dimensional finite-element model coupling electromagnetics and heat and mass transfer was developed to understand the interactions between the microwaves and fresh mashed potato in a 500 mL tray. The model was validated by performing heating of mashed potato from 25 °C on a rotating turntable in a microwave oven, rated at 1200 W, for 3 min. The simulated spatial temperature profiles on the top and bottom layer of the mashed potato showed similar hot and cold spots when compared to the thermal images acquired by an infrared camera. Transient temperature profiles at 6 locations collected by fiber-optic sensors showed good agreement with predicted results, with the root mean square error ranging from 1.6 to 11.7 °C. The predicted total moisture loss matched well with the observed result. Several input parameters, such as the evaporation rate constant, the intrinsic permeability of water and gas, and the diffusion coefficient of water and gas, are not readily available for mashed potato, and they cannot be easily measured experimentally. Reported values for raw potato were used as baseline values. A sensitivity analysis of these input parameters on the temperature profiles and the total moisture loss was evaluated by changing the baseline values to their 10% and 1000%. The sensitivity analysis showed that the gas diffusion coefficient, intrinsic water permeability, and the evaporation rate constant greatly influenced the predicted temperature and total moisture loss, while the intrinsic gas permeability and the water diffusion coefficient had little influence. This model can be used by the food product developers to understand microwave heating of food products spatially and temporally. This tool will allow food product developers to design food package systems that would heat more uniformly in various microwave ovens. The sensitivity analysis of this study will help us determine the most significant parameters that need to be measured accurately for reliable model prediction. © 2014 Institute of Food Technologists®

A theoretical framework for jamming in confluent biological tissues

NASA Astrophysics Data System (ADS)

Manning, M. Lisa

2015-03-01

For important biological functions such as wound healing, embryonic development, and cancer tumorogenesis, cells must initially rearrange and move over relatively large distances, like a liquid. Subsequently, these same tissues must undergo buckling and support shear stresses, like a solid. Our work suggests that biological tissues can accommodate these disparate requirements because the tissues are close to glass or jamming transition. While recent self propelled particle models generically predict a glass/jamming transition that is driven by packing density φ and happens at some critical φc less than unity, many biological tissues that are confluent with no gaps between cells appear to undergo a jamming transition at a constant density (φ = 1). I will discuss a new theoretical framework for predicting energy barriers and rates of cell migration in 2D tissue monolayers, and show that this model predicts a novel type of rigidity transition, which takes place at constant φ = 1 and depends only on single cell properties such as cell-cell adhesion, cortical tension and cell elasticity. This model additionally predicts that an experimentally observable parameter, the ratio between a cell's perimeter and the square root of its cross-sectional area, attains a specific, critical value at the jamming transition. We show that this prediction is precisely realized in primary epithelial cultures from human patients, with implications for asthma pathology.

Predicting elastic properties of β-HMX from first-principles calculations.

PubMed

Peng, Qing; Rahul; Wang, Guangyu; Liu, Gui-Rong; Grimme, Stefan; De, Suvranu

2015-05-07

We investigate the performance of van der Waals (vdW) functions in predicting the elastic constants of β cyclotetramethylene tetranitramine (HMX) energetic molecular crystals using density functional theory (DFT) calculations. We confirm that the accuracy of the elastic constants is significantly improved using the vdW corrections with environment-dependent C6 together with PBE and revised PBE exchange-correlation functionals. The elastic constants obtained using PBE-D3(0) calculations yield the most accurate mechanical response of β-HMX when compared with experimental stress-strain data. Our results suggest that PBE-D3 calculations are reliable in predicting the elastic constants of this material.

Determination of kinetic data for soot oxidation: Modeling of competition between oxygen diffusion and reaction during thermogravimetric analysis

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

Gilot, P.; Bonnefoy, F.; Marcuccilli, F.

1993-10-01

Kinetic data concerning carbon black oxidation in the temperature range between 600 and 900 C have been obtained using thermogravimetric analysis. Modeling of diffusion in a boundary layer above the pan and inside the porous medium coupled to oxygen reaction with carbon black is necessary to obtain kinetic constants as a function of temperature. These calculations require the knowledge of the oxidation rate at a given constant temperature as a function of the initial mass loading m[sub o]. This oxidation rate, expressed in milligrams of soot consumed per second and per milligram of initial soot loading, decreases when m[sub o]more » increases, in agreement with a reaction in an intermediary regime where the kinetics and the oxygen diffusion operate. The equivalent diffusivity of oxygen inside the porous medium is evaluated assuming two degrees of porosity: between soot aggregates and inside each aggregate. Below 700 C an activation energy of about 103 kJ/mol can be related to a combustion reaction probably kinetically controlled. Beyond 700 C the activation energy of about 20 kJ/ mol corresponds to a reaction essentially controlled by oxygen diffusion leading to a constant density oxidation with oxygen consumption at or near the particle surface. To validate these data, they are used in the modeling of a Diesel particulate trap regeneration. In this particular case, the oxidizing flux is forced across the carbon black deposit, oxygen diffusion being insignificant. A good agreement between experimental results and model predictions is obtained, proving the rate constants validity.« less

Prediction of growth of Pseudomonas fluorescens in milk during storage under fluctuating temperature.

PubMed

Lin, Hao; Shavezipur, Mohammad; Yousef, Ahmed; Maleky, Farnaz

2016-03-01

Accurate prediction of growth of undesirable organisms (e.g., Pseudomonas fluorescens) in perishable foods (e.g., milk), held under sub-ideal storage conditions, can help ensure the quality and safety of these foods at the point of consumption. In this investigation, we inoculated sterile milk with P. fluorescens (~10(3) cfu/mL) and monitored inoculum growth behavior at constant and fluctuating storage temperatures. Three storage temperatures, 4 °C, 15 °C and 29 °C, were selected to simulate proper refrigeration conditions (4 °C) and temperature abuse, respectively. To simulate temperature fluctuation, milk held at 4 °C was subjected to temperature shifts to 15 °C or 29 °C for 4 to 6h. A modified logistic model was used to obtain the best-fit curve for the microbial growth under constant storage temperature. The specific growth rates at 4 °C, 15 °C, and 29 °C, obtained from experimental data, were 0.056 ± 0.00, 0.17 ± 0.05, and 0.46 ± 0.02 h(-1), respectively, and the lag time values were 29.5 ± 4.2, 12.7 ± 4.4, and 2.8 ± 0.3h, respectively. A model predicting bacterial growth under different temperature fluctuations was obtained using the growth parameters extracted from constant temperature experiments. Growth behavior predicted by the fluctuating temperature model and that obtained experimentally were in good agreement. Lag time exhibited a larger variation compared with specific growth rate, suggesting that it depends not only on growth temperature but also on the sample population and temperature gradient. Additionally, experimental data showed that changing the temperature during the lag phase induced an additional lag time before growth; however, no significant lag time was observed under the temperature fluctuation during the exponential phase. The results of this study provide information for precise shelf-life determination and reduction of food waste, particularly for milk and milk-containing food products. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Using Computational Fluid Dynamics to Compare Shear Rate and Turbulence in the TIM-Automated Gastric Compartment With USP Apparatus II.

PubMed

Hopgood, Matthew; Reynolds, Gavin; Barker, Richard

2018-03-30

We use computational fluid dynamics to compare the shear rate and turbulence in an advanced in vitro gastric model (TIMagc) during its simulation of fasted state Migrating Motor Complex phases I and II, with the United States Pharmacopeia paddle dissolution apparatus II (USPII). A specific focus is placed on how shear rate in these apparatus affects erosion-based solid oral dosage forms. The study finds that tablet surface shear rates in TIMagc are strongly time dependant and fluctuate between 0.001 and 360 s -1 . In USPII, tablet surface shear rates are approximately constant for a given paddle speed and increase linearly from 9 s -1 to 36 s -1 as the paddle speed is increased from 25 to 100 rpm. A strong linear relationship is observed between tablet surface shear rate and tablet erosion rate in USPII, whereas TIMagc shows highly variable behavior. The flow regimes present in each apparatus are compared to in vivo predictions using Reynolds number analysis. Reynolds numbers for flow in TIMagc lie predominantly within the predicted in vivo bounds (0.01-30), whereas Reynolds numbers for flow in USPII lie above the predicted upper bound when operating with paddle speeds as low as 25 rpm (33). Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Physiological and ecological effects of increasing temperature on fish production in lakes of Arctic Alaska

USGS Publications Warehouse

Carey, Michael P.; Zimmerman, Christian E.

2014-01-01

Lake ecosystems in the Arctic are changing rapidly due to climate warming. Lakes are sensitive integrators of climate-induced changes and prominent features across the Arctic landscape, especially in lowland permafrost regions such as the Arctic Coastal Plain of Alaska. Despite many studies on the implications of climate warming, how fish populations will respond to lake changes is uncertain for Arctic ecosystems. Least Cisco (Coregonus sardinella) is a bellwether for Arctic lakes as an important consumer and prey resource. To explore the consequences of climate warming, we used a bioenergetics model to simulate changes in Least Cisco production under future climate scenarios for lakes on the Arctic Coastal Plain. First, we used current temperatures to fit Least Cisco consumption to observed annual growth. We then estimated growth, holding food availability, and then feeding rate constant, for future projections of temperature. Projected warmer water temperatures resulted in reduced Least Cisco production, especially for larger size classes, when food availability was held constant. While holding feeding rate constant, production of Least Cisco increased under all future scenarios with progressively more growth in warmer temperatures. Higher variability occurred with longer projections of time mirroring the expanding uncertainty in climate predictions further into the future. In addition to direct temperature effects on Least Cisco growth, we also considered changes in lake ice phenology and prey resources for Least Cisco. A shorter period of ice cover resulted in increased production, similar to warming temperatures. Altering prey quality had a larger effect on fish production in summer than winter and increased relative growth of younger rather than older age classes of Least Cisco. Overall, we predicted increased production of Least Cisco due to climate warming in lakes of Arctic Alaska. Understanding the implications of increased production of Least Cisco to the entire food web will be necessary to predict ecosystem responses in lakes of the Arctic.

Physiological and ecological effects of increasing temperature on fish production in lakes of Arctic Alaska

PubMed Central

Carey, Michael P; Zimmerman, Christian E

2014-01-01

Lake ecosystems in the Arctic are changing rapidly due to climate warming. Lakes are sensitive integrators of climate-induced changes and prominent features across the Arctic landscape, especially in lowland permafrost regions such as the Arctic Coastal Plain of Alaska. Despite many studies on the implications of climate warming, how fish populations will respond to lake changes is uncertain for Arctic ecosystems. Least Cisco (Coregonus sardinella) is a bellwether for Arctic lakes as an important consumer and prey resource. To explore the consequences of climate warming, we used a bioenergetics model to simulate changes in Least Cisco production under future climate scenarios for lakes on the Arctic Coastal Plain. First, we used current temperatures to fit Least Cisco consumption to observed annual growth. We then estimated growth, holding food availability, and then feeding rate constant, for future projections of temperature. Projected warmer water temperatures resulted in reduced Least Cisco production, especially for larger size classes, when food availability was held constant. While holding feeding rate constant, production of Least Cisco increased under all future scenarios with progressively more growth in warmer temperatures. Higher variability occurred with longer projections of time mirroring the expanding uncertainty in climate predictions further into the future. In addition to direct temperature effects on Least Cisco growth, we also considered changes in lake ice phenology and prey resources for Least Cisco. A shorter period of ice cover resulted in increased production, similar to warming temperatures. Altering prey quality had a larger effect on fish production in summer than winter and increased relative growth of younger rather than older age classes of Least Cisco. Overall, we predicted increased production of Least Cisco due to climate warming in lakes of Arctic Alaska. Understanding the implications of increased production of Least Cisco to the entire food web will be necessary to predict ecosystem responses in lakes of the Arctic. PMID:24963391

Physiological and ecological effects of increasing temperature on fish production in lakes of Arctic Alaska.

PubMed

Carey, Michael P; Zimmerman, Christian E

2014-05-01

Lake ecosystems in the Arctic are changing rapidly due to climate warming. Lakes are sensitive integrators of climate-induced changes and prominent features across the Arctic landscape, especially in lowland permafrost regions such as the Arctic Coastal Plain of Alaska. Despite many studies on the implications of climate warming, how fish populations will respond to lake changes is uncertain for Arctic ecosystems. Least Cisco (Coregonus sardinella) is a bellwether for Arctic lakes as an important consumer and prey resource. To explore the consequences of climate warming, we used a bioenergetics model to simulate changes in Least Cisco production under future climate scenarios for lakes on the Arctic Coastal Plain. First, we used current temperatures to fit Least Cisco consumption to observed annual growth. We then estimated growth, holding food availability, and then feeding rate constant, for future projections of temperature. Projected warmer water temperatures resulted in reduced Least Cisco production, especially for larger size classes, when food availability was held constant. While holding feeding rate constant, production of Least Cisco increased under all future scenarios with progressively more growth in warmer temperatures. Higher variability occurred with longer projections of time mirroring the expanding uncertainty in climate predictions further into the future. In addition to direct temperature effects on Least Cisco growth, we also considered changes in lake ice phenology and prey resources for Least Cisco. A shorter period of ice cover resulted in increased production, similar to warming temperatures. Altering prey quality had a larger effect on fish production in summer than winter and increased relative growth of younger rather than older age classes of Least Cisco. Overall, we predicted increased production of Least Cisco due to climate warming in lakes of Arctic Alaska. Understanding the implications of increased production of Least Cisco to the entire food web will be necessary to predict ecosystem responses in lakes of the Arctic.

Stress corrosion crack initiation of Zircaloy-4 cladding tubes in an iodine vapor environment during creep, relaxation, and constant strain rate tests

NASA Astrophysics Data System (ADS)

Jezequel, T.; Auzoux, Q.; Le Boulch, D.; Bono, M.; Andrieu, E.; Blanc, C.; Chabretou, V.; Mozzani, N.; Rautenberg, M.

2018-02-01

During accidental power transient conditions with Pellet Cladding Interaction (PCI), the synergistic effect of the stress and strain imposed on the cladding by thermal expansion of the fuel, and corrosion by iodine released as a fission product, may lead to cladding failure by Stress Corrosion Cracking (SCC). In this study, internal pressure tests were conducted on unirradiated cold-worked stress-relieved Zircaloy-4 cladding tubes in an iodine vapor environment. The goal was to investigate the influence of loading type (constant pressure tests, constant circumferential strain rate tests, or constant circumferential strain tests) and test temperature (320, 350, or 380 °C) on iodine-induced stress corrosion cracking (I-SCC). The experimental results obtained with different loading types were consistent with each other. The apparent threshold hoop stress for I-SCC was found to be independent of the test temperature. SEM micrographs of the tested samples showed many pits distributed over the inner surface, which tended to coalesce into large pits in which a microcrack could initiate. A model for the time-to-failure of a cladding tube was developed using finite element simulations of the viscoplastic mechanical behavior of the material and a modified Kachanov's damage growth model. The times-to-failure predicted by this model are consistent with the experimental data.

Characterizing Changes in the Rate of Protein-Protein Dissociation upon Interface Mutation Using Hotspot Energy and Organization

PubMed Central

Agius, Rudi; Torchala, Mieczyslaw; Moal, Iain H.; Fernández-Recio, Juan; Bates, Paul A.

2013-01-01

Predicting the effects of mutations on the kinetic rate constants of protein-protein interactions is central to both the modeling of complex diseases and the design of effective peptide drug inhibitors. However, while most studies have concentrated on the determination of association rate constants, dissociation rates have received less attention. In this work we take a novel approach by relating the changes in dissociation rates upon mutation to the energetics and architecture of hotspots and hotregions, by performing alanine scans pre- and post-mutation. From these scans, we design a set of descriptors that capture the change in hotspot energy and distribution. The method is benchmarked on 713 kinetically characterized mutations from the SKEMPI database. Our investigations show that, with the use of hotspot descriptors, energies from single-point alanine mutations may be used for the estimation of off-rate mutations to any residue type and also multi-point mutations. A number of machine learning models are built from a combination of molecular and hotspot descriptors, with the best models achieving a Pearson's Correlation Coefficient of 0.79 with experimental off-rates and a Matthew's Correlation Coefficient of 0.6 in the detection of rare stabilizing mutations. Using specialized feature selection models we identify descriptors that are highly specific and, conversely, broadly important to predicting the effects of different classes of mutations, interface regions and complexes. Our results also indicate that the distribution of the critical stability regions across protein-protein interfaces is a function of complex size more strongly than interface area. In addition, mutations at the rim are critical for the stability of small complexes, but consistently harder to characterize. The relationship between hotregion size and the dissociation rate is also investigated and, using hotspot descriptors which model cooperative effects within hotregions, we show how the contribution of hotregions of different sizes, changes under different cooperative effects. PMID:24039569

A new fitting law of rovibrationally inelastic rate constants for rapidly rotating molecules

NASA Astrophysics Data System (ADS)

Strekalov, M. L.

2005-04-01

Semiclassical scattering of a particle from a three-dimensional ellipsoid with internal structure is used to model vibration-rotation-translation (VRT) collisional transfer between atoms and diatomic molecules. The result is a very simple analytical expression containing two variable parameters that have a clear physical meaning. Predictions of the model for the Li 2 + Ne system are in reasonably good agreement with experimental results.

Simulating X-ray bursts during a transient accretion event

NASA Astrophysics Data System (ADS)

Johnston, Zac; Heger, Alexander; Galloway, Duncan K.

2018-06-01

Modelling of thermonuclear X-ray bursts on accreting neutron stars has to date focused on stable accretion rates. However, bursts are also observed during episodes of transient accretion. During such events, the accretion rate can evolve significantly between bursts, and this regime provides a unique test for burst models. The accretion-powered millisecond pulsar SAX J1808.4-3658 exhibits accretion outbursts every 2-3 yr. During the well-sampled month-long outburst of 2002 October, four helium-rich X-ray bursts were observed. Using this event as a test case, we present the first multizone simulations of X-ray bursts under a time-dependent accretion rate. We investigate the effect of using a time-dependent accretion rate in comparison to constant, averaged rates. Initial results suggest that using a constant, average accretion rate between bursts may underestimate the recurrence time when the accretion rate is decreasing, and overestimate it when the accretion rate is increasing. Our model, with an accreted hydrogen fraction of X = 0.44 and a CNO metallicity of ZCNO = 0.02, reproduces the observed burst arrival times and fluences with root mean square (rms) errors of 2.8 h, and 0.11× 10^{-6} erg cm^{-2}, respectively. Our results support previous modelling that predicted two unobserved bursts and indicate that additional bursts were also missed by observations.

Application of the compensated Arrhenius formalism to explain the dielectric constant dependence of rates for Menschutkin reactions.

PubMed

Petrowsky, Matt; Glatzhofer, Daniel T; Frech, Roger

2013-11-21

The dependence of the reaction rate on solvent dielectric constant is examined for the reaction of trihexylamine with 1-bromohexane in a series of 2-ketones over the temperature range 25-80 °C. The rate constant data are analyzed using the compensated Arrhenius formalism (CAF), where the rate constant assumes an Arrhenius-like equation that also contains a dielectric constant dependence in the exponential prefactor. The CAF activation energies are substantially higher than those obtained using the simple Arrhenius equation. A master curve of the data is observed by plotting the prefactors against the solvent dielectric constant. The master curve shows that the reaction rate has a weak dependence on dielectric constant for values approximately less than 10 and increases more rapidly for dielectric constant values greater than 10.

Potential of pressure solution for strain localization in the Baccu Locci Shear Zone (Sardinia, Italy)

NASA Astrophysics Data System (ADS)

Casini, Leonardo; Funedda, Antonio

2014-09-01

The mylonites of the Baccu Locci Shear Zone (BLSZ), Sardinia (Italy), were deformed during thrusting along a bottom-to-top strain gradient in lower greenschist facies. The microstructure of metavolcanic protoliths shows evidence for composite deformation accommodated by dislocation creep within strong quartz porphyroclasts, and pressure solution in the finer grained matrix. The evolution of mylonite is simulated in two sets of numerical experiments, assuming either a constant width of the deforming zone (model 1) or a narrowing shear zone (model 2). A 2-5 mm y-1 constant-external-velocity boundary condition is applied on the basis of geologic constraints. Inputs to the models are provided by inverting paleostress values obtained from quartz recrystallized grain-size paleopiezometry. Both models predict a significant stress drop across the shear zone. However, model 1 involves a dramatic decrease in strain rate towards the zone of apparent strain localization. In contrast, model 2 predicts an increase in strain rate with time (from 10-14 to 10-12 s-1), which is consistent with stabilization of the shear zone profile and localization of deformation near the hanging wall. Extrapolating these results to the general context of crust strength suggests that pressure-solution creep may be a critical process for strain softening and for the stabilization of deformation within shear zones.

Automated real time constant-specificity surveillance for disease outbreaks.

PubMed

Wieland, Shannon C; Brownstein, John S; Berger, Bonnie; Mandl, Kenneth D

2007-06-13

For real time surveillance, detection of abnormal disease patterns is based on a difference between patterns observed, and those predicted by models of historical data. The usefulness of outbreak detection strategies depends on their specificity; the false alarm rate affects the interpretation of alarms. We evaluate the specificity of five traditional models: autoregressive, Serfling, trimmed seasonal, wavelet-based, and generalized linear. We apply each to 12 years of emergency department visits for respiratory infection syndromes at a pediatric hospital, finding that the specificity of the five models was almost always a non-constant function of the day of the week, month, and year of the study (p < 0.05). We develop an outbreak detection method, called the expectation-variance model, based on generalized additive modeling to achieve a constant specificity by accounting for not only the expected number of visits, but also the variance of the number of visits. The expectation-variance model achieves constant specificity on all three time scales, as well as earlier detection and improved sensitivity compared to traditional methods in most circumstances. Modeling the variance of visit patterns enables real-time detection with known, constant specificity at all times. With constant specificity, public health practitioners can better interpret the alarms and better evaluate the cost-effectiveness of surveillance systems.

A full set of langatate high-temperature acoustic wave constants: elastic, piezoelectric, dielectric constants up to 900°C.

PubMed

Davulis, Peter M; da Cunha, Mauricio Pereira

2013-04-01

A full set of langatate (LGT) elastic, dielectric, and piezoelectric constants with their respective temperature coefficients up to 900°C is presented, and the relevance of the dielectric and piezoelectric constants and temperature coefficients are discussed with respect to predicted and measured high-temperature SAW propagation properties. The set of constants allows for high-temperature acoustic wave (AW) propagation studies and device design. The dielectric constants and polarization and conductive losses were extracted by impedance spectroscopy of parallel-plate capacitors. The measured dielectric constants at high temperatures were combined with previously measured LGT expansion coefficients and used to determine the elastic and piezoelectric constants using resonant ultrasound spectroscopy (RUS) measurements at temperatures up to 900°C. The extracted LGT piezoelectric constants and temperature coefficients show that e11 and e14 change by up to 62% and 77%, respectively, for the entire 25°C to 900°C range when compared with room-temperature values. The LGT high-temperature constants and temperature coefficients were verified by comparing measured and predicted phase velocities (vp) and temperature coefficients of delay (TCD) of SAW delay lines fabricated along 6 orientations in the LGT plane (90°, 23°, Ψ) up to 900°C. For the 6 tested orientations, the predicted SAW vp agree within 0.2% of the measured vp on average and the calculated TCD is within 9.6 ppm/°C of the measured value on average over the temperature range of 25°C to 900°C. By including the temperature dependence of both dielectric and piezoelectric constants, the average discrepancies between predicted and measured SAW properties were reduced, on average: 77% for vp, 13% for TCD, and 63% for the turn-over temperatures analyzed.

Additive effects on the energy barrier for synaptic vesicle fusion cause supralinear effects on the vesicle fusion rate

PubMed Central

Schotten, Sebastiaan; Meijer, Marieke; Walter, Alexander Matthias; Huson, Vincent; Mamer, Lauren; Kalogreades, Lawrence; ter Veer, Mirelle; Ruiter, Marvin; Brose, Nils; Rosenmund, Christian

2015-01-01

The energy required to fuse synaptic vesicles with the plasma membrane (‘activation energy’) is considered a major determinant in synaptic efficacy. From reaction rate theory, we predict that a class of modulations exists, which utilize linear modulation of the energy barrier for fusion to achieve supralinear effects on the fusion rate. To test this prediction experimentally, we developed a method to assess the number of releasable vesicles, rate constants for vesicle priming, unpriming, and fusion, and the activation energy for fusion by fitting a vesicle state model to synaptic responses induced by hypertonic solutions. We show that complexinI/II deficiency or phorbol ester stimulation indeed affects responses to hypertonic solution in a supralinear manner. An additive vs multiplicative relationship between activation energy and fusion rate provides a novel explanation for previously observed non-linear effects of genetic/pharmacological perturbations on synaptic transmission and a novel interpretation of the cooperative nature of Ca2+-dependent release. DOI: http://dx.doi.org/10.7554/eLife.05531.001 PMID:25871846

Future Declines of Coronary Heart Disease Mortality in England and Wales Could Counter the Burden of Population Ageing

PubMed Central

Guzman Castillo, Maria; Gillespie, Duncan O. S.; Allen, Kirk; Bandosz, Piotr; Schmid, Volker; Capewell, Simon; O’Flaherty, Martin

2014-01-01

Background Coronary Heart Disease (CHD) remains a major cause of mortality in the United Kingdom. Yet predictions of future CHD mortality are potentially problematic due to population ageing and increase in obesity and diabetes. Here we explore future projections of CHD mortality in England & Wales under two contrasting future trend assumptions. Methods In scenario A, we used the conventional counterfactual scenario that the last-observed CHD mortality rates from 2011 would persist unchanged to 2030. The future number of deaths was calculated by applying those rates to the 2012–2030 population estimates. In scenario B, we assumed that the recent falling trend in CHD mortality rates would continue. Using Lee-Carter and Bayesian Age Period Cohort (BAPC) models, we projected the linear trends up to 2030. We validate our methods using past data to predict mortality from 2002–2011. Then, we computed the error between observed and projected values. Results In scenario A, assuming that 2011 mortality rates stayed constant by 2030, the number of CHD deaths would increase 62% or approximately 39,600 additional deaths. In scenario B, assuming recent declines continued, the BAPC model (the model with lowest error) suggests the number of deaths will decrease by 56%, representing approximately 36,200 fewer deaths by 2030. Conclusions The decline in CHD mortality has been reasonably continuous since 1979, and there is little reason to believe it will soon halt. The commonly used assumption that mortality will remain constant from 2011 therefore appears slightly dubious. By contrast, using the BAPC model and assuming continuing mortality falls offers a more plausible prediction of future trends. Thus, despite population ageing, the number of CHD deaths might halve again between 2011 and 2030. This has implications for how the potential benefits of future cardiovascular strategies might best be calculated and presented. PMID:24918442

Modelling the influence of time and temperature on the respiration rate of fresh oyster mushrooms.

PubMed

Azevedo, Sílvia; Cunha, Luís M; Fonseca, Susana C

2015-12-01

The respiration rate of mushrooms is an important indicator of postharvest senescence. Storage temperature plays a major role in their rate of respiration and, therefore, in their postharvest life. In this context, reliable predictions of respiration rates are critical for the development of modified atmosphere packaging that ultimately will maximise the quality of the product to be presented to consumers. This work was undertaken to study the influence of storage time and temperature on the respiration rate of oyster mushrooms. For that purpose, oyster mushrooms were stored at constant temperatures of 2, 6, 10, 14 and 18 ℃ under ambient atmosphere. Respiration rate data were measured with 8-h intervals up to 240 h. A decrease of respiration rate was found after cutting of the carpophores. Therefore, time effect on respiration rate was modelled using a first-order decay model. The results also show the positive influence of temperature on mushroom respiration rate. The model explaining the effect of time on oyster mushroom's respiration rate included the temperature dependence according to the Arrhenius equation, and the inclusion of a parameter describing the decrease of the respiration rate, from the initial time until equilibrium. These yielded an overall model that fitted well to the experimental data. Moreover, results show that the overall model is useful to predict respiration rate of oyster mushrooms at different temperatures and times, using the initial respiration rate of mushrooms. Furthermore, predictive modelling can be relevant for the choice of an appropriate packaging system for fresh oyster mushrooms. © The Author(s) 2014.

Subepidermal moisture detection of pressure induced tissue damage on the trunk: The pressure ulcer detection study outcomes.

PubMed

Bates-Jensen, Barbara M; McCreath, Heather E; Patlan, Anabel

2017-05-01

We examined the relationship between subepidermal moisture measured using surface electrical capacitance and visual skin assessment of pressure ulcers at the trunk location (sacral, ischial tuberosities) in 417 nursing home residents residing in 19 facilities. Participants were on average older (mean age of 77 years), 58% were female, over half were ethnic minorities (29% African American, 12% Asian American, and 21% Hispanic), and at risk for pressure ulcers (mean score for Braden Scale for Predicting Pressure Ulcer Risk of 15.6). Concurrent visual assessments and subepidermal moisture were obtained at the sacrum and right and left ischium weekly for 16 weeks. Visual assessment was categorized as normal, erythema, stage 1 pressure ulcer, Deep Tissue Injury or stage 2+ pressure ulcer using the National Pressure Ulcer Advisory Panel 2009 classification system. Incidence of any skin damage was 52%. Subepidermal moisture was measured with a dermal phase meter where higher readings indicate greater moisture (range: 0-70 tissue dielectric constant), with values increasing significantly with the presence of skin damage. Elevated subepidermal moisture values co-occurred with concurrent skin damage in generalized multinomial logistic models (to control for repeated observations) at the sacrum, adjusting for age and risk. Higher subepidermal moisture values were associated with visual damage 1 week later using similar models. Threshold values for subepidermal moisture were compared to visual ratings to predict skin damage 1 week later. Subepidermal moisture of 39 tissue dielectric constant units predicted 41% of future skin damage while visual ratings predicted 27%. Thus, this method of detecting early skin damage holds promise for clinicians, especially as it is objective and equally valid for all groups of patients. © 2017 by the Wound Healing Society.

Bare soil respiration in a temperate climate: multiyear evaluation of a coupled CO2 transport and carbon turnover model

NASA Astrophysics Data System (ADS)

Herbst, M.; Hellebrand, H. J.; Bauer, J.; Vanderborght, J.; Vereecken, H.

2006-12-01

The modelling of soil respiration plays an important role in the prediction of climate change. Soil respiration is usually divided in autotrophic and heterotrophic fractions orginating from root respiration and microbial decomposition of soil organic carbon, respectively. We report on the coupling of a one dimensional water, heat and CO2 flux model (SOILCO2) with a model of carbon turnover (RothC) for the prediction of soil heterotrophic respiration. The coupled model was tested using soil temperature, soil moisture, and CO2 flux measurements in a bare soil experimental plot located in Bornim, Germany. A seven year record of soil and CO2 measurements covering a broad range of atmospheric and soil conditions was availabe to evaluate the model performance. After calibrating the decomposition rate constant of the humic fraction pool, the overall model performance on CO2 efflux prediction was acceptable. The root mean square error for the CO2 efflux prediction was 0.12 cm ³/cm ²/d. During the severe summer draught of 2003 very high CO2 efluxes were measured, which could not be explained by the model. Those high fluxes were attributed to a pressure pumping effect. The soil temperature dependency of CO2 production was well described by th e model, whereas the biggest opportunity for improvement is seen in a better description of the soil moisture dependency of CO2 production. The calibration of the humus decomposition rate constant revealed a value of 0.09 1/d, which is higher than the original value suggested by the RothC model developers but within the range of literature values.

Rate constants measured for hydrated electron reactions with peptides and proteins

NASA Technical Reports Server (NTRS)

Braams, R.

1968-01-01

Effects of ionizing radiation on the amino acids of proteins and the reactivity of the protonated amino group depends upon the pK subscript a of the group. Estimates of the rate constants for reactions involving the amino acid side chains are presented. These rate constants gave an approximate rate constant for three different protein molecules.

Fire ants perpetually rebuild sinking towers.

PubMed

Phonekeo, Sulisay; Mlot, Nathan; Monaenkova, Daria; Hu, David L; Tovey, Craig

2017-07-01

In the aftermath of a flood, fire ants, Solenopsis invicta , cluster into temporary encampments. The encampments can contain hundreds of thousands of ants and reach over 30 ants high. How do ants build such tall structures without being crushed? In this combined experimental and theoretical study, we investigate the shape and rate of construction of ant towers around a central support. The towers are bell shaped, consistent with towers of constant strength such as the Eiffel tower, where each element bears an equal load. However, unlike the Eiffel tower, the ant tower is built through a process of trial and error, whereby failed portions avalanche until the final shape emerges. High-speed and novel X-ray videography reveal that the tower constantly sinks and is rebuilt, reminiscent of large multicellular systems such as human skin. We combine the behavioural rules that produce rafts on water with measurements of adhesion and attachment strength to model the rate of growth of the tower. The model correctly predicts that the growth rate decreases as the support diameter increases. This work may inspire the design of synthetic swarms capable of building in vertical layers.

Fire ants perpetually rebuild sinking towers

NASA Astrophysics Data System (ADS)

Phonekeo, Sulisay; Mlot, Nathan; Monaenkova, Daria; Hu, David L.; Tovey, Craig

2017-07-01

In the aftermath of a flood, fire ants, Solenopsis invicta, cluster into temporary encampments. The encampments can contain hundreds of thousands of ants and reach over 30 ants high. How do ants build such tall structures without being crushed? In this combined experimental and theoretical study, we investigate the shape and rate of construction of ant towers around a central support. The towers are bell shaped, consistent with towers of constant strength such as the Eiffel tower, where each element bears an equal load. However, unlike the Eiffel tower, the ant tower is built through a process of trial and error, whereby failed portions avalanche until the final shape emerges. High-speed and novel X-ray videography reveal that the tower constantly sinks and is rebuilt, reminiscent of large multicellular systems such as human skin. We combine the behavioural rules that produce rafts on water with measurements of adhesion and attachment strength to model the rate of growth of the tower. The model correctly predicts that the growth rate decreases as the support diameter increases. This work may inspire the design of synthetic swarms capable of building in vertical layers.

Fire ants perpetually rebuild sinking towers

PubMed Central

Phonekeo, Sulisay; Mlot, Nathan; Monaenkova, Daria; Tovey, Craig

2017-01-01

In the aftermath of a flood, fire ants, Solenopsis invicta, cluster into temporary encampments. The encampments can contain hundreds of thousands of ants and reach over 30 ants high. How do ants build such tall structures without being crushed? In this combined experimental and theoretical study, we investigate the shape and rate of construction of ant towers around a central support. The towers are bell shaped, consistent with towers of constant strength such as the Eiffel tower, where each element bears an equal load. However, unlike the Eiffel tower, the ant tower is built through a process of trial and error, whereby failed portions avalanche until the final shape emerges. High-speed and novel X-ray videography reveal that the tower constantly sinks and is rebuilt, reminiscent of large multicellular systems such as human skin. We combine the behavioural rules that produce rafts on water with measurements of adhesion and attachment strength to model the rate of growth of the tower. The model correctly predicts that the growth rate decreases as the support diameter increases. This work may inspire the design of synthetic swarms capable of building in vertical layers. PMID:28791170

Acceleration and sensitivity analysis of lattice kinetic Monte Carlo simulations using parallel processing and rate constant rescaling

NASA Astrophysics Data System (ADS)

Núñez, M.; Robie, T.; Vlachos, D. G.

2017-10-01

Kinetic Monte Carlo (KMC) simulation provides insights into catalytic reactions unobtainable with either experiments or mean-field microkinetic models. Sensitivity analysis of KMC models assesses the robustness of the predictions to parametric perturbations and identifies rate determining steps in a chemical reaction network. Stiffness in the chemical reaction network, a ubiquitous feature, demands lengthy run times for KMC models and renders efficient sensitivity analysis based on the likelihood ratio method unusable. We address the challenge of efficiently conducting KMC simulations and performing accurate sensitivity analysis in systems with unknown time scales by employing two acceleration techniques: rate constant rescaling and parallel processing. We develop statistical criteria that ensure sufficient sampling of non-equilibrium steady state conditions. Our approach provides the twofold benefit of accelerating the simulation itself and enabling likelihood ratio sensitivity analysis, which provides further speedup relative to finite difference sensitivity analysis. As a result, the likelihood ratio method can be applied to real chemistry. We apply our methodology to the water-gas shift reaction on Pt(111).

Communication: Prediction of the rate constant of bimolecular hydrogen exchange in the water dimer using an ab initio potential energy surface.

PubMed

Wang, Yimin; Bowman, Joel M; Huang, Xinchuan

2010-09-21

We report the properties of two novel transition states of the bimolecular hydrogen exchange reaction in the water dimer, based on an ab initio water dimer potential [A. Shank et al., J. Chem. Phys. 130, 144314 (2009)]. The realism of the two transition states is assessed by comparing structures, energies, and harmonic frequencies obtained from the potential energy surface and new high-level ab initio calculations. The rate constant for the exchange is obtained using conventional transition state theory with a tunneling correction. We employ a one-dimensional approach for the tunneling calculations using a relaxed potential from the full-dimensional potential in the imaginary-frequency normal mode of the saddle point, Q(im). The accuracy of this one-dimensional approach has been shown for the ground-state tunneling splittings for H and D-transfer in malonaldehyde and for the D+H(2) reaction [Y. Wang and J. M. Bowman, J. Chem. Phys. 129, 121103 (2008)]. This approach is applied to calculate the rate constant for the H(2)O+H(2)O exchange and also for H(2)O+D(2)O→2HOD. The local zero-point energy is also obtained using diffusion Monte Carlo calculations in the space of real-frequency-saddle-point normal modes, as a function of Q(im).

Reactivity of substituted benzotrichlorides toward granular iron, Cr(II), and an iron(II) porphyrin: A correlation analysis.

PubMed

Kohn, Tamar; Arnold, William A; Roberts, A Lynn

2006-07-01

Cross-correlations of rate constants between a system of interest and a better-defined one have become popular as a tool in studying transformations of organic pollutants. A slope of unity (if the correlation is conducted on a log-log basis) in such plots has been invoked as evidence of a common mechanism. To explore this notion, benzotrichloride and several of its substituted analogues were reacted with Cr(H2O)6(2+), an iron(II) porphyrin (iron meso-tetra(4-carboxyphenyl)porphine chloride, Fe(II)TCP), and granular iron. The first two reductants react with organohalides by dissociative inner sphere single-electron transfer, while mechanism(s) for organohalide reduction by granular iron are still debated. Apartfrom sterically hindered compounds, good correlations were obtained in comparing any two systems, although slopes (on a log-log basis) deviated from unity. We argue that a slope of unity is neither necessary nor sufficient evidence of a common mechanism. Overall rate constants may be composite entities, consisting in part of rate or equilibrium constants for adsorption onto surfaces or for precursor formation in solution; these components may differ between systems in their susceptibility to substituent effects. Cross-correlations may prove useful in predicting reactivity in the absence of steric effects, but additional evidence is required in deducing reaction mechanisms.

Theoretical study of the vibrational relaxation of the methyl radical in collisions with helium

NASA Astrophysics Data System (ADS)

Ma, Qianli; Dagdigian, Paul J.; Alexander, Millard H.

2013-03-01

We report a theoretical investigation of the relaxation of the umbrella vibrational mode (the ν2 mode) of the CH3 molecule in its ground tilde{X}^2A_2^' ' } electronic state in collisions with helium. We have calculated a four-dimensional potential energy surface (PES) for the interaction between CH3 with different umbrella displacements and a helium atom, using a restricted open-shell coupled-cluster method with inclusion of all single, double, and (perturbatively) triple excitations [RCCSD(T)]. With this PES we carried out full close-coupling scattering calculations including all CH3 umbrella-rotational levels with v2 ⩽ 3. To our knowledge, this work represents the first fully quantum calculations of ro-vibrational relaxation of a polyatomic. In more detail, we investigate propensities in the calculated ro-vibrational cross sections and the dependence on initial rotational excitation, as well as determining thermal rate constants. Overall, ro-vibrational relaxation is nearly two orders of magnitude less efficient than pure-rotational relaxation, with a noticeable dependence on the initial rotational level. We predict the room temperature v2 = 1 vibrational relaxation rate constant to be 5.4 × 10-12 cm3 molecule-1 s-1, compared to the rate constants for pure-rotational relaxation of the lower rotational levels (˜2.0 × 10-10 cm3 molecule-1 s-1).

The theory of cyclic voltammetry of electrochemically heterogeneous surfaces: comparison of different models for surface geometry and applications to highly ordered pyrolytic graphite.

PubMed

Ward, Kristopher R; Lawrence, Nathan S; Hartshorne, R Seth; Compton, Richard G

2012-05-28

The cyclic voltammetry at electrodes composed of multiple electroactive materials, where zones of one highly active material are distributed over a substrate of a second, less active material, is investigated by simulation. The two materials are assumed to differ in terms of their electrochemical rate constants towards any given redox couple. For a one-electron oxidation or reduction, the effect on voltammetry of the size and relative surface coverages of the zones as well as the rate constant of the slower zone are considered for systems where it is much slower than the rate constant of the faster zones. The occurrence of split peak cyclic voltammetry where two peaks are observed in the forward sweep, is studied in terms of the diffusional effects present in the system. A number of surface geometries are compared: specifically the more active zones are modelled as long, thin bands, as steps in the surface, as discs, and as rings (similar to a partially blocked electrode). Similar voltammetry for the band, step and ring models is seen but the disc geometry shows significant differences. Finally, the simulation technique is applied to the modelling of highly-ordered pyrolytic graphite (HOPG) surface and experimental conditions under which it may be possible to observe split peak voltammetry are predicted.

Phi-value analysis of a linear, sequential reaction mechanism: theory and application to ion channel gating.

PubMed

Zhou, Yu; Pearson, John E; Auerbach, Anthony

2005-12-01

We derive the analytical form of a rate-equilibrium free-energy relationship (with slope Phi) for a bounded, linear chain of coupled reactions having arbitrary connecting rate constants. The results confirm previous simulation studies showing that Phi-values reflect the position of the perturbed reaction within the chain, with reactions occurring earlier in the sequence producing higher Phi-values than those occurring later in the sequence. The derivation includes an expression for the transmission coefficients of the overall reaction based on the rate constants of an arbitrary, discrete, finite Markov chain. The results indicate that experimental Phi-values can be used to calculate the relative heights of the energy barriers between intermediate states of the chain but provide no information about the energies of the wells along the reaction path. Application of the equations to the case of diliganded acetylcholine receptor channel gating suggests that the transition-state ensemble for this reaction is nearly flat. Although this mechanism accounts for many of the basic features of diliganded and unliganded acetylcholine receptor channel gating, the experimental rate-equilibrium free-energy relationships appear to be more linear than those predicted by the theory.

Effects of multiple predator species on green treefrog (Hyla cinerea) tadpoles

USGS Publications Warehouse

Gunzburger, M.S.; Travis, J.

2005-01-01

Prey species that occur across a range of habitats may be exposed to variable communities of multiple predator species across habitats. Predicting the combined effects of multiple predators can be complex. Many experiments evaluating the effects of multiple predators on prey confound either variation in predator density with predator identity or variation in relative predator frequency with overall predation rates. We develop a new experimental design of factorial predator combinations that maintains a constant expected predation rate, under the null hypothesis of additive predator effects. We implement this design to evaluate the combined effects of three predator species (bass, aeshnid and libellulid odonate naiads) on mortality rate of a prey species, Hyla cinerea (Schneider, 1799) tadpoles, that occurs across a range of aquatic habitats. Two predator treatments (libellulid and aeshnid + libellulid) resulted in lower tadpole mortality than any of the other predator treatments. Variation in tadpole mortality across treatments was not related to coarse variation in microhabitat use, but was likely due to intraguild predation, which occurred in all predator treatments. Hyla cinerea tadpoles have constant, low survival values when exposed to many different combinations of predator species, and predation rate probably increases linearly with predator density.

A kinetic model of the formation of organic monolayers on hydrogen-terminated silicon by hydrosilation of alkenes.

PubMed

Woods, M; Carlsson, S; Hong, Q; Patole, S N; Lie, L H; Houlton, A; Horrocks, B R

2005-12-22

We have analyzed a kinetic model for the formation of organic monolayers based on a previously suggested free radical chain mechanism for the reaction of unsaturated molecules with hydrogen-terminated silicon surfaces (Linford, M. R.; Fenter, P. M.; Chidsey, C. E. D. J. Am. Chem. Soc 1995, 117, 3145). A direct consequence of this mechanism is the nonexponential growth of the monolayer, and this has been observed spectroscopically. In the model, the initiation of silyl radicals on the surface is pseudo first order with rate constant, ki, and the rate of propagation is determined by the concentration of radicals and unreacted Si-H nearest neighbor sites with a rate constant, kp. This propagation step determines the rate at which the monolayer forms by addition of alkene molecules to form a track of molecules that constitute a self-avoiding random walk on the surface. The initiation step describes how frequently new random walks commence. A termination step by which the radicals are destroyed is also included. The solution of the kinetic equations yields the fraction of alkylated surface sites and the mean length of the random walks as a function of time. In mean-field approximation we show that (1) the average length of the random walk is proportional to (kp/ki)1/2, (2) the monolayer surface coverage grows exponentially only after an induction period, (3) the effective first-order rate constant describing the growth of the monolayer and the induction period (kt) is k = (2ki kp)1/2, (4) at long times the effective first-order rate constant drops to ki, and (5) the overall activation energy for the growth kinetics is the mean of the activation energies for the initiation and propagation steps. Monte Carlo simulations of the mechanism produce qualitatively similar kinetic plots, but the mean random walk length (and effective rate constant) is overestimated by the mean field approximation and when kp > ki, we find k approximately ki0.7kp0.3 and Ea = (0.7Ei+ 0.3Ep). However the most striking prediction of the Monte Carlo simulations is that at long times, t > 1/k, the effective first-order rate constant decreases to ki even in the absence of a chemical termination step. Experimental kinetic data for the reaction of undec-1-ene with hydrogen-terminated porous silicon under thermal reflux in toluene and ethylbenzene gave a value of k = 0.06 min(-1) and an activation energy of 107 kJ mol(-1). The activation energy is in reasonable agreement with density functional calculations of the transition state energies for the initiation and propagation steps.

Life Prediction/Reliability Data of Glass-Ceramic Material Determined for Radome Applications

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Gyekenyesi, John P.

2002-01-01

Brittle materials, ceramics, are candidate materials for a variety of structural applications for a wide range of temperatures. However, the process of slow crack growth, occurring in any loading configuration, limits the service life of structural components. Therefore, it is important to accurately determine the slow crack growth parameters required for component life prediction using an appropriate test methodology. This test methodology also should be useful in determining the influence of component processing and composition variables on the slow crack growth behavior of newly developed or existing materials, thereby allowing the component processing and composition to be tailored and optimized to specific needs. Through the American Society for Testing and Materials (ASTM), the authors recently developed two test methods to determine the life prediction parameters of ceramics. The two test standards, ASTM 1368 for room temperature and ASTM C 1465 for elevated temperatures, were published in the 2001 Annual Book of ASTM Standards, Vol. 15.01. Briefly, the test method employs constant stress-rate (or dynamic fatigue) testing to determine flexural strengths as a function of the applied stress rate. The merit of this test method lies in its simplicity: strengths are measured in a routine manner in flexure at four or more applied stress rates with an appropriate number of test specimens at each applied stress rate. The slow crack growth parameters necessary for life prediction are then determined from a simple relationship between the strength and the applied stress rate. Extensive life prediction testing was conducted at the NASA Glenn Research Center using the developed ASTM C 1368 test method to determine the life prediction parameters of a glass-ceramic material that the Navy will use for radome applications.

Impacts of Daily Bag Limit Reductions on Angler Effort in Wisconsin Walleye Lakes

USGS Publications Warehouse

Beard, T.D.; Cox, S.P.; Carpenter, S.R.

2003-01-01

Angler effort is an important factor affecting recreational fisheries. However, angler responses are rarely incorporated into recreational fisheries regulations or predictions. Few have attempted to examine how daily bag limit regulations affect total angling pressure and subsequent stock densities. Our paper develops a theoretical basis for predicting angler effort and harvest rate based on stock densities and bag limit regulations. We examined data from a management system that controls the total exploitation of walleyes Sander vitreus (formerly Stizostedion vitreum) in northern Wisconsin lakes and compared these empirical results with the predictions from a theoretical effort and harvest rate response model. The data indicated that higher general angler effort occurs on lakes regulated with a 5-walleye daily limit than on lakes regulated with either a 2- or 3-walleye daily limit. General walleye catch rates were lower on lakes with a 5-walleye limit than on lakes with either a 2- or 3-walleye daily limit. An effort response model predicted a logarithmic relationship between angler effort and adult walleye density and that an index of attractiveness would be greater on lakes with high bag limits. Predictions from the harvest rate model with constant walleye catchability indicated that harvest rates increased nonlinearly with increasing density. When the effort model was fitted to data from northern Wisconsin, we found higher lake attractiveness at 5-walleye-limit lakes. We conclude that different groups of anglers respond differently to bag limit changes and that reliance on daily bag limits may not be sufficient to maintain high walleye densities in some lakes in this region.

Analysis of turbulence and surface growth models on the estimation of soot level in ethylene non-premixed flames

NASA Astrophysics Data System (ADS)

Yunardi, Y.; Munawar, Edi; Rinaldi, Wahyu; Razali, Asbar; Iskandar, Elwina; Fairweather, M.

2018-02-01

Soot prediction in a combustion system has become a subject of attention, as many factors influence its accuracy. An accurate temperature prediction will likely yield better soot predictions, since the inception, growth and destruction of the soot are affected by the temperature. This paper reported the study on the influences of turbulence closure and surface growth models on the prediction of soot levels in turbulent flames. The results demonstrated that a substantial distinction was observed in terms of temperature predictions derived using the k-ɛ and the Reynolds stress models, for the two ethylene flames studied here amongst the four types of surface growth rate model investigated, the assumption of the soot surface growth rate proportional to the particle number density, but independent on the surface area of soot particles, f ( A s ) = ρ N s , yields in closest agreement with the radial data. Without any adjustment to the constants in the surface growth term, other approaches where the surface growth directly proportional to the surface area and square root of surface area, f ( A s ) = A s and f ( A s ) = √ A s , result in an under- prediction of soot volume fraction. These results suggest that predictions of soot volume fraction are sensitive to the modelling of surface growth.

Constraining slip rates and spacings for active normal faults

NASA Astrophysics Data System (ADS)

Cowie, Patience A.; Roberts, Gerald P.

2001-12-01

Numerous observations of extensional provinces indicate that neighbouring faults commonly slip at different rates and, moreover, may be active over different time intervals. These published observations include variations in slip rate measured along-strike of a fault array or fault zone, as well as significant across-strike differences in the timing and rates of movement on faults that have a similar orientation with respect to the regional stress field. Here we review published examples from the western USA, the North Sea, and central Greece, and present new data from the Italian Apennines that support the idea that such variations are systematic and thus to some extent predictable. The basis for the prediction is that: (1) the way in which a fault grows is fundamentally controlled by the ratio of maximum displacement to length, and (2) the regional strain rate must remain approximately constant through time. We show how data on fault lengths and displacements can be used to model the observed patterns of long-term slip rate where measured values are sparse. Specifically, we estimate the magnitude of spatial variation in slip rate along-strike and relate it to the across-strike spacing between active faults.

Computational study of duct and pipe flows using the method of pseudocompressibility

NASA Technical Reports Server (NTRS)

Williams, Robert W.

1991-01-01

A viscous, three-dimensional, incompressible, Navier-Stokes Computational Fluid Dynamics code employing pseudocompressibility is used for the prediction of laminar primary and secondary flows in two 90-degree bends of constant cross section. Under study are a square cross section duct bend with 2.3 radius ratio and a round cross section pipe bend with 2.8 radius ratio. Sensitivity of predicted primary and secondary flow to inlet boundary conditions, grid resolution, and code convergence is investigated. Contour and velocity versus spanwise coordinate plots comparing prediction to experimental data flow components are shown at several streamwise stations before, within, and after the duct and pipe bends. Discussion includes secondary flow physics, computational method, computational requirements, grid dependence, and convergence rates.

Simulating the volatilization of solvents in unsaturated soils during laboratory and field infiltration experiments

USGS Publications Warehouse

Cho, H. Jean; Jaffe, Peter R.; Smith, James A.

1993-01-01

This paper describes laboratory and field experiments which were conducted to study the dynamics of trichloroethylene (TCE) as it volatilized from contaminated groundwater and diffused in the presence of infiltrating water through the unsaturated soil zone to the land surface. The field experiments were conducted at the Picatinny Arsenal, which is part of the United States Geological Survey Toxic Substances Hydrology Program. In both laboratory and field settings the gas and water phase concentrations of TCE were not in equilibrium during infiltration. Gas-water mass transfer rate constants were calibrated to the experimental data using a model in which the water phase was treated as two phases: a mobile water phase and an immobile water phase. The mass transfer limitations of a volatile organic compound between the gas and liquid phases were described explicitly in the model. In the laboratory experiment the porous medium was nonsorbing, and water infiltration rates ranged from 0.076 to 0.28 cm h−1. In the field experiment the water infiltration rate was 0.34 cm h−1, and sorption onto the soil matrix was significant. The laboratory-calibrated gas-water mass transfer rate constant is 3.3×10−4 h−1 for an infiltration rate of 0.076 cm h−1 and 1.4×10−3 h−1 for an infiltration rate of 0.28 cm h−1. The overall mass transfer rate coefficients, incorporating the contribution of mass transfer between mobile and immobile water phases and the variation of interfacial area with moisture content, range from 3×10−4 h−1 to 1×10−2 h−1. A power law model relates the gas-water mass transfer rate constant to the infiltration rate and the fraction of the water phase which is mobile. It was found that the results from the laboratory experiments could not be extrapolated to the field. In order to simulate the field experiment the very slow desorption of TCE from the soil matrix was incorporated into the mathematical model. When desorption from the soil matrix was added to the model, the calibrated gas-water mass transfer rate constant is 2 orders of magnitude lower than that predicted using the power law model developed for the nonsorbing laboratory soil.

Theoretical aspects of stress corrosion cracking of Alloy 22

NASA Astrophysics Data System (ADS)

Lee, Sang-Kwon; Macdonald, Digby D.

2018-05-01

Theoretical aspects of the stress corrosion cracking of Alloy 22 in contact with saturated NaCl solution are explored in terms of the Coupled Environment Fracture Model (CEFM), which was calibrated upon available experimental crack growth rate data. Crack growth rate (CGR) was then predicted as a function of stress intensity, electrochemical potential, solution conductivity, temperature, and electrochemical crack length (ECL). From the dependence of the CGR on the ECL and the evolution of a semi-elliptical surface crack in a planar surface under constant loading conditions it is predicted that penetration through the 2.5-cm thick Alloy 22 corrosion resistant layer of the waste package (WP) could occur 32,000 years after nucleation. Accordingly, the crack must nucleate within the first 968,000 years of storage. However, we predict that the Alloy 22 corrosion resistant layer will not be penetrated by SCC within the 10,000-year Intermediate Performance Period, even if a crack nucleates immediately upon placement of the WP in the repository.

The effects of surface evaporation parameterizations on climate sensitivity to solar constant variations

NASA Technical Reports Server (NTRS)

Chou, S.-H.; Curran, R. J.; Ohring, G.

1981-01-01

The effects of two different evaporation parameterizations on the sensitivity of simulated climate to solar constant variations are investigated by using a zonally averaged climate model. One parameterization is a nonlinear formulation in which the evaporation is nonlinearly proportional to the sensible heat flux, with the Bowen ratio determined by the predicted vertical temperature and humidity gradients near the earth's surface (model A). The other is the formulation of Saltzman (1968) with the evaporation linearly proportional to the sensible heat flux (model B). The computed climates of models A and B are in good agreement except for the energy partition between sensible and latent heat at the earth's surface. The difference in evaporation parameterizations causes a difference in the response of temperature lapse rate to solar constant variations and a difference in the sensitivity of longwave radiation to surface temperature which leads to a smaller sensitivity of surface temperature to solar constant variations in model A than in model B. The results of model A are qualitatively in agreement with those of the general circulation model calculations of Wetherald and Manabe (1975).

[Effect of heat transfer in the packages on the stability of thiamine nitrate under uncontrolled temperature conditions].

PubMed

Nakamura, Toru; Yamaji, Takayuki; Takayama, Kozo

2013-01-01

To accurately predict the stability of thiamine nitrate as a model drug in pharmaceutical products under uncontrolled temperature conditions, the average reaction rate constant was determined, taking into account the heat transfer from the atmosphere to the product. The stability tests of thiamine nitrate in the three packages with different heat transfers were performed under non-isothermal conditions. The stability data observed were compared with the predictions based on a newly developed method, showing that the stability was well predicted by the method involving the heat transfer. By contrast, there were some deviations observed from the predicted data, without considering heat transfer in the packages with low heat transfer. The above-mentioned result clearly shows that heat transfer should be considered to ensure accurate prediction of the stability of commercial pharmaceutical products under non-isothermal atmospheres.

SU-G-201-06: Directional Low-Dose Rate Brachytherapy: Determination of the TG-43 Dose-Rate Constant Analog for a New Pd-103 Source

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

Aima, M; Culberson, W; Hammer, C

Purpose: The aim of this work is to determine the TG-43 dose-rate constant analog for a new directional low-dose rate brachytherapy source based on experimental methods and comparison to Monte Carlo simulations. The CivaSheet™ is a new commercially available planar source array comprised of a variable number of discrete directional source elements called “CivaDots”. Given the directional nature and non-conventional design of the source, modifications to the AAPM TG-43 protocol for dosimetry are required. As a result, various parameters of the TG-43 dosimetric formalism have to be adapted to accommodate this source. This work focuses on the dose-rate constant analogmore » determination for a CivaDot. Methods: Dose to water measurements of the CivaDot were performed in a polymethyl methacrylate phantom (20×20×12 cm{sup 3}) using thermoluminescent dosimeters (TLDs) and Gafchromic EBT3 film. The source was placed in the center of the phantom, and nine TLD micro-cubes were irradiated along its central axis at a distance of 1 cm. For the film measurements, the TLDs were substituted by a (3×3) cm{sup 2} EBT3 film. Primary air-kerma strength measurements of the source were performed using a variable-aperture free-air chamber. Finally, the source was modeled using the Monte Carlo N-Particle Transport Code 6. Results: Dose-rate constant analog observed for a total of eight CivaDots using TLDs and five CivaDots using EBT3 film was within ±7.0% and ±2.9% of the Monte Carlo predicted value respectively. The average difference observed was −4.8% and −0.1% with a standard deviation of 1.7% and 2.1% for the TLD and the film measurements respectively, which are both within the comparison uncertainty. Conclusion: A preliminary investigation to determine the doserate constant analog for a CivaDot was conducted successfully with good agreement between experimental and Monte Carlo based methods. This work will aid in the eventual realization of a clinically-viable dosimetric framework for the CivaSheet. This work was partially supported by NCI contract (HHSN261201200052C) through CivaTech Oncology Inc.« less

A mixing timescale model for TPDF simulations of turbulent premixed flames

DOE PAGES

Kuron, Michael; Ren, Zhuyin; Hawkes, Evatt R.; ...

2017-02-06

Transported probability density function (TPDF) methods are an attractive modeling approach for turbulent flames as chemical reactions appear in closed form. However, molecular micro-mixing needs to be modeled and this modeling is considered a primary challenge for TPDF methods. In the present study, a new algebraic mixing rate model for TPDF simulations of turbulent premixed flames is proposed, which is a key ingredient in commonly used molecular mixing models. The new model aims to properly account for the transition in reactive scalar mixing rate behavior from the limit of turbulence-dominated mixing to molecular mixing behavior in flamelets. An a priorimore » assessment of the new model is performed using direct numerical simulation (DNS) data of a lean premixed hydrogen–air jet flame. The new model accurately captures the mixing timescale behavior in the DNS and is found to be a significant improvement over the commonly used constant mechanical-to-scalar mixing timescale ratio model. An a posteriori TPDF study is then performed using the same DNS data as a numerical test bed. The DNS provides the initial conditions and time-varying input quantities, including the mean velocity, turbulent diffusion coefficient, and modeled scalar mixing rate for the TPDF simulations, thus allowing an exclusive focus on the mixing model. Here, the new mixing timescale model is compared with the constant mechanical-to-scalar mixing timescale ratio coupled with the Euclidean Minimum Spanning Tree (EMST) mixing model, as well as a laminar flamelet closure. It is found that the laminar flamelet closure is unable to properly capture the mixing behavior in the thin reaction zones regime while the constant mechanical-to-scalar mixing timescale model under-predicts the flame speed. Furthermore, the EMST model coupled with the new mixing timescale model provides the best prediction of the flame structure and flame propagation among the models tested, as the dynamics of reactive scalar mixing across different flame regimes are appropriately accounted for.« less

Density functional theory study on aqueous aluminum-fluoride complexes: exploration of the intrinsic relationship between water-exchange rate constants and structural parameters for monomer aluminum complexes.

PubMed

Jin, Xiaoyan; Qian, Zhaosheng; Lu, Bangmei; Yang, Wenjing; Bi, Shuping

2011-01-01

Density functional theory (DFT) calculation is carried out to investigate the structures, (19)F and (27)Al NMR chemical shifts of aqueous Al-F complexes and their water-exchange reactions. The following investigations are performed in this paper: (1) the microscopic properties of typical aqueous Al-F complexes are obtained at the level of B3LYP/6-311+G**. Al-OH(2) bond lengths increase with F(-) replacing inner-sphere H(2)O progressively, indicating labilizing effect of F(-) ligand. The Al-OH(2) distance trans to fluoride is longer than other Al-OH(2) distance, accounting for trans effect of F(-) ligand. (19)F and (27)Al NMR chemical shifts are calculated using GIAO method at the HF/6-311+G** level relative to F(H(2)O)(6)(-) and Al(H(2)O)(6)(3+) references, respectively. The results are consistent with available experimental values; (2) the dissociative (D) activated mechanism is observed by modeling water-exchange reaction for [Al(H(2)O)(6-i)F(i)]((3-i)+) (i = 1-4). The activation energy barriers are found to decrease with increasing F(-) substitution, which is in line with experimental rate constants (k(ex)). The log k(ex) of AlF(3)(H(2)O)(3)(0) and AlF(4)(H(2)O)(2)(-) are predicted by three ways. The results indicate that the correlation between log k(ex) and Al-O bond length as well as the given transmission coefficient allows experimental rate constants to be predicted, whereas the correlation between log k(ex) and activation free energy is poor; (3) the environmental significance of this work is elucidated by the extension toward three fields, that is, polyaluminum system, monomer Al-organic system and other metal ions system with high charge-to-radius ratio.

A mixing timescale model for TPDF simulations of turbulent premixed flames

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

Kuron, Michael; Ren, Zhuyin; Hawkes, Evatt R.

Transported probability density function (TPDF) methods are an attractive modeling approach for turbulent flames as chemical reactions appear in closed form. However, molecular micro-mixing needs to be modeled and this modeling is considered a primary challenge for TPDF methods. In the present study, a new algebraic mixing rate model for TPDF simulations of turbulent premixed flames is proposed, which is a key ingredient in commonly used molecular mixing models. The new model aims to properly account for the transition in reactive scalar mixing rate behavior from the limit of turbulence-dominated mixing to molecular mixing behavior in flamelets. An a priorimore » assessment of the new model is performed using direct numerical simulation (DNS) data of a lean premixed hydrogen–air jet flame. The new model accurately captures the mixing timescale behavior in the DNS and is found to be a significant improvement over the commonly used constant mechanical-to-scalar mixing timescale ratio model. An a posteriori TPDF study is then performed using the same DNS data as a numerical test bed. The DNS provides the initial conditions and time-varying input quantities, including the mean velocity, turbulent diffusion coefficient, and modeled scalar mixing rate for the TPDF simulations, thus allowing an exclusive focus on the mixing model. Here, the new mixing timescale model is compared with the constant mechanical-to-scalar mixing timescale ratio coupled with the Euclidean Minimum Spanning Tree (EMST) mixing model, as well as a laminar flamelet closure. It is found that the laminar flamelet closure is unable to properly capture the mixing behavior in the thin reaction zones regime while the constant mechanical-to-scalar mixing timescale model under-predicts the flame speed. Furthermore, the EMST model coupled with the new mixing timescale model provides the best prediction of the flame structure and flame propagation among the models tested, as the dynamics of reactive scalar mixing across different flame regimes are appropriately accounted for.« less

A method for estimating the rolling moment due to spin rate for arbitrary planform wings

NASA Technical Reports Server (NTRS)

Poppen, W. A., Jr.

1985-01-01

The application of aerodynamic theory for estimating the force and moments acting upon spinning airplanes is of interest. For example, strip theory has been used to generate estimates of the aerodynamic characteristics as a function of spin rate for wing-dominated configurations for angles of attack up to 90 degrees. This work, which had been limited to constant chord wings, is extended here to wings comprised of tapered segments. Comparison of the analytical predictions with rotary balance wind tunnel results shows that large discrepancies remain, particularly for those angles-of-attack greater than 40 degrees.

Chemical kinetics of homogeneous atmospheric oxidation of sulfur dioxide

NASA Technical Reports Server (NTRS)

Sander, S. P.; Seinfeld, J. H.

1976-01-01

A systematic evaluation of known homogeneous SO2 reactions which might be important in air pollution chemistry is carried out. A mechanism is developed to represent the chemistry of NOx/hydrocarbon/SO2 systems, and the mechanism is used to analyze available experimental data appropriate for quantitative analysis of SO2 oxidation kinetics. Detailed comparisons of observed and predicted concentration behavior are presented. In all cases, observed SO2 oxidation rates cannot be explained solely on the basis of those SO2 reactions for which rate constants have been measured. The role of ozone-olefin reactions in SO2 oxidation is elucidated.

Hemolytic potential of hydrodynamic cavitation.

PubMed

Chambers, S D; Bartlett, R H; Ceccio, S L

2000-08-01

The purpose of this study was to determine the hemolytic potentials of discrete bubble cavitation and attached cavitation. To generate controlled cavitation events, a venturigeometry hydrodynamic device, called a Cavitation Susceptibility Meter (CSM), was constructed. A comparison between the hemolytic potential of discrete bubble cavitation and attached cavitation was investigated with a single-pass flow apparatus and a recirculating flow apparatus, both utilizing the CSM. An analytical model, based on spherical bubble dynamics, was developed for predicting the hemolysis caused by discrete bubble cavitation. Experimentally, discrete bubble cavitation did not correlate with a measurable increase in plasma-free hemoglobin (PFHb), as predicted by the analytical model. However, attached cavitation did result in significant PFHb generation. The rate of PFHb generation scaled inversely with the Cavitation number at a constant flow rate, suggesting that the size of the attached cavity was the dominant hemolytic factor.

Assessment of CFD Hypersonic Turbulent Heating Rates for Space Shuttle Orbiter

NASA Technical Reports Server (NTRS)

Wood, William A.; Oliver, A. Brandon

2011-01-01

Turbulent CFD codes are assessed for the prediction of convective heat transfer rates at turbulent, hypersonic conditions. Algebraic turbulence models are used within the DPLR and LAURA CFD codes. The benchmark heat transfer rates are derived from thermocouple measurements of the Space Shuttle orbiter Discovery windward tiles during the STS-119 and STS-128 entries. The thermocouples were located underneath the reaction-cured glass coating on the thermal protection tiles. Boundary layer transition flight experiments conducted during both of those entries promoted turbulent flow at unusually high Mach numbers, with the present analysis considering Mach 10{15. Similar prior comparisons of CFD predictions directly to the flight temperature measurements were unsatisfactory, showing diverging trends between prediction and measurement for Mach numbers greater than 11. In the prior work, surface temperatures and convective heat transfer rates had been assumed to be in radiative equilibrium. The present work employs a one-dimensional time-accurate conduction analysis to relate measured temperatures to surface heat transfer rates, removing heat soak lag from the flight data, in order to better assess the predictive accuracy of the numerical models. The turbulent CFD shows good agreement for turbulent fuselage flow up to Mach 13. But on the wing in the wake of the boundary layer trip, the inclusion of tile conduction effects does not explain the prior observed discrepancy in trends between simulation and experiment; the flight heat transfer measurements are roughly constant over Mach 11-15, versus an increasing trend with Mach number from the CFD.

Kinetics of protein–ligand unbinding: Predicting pathways, rates, and rate-limiting steps

PubMed Central

Tiwary, Pratyush; Limongelli, Vittorio; Salvalaglio, Matteo; Parrinello, Michele

2015-01-01

The ability to predict the mechanisms and the associated rate constants of protein–ligand unbinding is of great practical importance in drug design. In this work we demonstrate how a recently introduced metadynamics-based approach allows exploration of the unbinding pathways, estimation of the rates, and determination of the rate-limiting steps in the paradigmatic case of the trypsin–benzamidine system. Protein, ligand, and solvent are described with full atomic resolution. Using metadynamics, multiple unbinding trajectories that start with the ligand in the crystallographic binding pose and end with the ligand in the fully solvated state are generated. The unbinding rate koff is computed from the mean residence time of the ligand. Using our previously computed binding affinity we also obtain the binding rate kon. Both rates are in agreement with reported experimental values. We uncover the complex pathways of unbinding trajectories and describe the critical rate-limiting steps with unprecedented detail. Our findings illuminate the role played by the coupling between subtle protein backbone fluctuations and the solvation by water molecules that enter the binding pocket and assist in the breaking of the shielded hydrogen bonds. We expect our approach to be useful in calculating rates for general protein–ligand systems and a valid support for drug design. PMID:25605901

Thermal niche estimators and the capability of poor dispersal species to cope with climate change

NASA Astrophysics Data System (ADS)

Sánchez-Fernández, David; Rizzo, Valeria; Cieslak, Alexandra; Faille, Arnaud; Fresneda, Javier; Ribera, Ignacio

2016-03-01

For management strategies in the context of global warming, accurate predictions of species response are mandatory. However, to date most predictions are based on niche (bioclimatic) models that usually overlook biotic interactions, behavioral adjustments or adaptive evolution, and assume that species can disperse freely without constraints. The deep subterranean environment minimises these uncertainties, as it is simple, homogeneous and with constant environmental conditions. It is thus an ideal model system to study the effect of global change in species with poor dispersal capabilities. We assess the potential fate of a lineage of troglobitic beetles under global change predictions using different approaches to estimate their thermal niche: bioclimatic models, rates of thermal niche change estimated from a molecular phylogeny, and data from physiological studies. Using bioclimatic models, at most 60% of the species were predicted to have suitable conditions in 2080. Considering the rates of thermal niche change did not improve this prediction. However, physiological data suggest that subterranean species have a broad thermal tolerance, allowing them to stand temperatures never experienced through their evolutionary history. These results stress the need of experimental approaches to assess the capability of poor dispersal species to cope with temperatures outside those they currently experience.

Comparison of Primary Models to Predict Microbial Growth by the Plate Count and Absorbance Methods.

PubMed

Pla, María-Leonor; Oltra, Sandra; Esteban, María-Dolores; Andreu, Santiago; Palop, Alfredo

2015-01-01

The selection of a primary model to describe microbial growth in predictive food microbiology often appears to be subjective. The objective of this research was to check the performance of different mathematical models in predicting growth parameters, both by absorbance and plate count methods. For this purpose, growth curves of three different microorganisms (Bacillus cereus, Listeria monocytogenes, and Escherichia coli) grown under the same conditions, but with different initial concentrations each, were analysed. When measuring the microbial growth of each microorganism by optical density, almost all models provided quite high goodness of fit (r(2) > 0.93) for all growth curves. The growth rate remained approximately constant for all growth curves of each microorganism, when considering one growth model, but differences were found among models. Three-phase linear model provided the lowest variation for growth rate values for all three microorganisms. Baranyi model gave a variation marginally higher, despite a much better overall fitting. When measuring the microbial growth by plate count, similar results were obtained. These results provide insight into predictive microbiology and will help food microbiologists and researchers to choose the proper primary growth predictive model.

Wind assistance: A requirement for migration of shorebirds?

USGS Publications Warehouse

Butler, Robert W.; Williams, Tony D.; Warnock, Nils; Bishop, Mary Anne

1997-01-01

We investigated the importance of wind-assisted flight for northward (spring) migration by Western Sandpipers (Calidris mauri) along the Pacific Coast of North America. Using current models of energy costs of flight and recent data on the phenology of migration, we estimated the energy (fat) requirements for migration in calm winds and with wind-assisted flight for different rates of fat deposition: (1) a variable rate, assuming that birds deposit the minimum amount of fat required to reach the next stopover site; (2) a constant maximum rate of 1.0 g/day; and (3) a lower constant rate of 0.4 g/day. We tested these models by comparing conservative estimates of predicted body mass along the migration route with empirical data on body mass of Western Sandpipers at different stopover sites and upon arrival at the breeding grounds. In calm conditions, birds would have to deposit unrealistically high amounts of fat (up to 330% of observed values) to maintain body mass above absolute lean mass values. Fat-deposition rates of 1.0 g/day and 0.4 g/day, in calm conditions, resulted in a steady decline in body mass along the migration route, with predicted body masses on arrival in Alaska of only 60% (13.6 g) and 26% (5.9 g) of average lean mass (22.7 g). Conversely, birds migrating with wind assistance would be able to complete migration with fat-deposition rates as low as 0.4 g/day, similar to values reported for this size bird from field studies. Our results extend the conclusion of the importance of winds for large, long-distance migrants to a small, short-distance migrant. We suggest that the migratory decisions of birds are more strongly influenced by the frequency and duration of winds aloft, i.e. by events during the flight phase, than by events during the stopover phase of migration, such as fat-deposition rate, that have been the focus of much recent migration theory.

Biogeochemical controls of uranium bioavailability from the dissolved phase in natural freshwaters

USGS Publications Warehouse

Croteau, Marie-Noele; Fuller, Christopher C.; Cain, Daniel J.; Campbell, Kate M.; Aiken, George R.

2016-01-01

To gain insights into the risks associated with uranium (U) mining and processing, we investigated the biogeochemical controls of U bioavailability in the model freshwater speciesLymnaea stagnalis (Gastropoda). Bioavailability of dissolved U(VI) was characterized in controlled laboratory experiments over a range of water hardness, pH, and in the presence of complexing ligands in the form of dissolved natural organic matter (DOM). Results show that dissolved U is bioavailable under all the geochemical conditions tested. Uranium uptake rates follow first order kinetics over a range encompassing most environmental concentrations. Uranium uptake rates in L. stagnalis ultimately demonstrate saturation uptake kinetics when exposure concentrations exceed 100 nM, suggesting uptake via a finite number of carriers or ion channels. The lack of a relationship between U uptake rate constants and Ca uptake rates suggest that U does not exclusively use Ca membrane transporters. In general, U bioavailability decreases with increasing pH, increasing Ca and Mg concentrations, and when DOM is present. Competing ions did not affect U uptake rates. Speciation modeling that includes formation constants for U ternary complexes reveals that the aqueous concentration of dicarbonato U species (UO2(CO3)2–2) best predicts U bioavailability to L. stagnalis, challenging the free-ion activity model postulate.

Micromechanical Prediction of the Effective Coefficients of Thermo-Piezoelectric Multiphase Composites

NASA Technical Reports Server (NTRS)

Aboudi, Jacob

1998-01-01

The micromechanical generalized method of cells model is employed for the prediction of the effective elastic, piezoelectric, dielectric, pyroelectric and thermal-expansion constants of multiphase composites with embedded piezoelectric materials. The predicted effective constants are compared with other micromechanical methods available in the literature and good agreements are obtained.

An Examination of Environment Perturbation Effects on Single Event Upset Rates

NASA Technical Reports Server (NTRS)

Gates, Michele M.; Leidecker, Henning W.; Lewis, Mark J.

1997-01-01

This paper presents an analysis of the sensitivity of single event upset (SEU) rate predictions to changes in the direct ionization-inducing environment. An examination based on the nature of the SEU rate equation is presented for the case in which the perturbation is constant across varying particle linear energy transfer (LET). It is shown that the relative variation in SEU rate is equal to the relative perturbation in flux. Results are also presented for the case in which the environment perturbations exist in small LET bins. Through this analysis it is shown that the relative variation in expected SEU rate is equal to that in flux only for the LET regime in which the product of the cross section and differential flux is maximum.

Higher success rate with transcranial electrical stimulation of motor-evoked potentials using constant-voltage stimulation compared with constant-current stimulation in patients undergoing spinal surgery.

PubMed

Shigematsu, Hideki; Kawaguchi, Masahiko; Hayashi, Hironobu; Takatani, Tsunenori; Iwata, Eiichiro; Tanaka, Masato; Okuda, Akinori; Morimoto, Yasuhiko; Masuda, Keisuke; Tanaka, Yuu; Tanaka, Yasuhito

2017-10-01

During spine surgery, the spinal cord is electrophysiologically monitored via transcranial electrical stimulation of motor-evoked potentials (TES-MEPs) to prevent injury. Transcranial electrical stimulation of motor-evoked potential involves the use of either constant-current or constant-voltage stimulation; however, there are few comparative data available regarding their ability to adequately elicit compound motor action potentials. We hypothesized that the success rates of TES-MEP recordings would be similar between constant-current and constant-voltage stimulations in patients undergoing spine surgery. The objective of this study was to compare the success rates of TES-MEP recordings between constant-current and constant-voltage stimulation. This is a prospective, within-subject study. Data from 100 patients undergoing spinal surgery at the cervical, thoracic, or lumbar level were analyzed. The success rates of the TES-MEP recordings from each muscle were examined. Transcranial electrical stimulation with constant-current and constant-voltage stimulations at the C3 and C4 electrode positions (international "10-20" system) was applied to each patient. Compound muscle action potentials were bilaterally recorded from the abductor pollicis brevis (APB), deltoid (Del), abductor hallucis (AH), tibialis anterior (TA), gastrocnemius (GC), and quadriceps (Quad) muscles. The success rates of the TES-MEP recordings from the right Del, right APB, bilateral Quad, right TA, right GC, and bilateral AH muscles were significantly higher using constant-voltage stimulation than those using constant-current stimulation. The overall success rates with constant-voltage and constant-current stimulations were 86.3% and 68.8%, respectively (risk ratio 1.25 [95% confidence interval: 1.20-1.31]). The success rates of TES-MEP recordings were higher using constant-voltage stimulation compared with constant-current stimulation in patients undergoing spinal surgery. Copyright © 2017 Elsevier Inc. All rights reserved.

Instanton rate constant calculations close to and above the crossover temperature.

PubMed

McConnell, Sean; Kästner, Johannes

2017-11-15

Canonical instanton theory is known to overestimate the rate constant close to a system-dependent crossover temperature and is inapplicable above that temperature. We compare the accuracy of the reaction rate constants calculated using recent semi-classical rate expressions to those from canonical instanton theory. We show that rate constants calculated purely from solving the stability matrix for the action in degrees of freedom orthogonal to the instanton path is not applicable at arbitrarily low temperatures and use two methods to overcome this. Furthermore, as a by-product of the developed methods, we derive a simple correction to canonical instanton theory that can alleviate this known overestimation of rate constants close to the crossover temperature. The combined methods accurately reproduce the rate constants of the canonical theory along the whole temperature range without the spurious overestimation near the crossover temperature. We calculate and compare rate constants on three different reactions: H in the Müller-Brown potential, methylhydroxycarbene → acetaldehyde and H 2  + OH → H + H 2 O. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Low Pressure Spark Gap

DTIC Science & Technology

1981-06-01

voltage electrode and forms the interface between the water and vacuum. Figure 1 Low Pressure Switch Apparatus 380 The water Blumlein, the...buildup of current and can predict the rate constant within 30%, it appears that we understand the basic mechanism of the low pressure switch . 0.22...E. J. Lauer, "Status of Low Pressure Switch Research and Development," UCID 17998, Dec. 12, 1978. 4. E. J. Lauer, S. S. Yu and D. M. Cox, "Onset

Utilisation of chip thickness models in grinding

NASA Astrophysics Data System (ADS)

Singleton, Roger

Grinding is now a well established process utilised for both stock removal and finish applications. Although significant research is performed in this field, grinding still experiences problems with burn and high forces which can lead to poor quality components and damage to equipment. This generally occurs in grinding when the process deviates from its safe working conditions. In milling, chip thickness parameters are utilised to predict and maintain process outputs leading to improved control of the process. This thesis looks to further the knowledge of the relationship between chip thickness and the grinding process outputs to provide an increased predictive and maintenance modelling capability. Machining trials were undertaken using different chip thickness parameters to understand how these affect the process outputs. The chip thickness parameters were maintained at different grinding wheel diameters for a constant productivity process to determine the impact of chip thickness at a constant material removal rate.. Additional testing using a modified pin on disc test rig was performed to provide further information on process variables. The different chip thickness parameters provide control of different process outputs in the grinding process. These relationships can be described using contact layer theory and heat flux partitioning. The contact layer is defined as the immediate layer beneath the contact arc at the wheel workpiece interface. The size of the layer governs the force experienced during the process. The rate of contact layer removal directly impacts the net power required from the system. It was also found that the specific grinding energy of a process is more dependent on the productivity of a grinding process rather than the value of chip thickness. Changes in chip thickness at constant material removal rate result in microscale changes in the rate of contact layer removal when compared to changes in process productivity. This is a significant piece of information in relation to specific grinding energy where conventional theory states it is primarily dependent on chip thickness..

A Screening Model to Predict Microalgae Biomass Growth in Photobioreactors and Raceway Ponds

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

Huesemann, Michael H.; Van Wagenen, Jonathan M.; Miller, Tyler W.

A microalgae biomass growth model was developed for screening novel strains for their potential to exhibit high biomass productivities under nutrient-replete conditions in photobioreactors or outdoor ponds. Growth is modeled by first estimating the light attenuation by biomass according to Beer-Lambert’s law, and then calculating the specific growth rate in discretized culture volume slices that receive declining light intensities due to attenuation. The model requires only two physical and two species-specific biological input parameters, all of which are relatively easy to determine: incident light intensity, culture depth, as well as the biomass light absorption coefficient and the specific growth ratemore » as a function of light intensity. Roux bottle culture experiments were performed with Nannochloropsis salina at constant temperature (23 °C) at six different incident light intensities (5, 10, 25, 50, 100, 250, and 850 μmol/m2∙ sec) to determine both the specific growth rate under non-shading conditions and the biomass light absorption coefficient as a function of light intensity. The model was successful in predicting the biomass growth rate in these Roux bottle cultures during the light-limited linear phase at different incident light intensities. Model predictions were moderately sensitive to minor variations in the values of input parameters. The model was also successful in predicting the growth performance of Chlorella sp. cultured in LED-lighted 800 L raceway ponds operated at constant temperature (30 °C) and constant light intensity (1650 μmol/m2∙ sec). Measurements of oxygen concentrations as a function of time demonstrated that following exposure to darkness, it takes at least 5 seconds for cells to initiate dark respiration. As a result, biomass loss due to dark respiration in the aphotic zone of a culture is unlikely to occur in highly mixed small-scale photobioreactors where cells move rapidly in and out of the light. By contrast, as supported also by the growth model, biomass loss due to dark respiration occurs in the dark zones of the relatively less well mixed pond cultures. In addition to screening novel microalgae strains for high biomass productivities, the model can also be used for optimizing the pond design and operation. Additional research is needed to validate the biomass growth model for other microalgae species and for the more realistic case of fluctuating temperatures and light intensities observed in outdoor pond cultures.« less

Characterization and prediction of rate-dependent flexibility in lumbar spine biomechanics at room and body temperature.

PubMed

Stolworthy, Dean K; Zirbel, Shannon A; Howell, Larry L; Samuels, Marina; Bowden, Anton E

2014-05-01

The soft tissues of the spine exhibit sensitivity to strain-rate and temperature, yet current knowledge of spine biomechanics is derived from cadaveric testing conducted at room temperature at very slow, quasi-static rates. The primary objective of this study was to characterize the change in segmental flexibility of cadaveric lumbar spine segments with respect to multiple loading rates within the range of physiologic motion by using specimens at body or room temperature. The secondary objective was to develop a predictive model of spine flexibility across the voluntary range of loading rates. This in vitro study examines rate- and temperature-dependent viscoelasticity of the human lumbar cadaveric spine. Repeated flexibility tests were performed on 21 lumbar function spinal units (FSUs) in flexion-extension with the use of 11 distinct voluntary loading rates at body or room temperature. Furthermore, six lumbar FSUs were loaded in axial rotation, flexion-extension, and lateral bending at both body and room temperature via a stepwise, quasi-static loading protocol. All FSUs were also loaded using a control loading test with a continuous-speed loading-rate of 1-deg/sec. The viscoelastic torque-rotation response for each spinal segment was recorded. A predictive model was developed to accurately estimate spine segment flexibility at any voluntary loading rate based on measured flexibility at a single loading rate. Stepwise loading exhibited the greatest segmental range of motion (ROM) in all loading directions. As loading rate increased, segmental ROM decreased, whereas segmental stiffness and hysteresis both increased; however, the neutral zone remained constant. Continuous-speed tests showed that segmental stiffness and hysteresis are dependent variables to ROM at voluntary loading rates in flexion-extension. To predict the torque-rotation response at different loading rates, the model requires knowledge of the segmental flexibility at a single rate and specified temperature, and a scaling parameter. A Bland-Altman analysis showed high coefficients of determination for the predictive model. The present work demonstrates significant changes in spine segment flexibility as a result of loading rate and testing temperature. Loading rate effects can be accounted for using the predictive model, which accurately estimated ROM, neutral zone, stiffness, and hysteresis within the range of voluntary motion. Copyright © 2014 Elsevier Inc. All rights reserved.

Creep of Ni(3)Al in the temperature regime of anomalous flow behavior

NASA Astrophysics Data System (ADS)

Uchic, Michael David

Much attention has been paid to understanding the dynamics of dislocation motion and substructure formation in Ni3Al in the anomalous flow regime. However, most of the experimental work that has been performed in the lowest temperatures of the anomalous flow regime has been under constant-strain-rate conditions. An alternative and perhaps more fundamental way to probe the plastic behavior of materials is a monotonic creep test, in which the stress and temperature are held constant while the time-dependent strain is measured. The aim of this study is to use constant-stress experiments to further explore the plastic flow anomaly in L12 alloys at low temperatures. Tension creep experiments have been carried out on <123> oriented single crystals of Ni75Al24Ta1 at temperatures between 293 and 473 K. We have observed primary creep leading to exhaustion at all temperatures and stresses, with creep rates declining faster than predicted by the logarithmic creep law. The total strain and creep strain have an anomalous dependence on temperature, which is consistent with the flow stress anomaly. We have also observed other unusual behavior in our creep experiments; for example, the reinitiation of plastic flow at low temperatures after a modest increment in applied stress shows a sigmoidal response, i.e., there is a significant time delay before the plastic strain rate accelerates to a maximum value. We also examined the ability to reinitiate plastic flow in samples that have been crept to exhaustion by simply lowering the test temperature. In addition, we have also performed conventional constant-displacement-rate experiments in the same temperature range. From these experiments, we have discovered that unlike most metals, Ni3Al displays a negative dependence of the work hardening rate (WHR) with increasing strain rate. For tests at intermediate temperatures (373 and 423 K), the WHRs of crystals tested at moderately high strain rates (10-2 s-1) are half the WHRs of crystals tested at conventional strain rates (10 -5 s-1), and this anomalous dependence has also been shown to be reversible with changes in strain rate. The implications of all results are discussed in light of our efforts to model plastic deformation in these alloys.

Henry's Constants of Persistent Organic Pollutants by a Group-Contribution Method Based on Scaled-Particle Theory.

PubMed

Razdan, Neil K; Koshy, David M; Prausnitz, John M

2017-11-07

A group-contribution method based on scaled-particle theory was developed to predict Henry's constants for six families of persistent organic pollutants: polychlorinated benzenes, polychlorinated biphenyls, polychlorinated dibenzodioxins, polychlorinated dibenzofurans, polychlorinated naphthalenes, and polybrominated diphenyl ethers. The group-contribution model uses limited experimental data to obtain group-interaction parameters for an easy-to-use method to predict Henry's constants for systems where reliable experimental data are scarce. By using group-interaction parameters obtained from data reduction, scaled-particle theory gives the partial molar Gibbs energy of dissolution, Δg̅ 2 , allowing calculation of Henry's constant, H 2 , for more than 700 organic pollutants. The average deviation between predicted values of log H 2 and experiment is 4%. Application of an approximate van't Hoff equation gives the temperature dependence of Henry's constants for polychlorinated biphenyls, polychlorinated naphthalenes, and polybrominated diphenyl ethers in the environmentally relevant range 0-40 °C.

Application of the Zero-Order Reaction Rate Model and Transition State Theory to predict porous Ti6Al4V bending strength.

PubMed

Reig, L; Amigó, V; Busquets, D; Calero, J A; Ortiz, J L

2012-08-01

Porous Ti6Al4V samples were produced by microsphere sintering. The Zero-Order Reaction Rate Model and Transition State Theory were used to model the sintering process and to estimate the bending strength of the porous samples developed. The evolution of the surface area during the sintering process was used to obtain sintering parameters (sintering constant, activation energy, frequency factor, constant of activation and Gibbs energy of activation). These were then correlated with the bending strength in order to obtain a simple model with which to estimate the evolution of the bending strength of the samples when the sintering temperature and time are modified: σY=P+B·[lnT·t-ΔGa/R·T]. Although the sintering parameters were obtained only for the microsphere sizes analysed here, the strength of intermediate sizes could easily be estimated following this model. Copyright © 2012 Elsevier B.V. All rights reserved.

Collision cross sections of N2 by H+ impact at keV energies within time-dependent density-functional theory

NASA Astrophysics Data System (ADS)

Yu, W.; Gao, C.-Z.; Zhang, Y.; Zhang, F. S.; Hutton, R.; Zou, Y.; Wei, B.

2018-03-01

We calculate electron capture and ionization cross sections of N2 impacted by the H+ projectile at keV energies. To this end, we employ the time-dependent density-functional theory coupled nonadiabatically to molecular dynamics. To avoid the explicit treatment of the complex density matrix in the calculation of cross sections, we propose an approximate method based on the assumption of constant ionization rate over the period of the projectile passing the absorbing boundary. Our results agree reasonably well with experimental data and semi-empirical results within the measurement uncertainties in the considered energy range. The discrepancies are mainly attributed to the inadequate description of exchange-correlation functional and the crude approximation for constant ionization rate. Although the present approach does not predict the experiments quantitatively for collision energies below 10 keV, it is still helpful to calculate total cross sections of ion-molecule collisions within a certain energy range.

Is the continuous matter creation cosmology an alternative to ΛCDM?

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

Fabris, J.C.; Pacheco, J.A. de Freitas; Piattella, O.F., E-mail: fabris@pq.cnpq.br, E-mail: pacheco@oca.eu, E-mail: oliver.piattella@pq.cnpq.br

2014-06-01

The matter creation cosmology is revisited, including the evolution of baryons and dark matter particles. The creation process affects only dark matter and not baryons. The dynamics of the ΛCDM model can be reproduced only if two conditions are satisfied: 1) the entropy density production rate and the particle density variation rate are equal and 2) the (negative) pressure associated to the creation process is constant. However, the matter creation model predicts a present dark matter-to-baryon ratio much larger than that observed in massive X-ray clusters of galaxies, representing a potential difficulty for the model. In the linear regime, amore » fully relativistic treatment indicates that baryons are not affected by the creation process but this is not the case for dark matter. Both components evolve together at early phases but lately the dark matter density contrast decreases since the background tends to a constant value. This behaviour produces a negative growth factor, in disagreement with observations, being a further problem for this cosmology.« less

Constant proportion harvest policies: dynamic implications in the Pacific halibut and Atlantic cod fisheries.

PubMed

Yakubu, Abdul-Aziz; Li, Nianpeng; Conrad, Jon M; Zeeman, Mary-Lou

2011-07-01

Overfishing, pollution and other environmental factors have greatly reduced commercially valuable stocks of fish. In a 2006 Science article, a group of ecologists and economists warned that the world may run out of seafood from natural stocks if overfishing continues at current rates. In this paper, we explore the interaction between a constant proportion harvest policy and recruitment dynamics. We examine the discrete-time constant proportion harvest policy discussed in Ang et al. (2009) and then expand the framework to include stock-recruitment functions that are compensatory and overcompensatory, both with and without the Allee effect. We focus on constant proportion policies (CPPs). CPPs have the potential to stabilize complex overcompensatory stock dynamics, with or without the Allee effect, provided the rates of harvest stay below a threshold. If that threshold is exceeded, CPPs are known to result in the sudden collapse of a fish stock when stock recruitment exhibits the Allee effect. In case studies, we analyze CPPs as they might be applied to Gulf of Alaska Pacific halibut fishery and the Georges Bank Atlantic cod fishery based on harvest rates from 1975 to 2007. The best fit models suggest that, under high fishing mortalities, the halibut fishery is vulnerable to sudden population collapse while the cod fishery is vulnerable to steady decline to zero. The models also suggest that CPP with mean harvesting levels from the last 30 years can be effective at preventing collapse in the halibut fishery, but these same policies would lead to steady decline to zero in the Atlantic cod fishery. We observe that the likelihood of collapse in both fisheries increases with increased stochasticity (for example, weather variability) as predicted by models of global climate change. Copyright © 2011 Elsevier Inc. All rights reserved.

The temperature dependence of the rate constant for the reaction of hydroxyl radicals with nitric acid

NASA Technical Reports Server (NTRS)

Kurylo, M. J.; Cornett, K. D.; Murphy, J. L.

1982-01-01

The rate constant for the reaction of hydroxyl radicals with nitric acid in the 225-443 K temperature range has been measured by means of the flash photolysis resonance fluorescence technique. Above 300 K, the rate constant levels off in a way that can only be explained by the occurrence of two reaction channels, of which one, operative at low temperatures, proceeds through the formation of an adduct intermediate. The implications of these rate constant values for stratospheric reaction constants is discussed.

Very high pressure liquid chromatography using core-shell particles: quantitative analysis of fast gradient separations without post-run times.

PubMed

Stankovich, Joseph J; Gritti, Fabrice; Stevenson, Paul G; Beaver, Lois A; Guiochon, Georges

2014-01-17

Five methods for controlling the mobile phase flow rate for gradient elution analyses using very high pressure liquid chromatography (VHPLC) were tested to determine thermal stability of the column during rapid gradient separations. To obtain rapid separations, instruments are operated at high flow rates and high inlet pressure leading to uneven thermal effects across columns and additional time needed to restore thermal equilibrium between successive analyses. The purpose of this study is to investigate means to minimize thermal instability and obtain reliable results by measuring the reproducibility of the results of six replicate gradient separations of a nine component RPLC standard mixture under various experimental conditions with no post-run times. Gradient separations under different conditions were performed: constant flow rates, two sets of constant pressure operation, programmed flow constant pressure operation, and conditions which theoretically should yield a constant net heat loss at the column's wall. The results show that using constant flow rates, programmed flow constant pressures, and constant heat loss at the column's wall all provide reproducible separations. However, performing separations using a high constant pressure with programmed flow reduces the analysis time by 16% compared to constant flow rate methods. For the constant flow rate, programmed flow constant pressure, and constant wall heat experiments no equilibration time (post-run time) was required to obtain highly reproducible data. Copyright © 2013 Elsevier B.V. All rights reserved.

Myosin concentration underlies cell size–dependent scalability of actomyosin ring constriction

PubMed Central

Wright, Graham D.; Leong, Fong Yew; Chiam, Keng-Hwee; Chen, Yinxiao; Jedd, Gregory; Balasubramanian, Mohan K.

2011-01-01

In eukaryotes, cytokinesis is accomplished by an actomyosin-based contractile ring. Although in Caenorhabditis elegans embryos larger cells divide at a faster rate than smaller cells, it remains unknown whether a similar mode of scalability operates in other cells. We investigated cytokinesis in the filamentous fungus Neurospora crassa, which exhibits a wide range of hyphal circumferences. We found that N. crassa cells divide using an actomyosin ring and larger rings constricted faster than smaller rings. However, unlike in C. elegans, the total amount of myosin remained constant throughout constriction, and there was a size-dependent increase in the starting concentration of myosin in the ring. We predict that the increased number of ring-associated myosin motors in larger rings leads to the increased constriction rate. Accordingly, reduction or inhibition of ring-associated myosin slows down the rate of constriction. Because the mechanical characteristics of contractile rings are conserved, we predict that these findings will be relevant to actomyosin ring constriction in other cell types. PMID:22123864

Capillary pumping independent of the liquid surface energy and viscosity

NASA Astrophysics Data System (ADS)

Guo, Weijin; Hansson, Jonas; van der Wijngaart, Wouter

2018-03-01

Capillary pumping is an attractive means of liquid actuation because it is a passive mechanism, i.e., it does not rely on an external energy supply during operation. The capillary flow rate generally depends on the liquid sample viscosity and surface energy. This poses a problem for capillary-driven systems that rely on a predictable flow rate and for which the sample viscosity or surface energy are not precisely known. Here, we introduce the capillary pumping of sample liquids with a flow rate that is constant in time and independent of the sample viscosity and sample surface energy. These features are enabled by a design in which a well-characterized pump liquid is capillarily imbibed into the downstream section of the pump and thereby pulls the unknown sample liquid into the upstream pump section. The downstream pump geometry is designed to exert a Laplace pressure and fluidic resistance that are substantially larger than those exerted by the upstream pump geometry on the sample liquid. Hence, the influence of the unknown sample liquid on the flow rate is negligible. We experimentally tested pumps of the new design with a variety of sample liquids, including water, different samples of whole blood, different samples of urine, isopropanol, mineral oil, and glycerol. The capillary filling speeds of these liquids vary by more than a factor 1000 when imbibed to a standard constant cross-section glass capillary. In our new pump design, 20 filling tests involving these liquid samples with vastly different properties resulted in a constant volumetric flow rate in the range of 20.96-24.76 μL/min. We expect this novel capillary design to have immediate applications in lab-on-a-chip systems and diagnostic devices.

Mercury photoreduction and photooxidation in lakes: Effects of filtration and dissolved organic carbon concentration.

PubMed

O'Driscoll, Nelson J; Vost, Emma; Mann, Erin; Klapstein, Sara; Tordon, Robert; Lukeman, Matthew

2018-06-01

Mercury is a globally distributed, environmental contaminant. Quantifying the retention and loss of mercury is integral for predicting mercury-sensitive ecosystems. There is little information on how dissolved organic carbon (DOC) concentrations and particulates affect mercury photoreaction kinetics in freshwater lakes. To address this knowledge gap, samples were collected from ten lakes in Kejimkujik National Park, Nova Scotia (DOC: 2.6-15.4mg/L). Filtered (0.2μm) and unfiltered samples were analysed for gross photoreduction, gross photooxidation, and net reduction rates of mercury using pseudo first-order curves. Unfiltered samples had higher concentrations (p=0.04) of photoreducible divalent mercury (Hg(II) RED ) (mean of 754±253pg/L) than filtered samples (mean of 482±206pg/L); however, gross photoreduction and photooxidation rate constants were not significantly different in filtered or unfiltered samples in early summer. DOC was not significantly related to gross photoreduction rate constants in filtered (R 2 =0.43; p=0.08) and unfiltered (R 2 =0.02; p=0.71) samples; DOC was also not significantly related to gross photooxidation rate constants in filtered or unfiltered samples. However, DOC was significantly negatively related with Hg(II) RED in unfiltered (R 2 =0.53; p=0.04), but not in filtered samples (R 2 =0.04; p=0.60). These trends indicate that DOC is a factor in determining dissolved mercury photoreduction rates and particles partially control available Hg(II) RED in lake water. This research also demonstrates that within these lakes gross photoreduction and photooxidation processes are close to being in balance. Changes to catchment inputs of particulate matter and DOC may alter mercury retention in these lakes and could partially explain observed increases of mercury accumulation in biota. Copyright © 2017. Published by Elsevier B.V.

Explanation of the unusual temperature dependence of the atmospherically important OH + H(2)S --> H(2)O + HS reaction and prediction of the rate constant at combustion temperatures.

PubMed

Ellingson, Benjamin A; Truhlar, Donald G

2007-10-24

Rate constants for the OH + H2S --> H2O + HS reaction, which is important for both atmospheric chemistry and combustion, are calculated by direct dynamics with the M06-2X density functional using the MG3S basis set. Energetics are compared to high-level MCG3/3//MC-QCISD/3 wave function theory and to results obtained by other density functionals. We employ canonical variational transition-state theory with multidimensional tunneling contributions and scaled generalized normal-mode frequencies evaluated in redundant curvilinear coordinates with anharmonicity included in the torsion. The transition state has a quantum mechanically distinguishable, nonsuperimposable mirror image that corresponds to a separate classical reaction path; the effect of the multiple paths is examined through use of a symmetry number and by torsional methods. Calculations with the reference-potential Pitzer-Gwinn treatment of the torsional mode agree with experiment, within experimental scatter, and predict a striking temperature dependence of the activation energy, increasing from -0.1 kcal/mol at 200 K to 0.2, 1.0, 3.4, and 9.8 kcal/mol at 300, 500, 1000, and 2400 K. The unusual temperature dependence arises from a dynamical bottleneck at an energy below reactants, following an addition complex on the reaction path with a classical binding energy of 4.4 kcal/mol. As a way to check the mechanism, kinetic isotope effects of the OH + D2S and OD + D2S reactions have been predicted.

An improved probabilistic approach for linking progenitor and descendant galaxy populations using comoving number density

NASA Astrophysics Data System (ADS)

Wellons, Sarah; Torrey, Paul

2017-06-01

Galaxy populations at different cosmic epochs are often linked by cumulative comoving number density in observational studies. Many theoretical works, however, have shown that the cumulative number densities of tracked galaxy populations not only evolve in bulk, but also spread out over time. We present a method for linking progenitor and descendant galaxy populations which takes both of these effects into account. We define probability distribution functions that capture the evolution and dispersion of galaxy populations in number density space, and use these functions to assign galaxies at redshift zf probabilities of being progenitors/descendants of a galaxy population at another redshift z0. These probabilities are used as weights for calculating distributions of physical progenitor/descendant properties such as stellar mass, star formation rate or velocity dispersion. We demonstrate that this probabilistic method provides more accurate predictions for the evolution of physical properties than the assumption of either a constant number density or an evolving number density in a bin of fixed width by comparing predictions against galaxy populations directly tracked through a cosmological simulation. We find that the constant number density method performs least well at recovering galaxy properties, the evolving method density slightly better and the probabilistic method best of all. The improvement is present for predictions of stellar mass as well as inferred quantities such as star formation rate and velocity dispersion. We demonstrate that this method can also be applied robustly and easily to observational data, and provide a code package for doing so.

VTST/MT studies of the catalytic mechanism of C-H activation by transition metal complexes with [Cu2(μ-O2)], [Fe2(μ-O2)] and Fe(IV)-O cores based on DFT potential energy surfaces.

PubMed

Kim, Yongho; Mai, Binh Khanh; Park, Sumin

2017-04-01

High-valent Cu and Fe species, which are generated from dioxygen activation in metalloenzymes, carry out the functionalization of strong C-H bonds. Understanding the atomic details of the catalytic mechanism has long been one of the main objectives of bioinorganic chemistry. Large H/D kinetic isotope effects (KIEs) were observed in the C-H activation by high-valent non-heme Cu or Fe complexes in enzymes and their synthetic models. The H/D KIE depends significantly on the transition state properties, such as structure, energies, frequencies, and shape of the potential energy surface, when the tunneling effect is large. Therefore, theoretical predictions of kinetic parameters such as rate constants and KIEs can provide a reliable link between atomic-level quantum mechanical mechanisms and experiments. The accurate prediction of the tunneling effect is essential to reproduce the kinetic parameters. The rate constants and HD/KIE have been calculated using the variational transition-state theory including multidimensional tunneling based on DFT potential energy surfaces along the reaction coordinate. Excellent agreement was observed between the predicted and experimental results, which assures the validity of the DFT potential energy surfaces and, therefore, the proposed atomic-level mechanisms. The [Cu 2 (μ-O) 2 ], [Fe 2 (μ-O) 2 ], and Fe(IV)-oxo species were employed for C-H activation, and their role as catalysts was discussed at an atomic level.

Impact of mutation on proton transfer reactions in ketosteroid isomerase: insights from molecular dynamics simulations.

PubMed

Chakravorty, Dhruva K; Hammes-Schiffer, Sharon

2010-06-02

The two proton transfer reactions catalyzed by ketosteroid isomerase (KSI) involve a dienolate intermediate stabilized by hydrogen bonds with Tyr14 and Asp99. Molecular dynamics simulations based on an empirical valence bond model are used to examine the impact of mutating these residues on the hydrogen-bonding patterns, conformational changes, and van der Waals and electrostatic interactions during the proton transfer reactions. While the rate constants for the two proton transfer steps are similar for wild-type (WT) KSI, the simulations suggest that the rate constant for the first proton transfer step is smaller in the mutants due to the significantly higher free energy of the dienolate intermediate relative to the reactant. The calculated rate constants for the mutants D99L, Y14F, and Y14F/D99L relative to WT KSI are qualitatively consistent with the kinetic experiments indicating a significant reduction in the catalytic rates along the series of mutants. In the simulations, WT KSI retained two hydrogen-bonding interactions between the substrate and the active site, while the mutants typically retained only one hydrogen-bonding interaction. A new hydrogen-bonding interaction between the substrate and Tyr55 was observed in the double mutant, leading to the prediction that mutation of Tyr55 will have a greater impact on the proton transfer rate constants for the double mutant than for WT KSI. The electrostatic stabilization of the dienolate intermediate relative to the reactant was greater for WT KSI than for the mutants, providing a qualitative explanation for the significantly reduced rates of the mutants. The active site exhibited restricted motion during the proton transfer reactions, but small conformational changes occurred to facilitate the proton transfer reactions by strengthening the hydrogen-bonding interactions and by bringing the proton donor and acceptor closer to each other with the proper orientation for proton transfer. Thus, these calculations suggest that KSI forms a preorganized active site but that the structure of this preorganized active site is altered upon mutation. Moreover, small conformational changes due to stochastic thermal motions are required within this preorganized active site to facilitate the proton transfer reactions.

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

NASA Astrophysics Data System (ADS)

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.

2011-11-01

The neutral muonic helium atom 4Heμ, 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 4Heμ with molecular hydrogen, 4Heμ + H2 → 4HeμH + 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, kHeμ, 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 kHeμ 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 kHeμ 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 + H2 and Mu + H2 reactions in a novel study of kinetic isotope effects for the H + H2 reactions over a factor of 36.1 in isotopic mass of the atomic reactant.

Temporal clustering of tropical cyclones and its ecosystem impacts

PubMed Central

Mumby, Peter J.; Vitolo, Renato; Stephenson, David B.

2011-01-01

Tropical cyclones have massive economic, social, and ecological impacts, and models of their occurrence influence many planning activities from setting insurance premiums to conservation planning. Most impact models allow for geographically varying cyclone rates but assume that individual storm events occur randomly with constant rate in time. This study analyzes the statistical properties of Atlantic tropical cyclones and shows that local cyclone counts vary in time, with periods of elevated activity followed by relative quiescence. Such temporal clustering is particularly strong in the Caribbean Sea, along the coasts of Belize, Honduras, Costa Rica, Jamaica, the southwest of Haiti, and in the main hurricane development region in the North Atlantic between Africa and the Caribbean. Failing to recognize this natural nonstationarity in cyclone rates can give inaccurate impact predictions. We demonstrate this by exploring cyclone impacts on coral reefs. For a given cyclone rate, we find that clustered events have a less detrimental impact than independent random events. Predictions using a standard random hurricane model were overly pessimistic, predicting reef degradation more than a decade earlier than that expected under clustered disturbance. The presence of clustering allows coral reefs more time to recover to healthier states, but the impacts of clustering will vary from one ecosystem to another. PMID:22006300

Turbulence effects on volatilization rates of liquids and solutes

USGS Publications Warehouse

Lee, J.-F.; Chao, H.-P.; Chiou, C.T.; Manes, M.

2004-01-01

Volatilization rates of neat liquids (benzene, toluene, fluorobenzene, bromobenzene, ethylbenzene, m-xylene, o-xylene, o-dichlorobenzene, and 1-methylnaphthalene) and of solutes (phenol, m-cresol, benzene, toluene, ethylbenzene, o-xylene, and ethylene dibromide) from dilute water solutions have been measured in the laboratory over a wide range of air speeds and water-stirring rates. The overall transfer coefficients (KL) for individual solutes are independent of whether they are in single- or multi-solute solutions. The gas-film transfer coefficients (kG) for solutes in the two-film model, which have hitherto been estimated by extrapolation from reference coefficients, can now be determined directly from the volatilization rates of neatliquids through anew algorithm. The associated liquid-film transfer coefficients (KL) can then be obtained from measured KL and kG values and solute Henry law constants (H). This approach provides a novel means for checking the precision of any kL and kG estimation methods for ultimate prediction of KL. The improved kG estimation enables accurate K L predictions for low-volatility (i.e., low-H) solutes where K L and kGH are essentially equal. In addition, the prediction of KL values for high-volatility (i.e., high-H) solutes, where KL ??? kL, is also improved by using appropriate reference kL values.

Attrition and changes in size distribution of lime sorbents during fluidization in a circulating fluidized bed absorber. Double quarterly report, January 1--August 31, 1993

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

Lee, Sang-Kwun; Keener, T.C.; Cook, J.L.

1993-12-31

The experimental data of lime sorbent attrition obtained from attriton tests in a circulating fluidized bed absorber (CFBA) are represented. The results are interpreted as both the weight-based attrition rate and size-based attrition rate. The weight-based attrition rate constants are obtained from a modified second-order attrition model, incorporating a minimum fluidization weight, W{sub min}, and excess velocity. Furthermore, this minimum fluidization weight, or W{sub min} was found to be a function of both particle size and velocity. A plot of the natural log of the overall weight-based attrition rate constants (ln K{sub a}) for Lime 1 (903 MMD) at superficialmore » gas velocities of 2 m/s, 2.35 m/s, and 2.69 m/s and for Lime 2 (1764 MMD) at superficial gas velocities of 2 m/s, 3 m/s, 4 m/s and 5 m/s versus the energy term, 1/(U-U{sub mf}){sup 2}, yielded a linear relationship. And, a regression coefficient of 0.9386 for the linear regression confirms that K{sub a} may be expressed in Arrhenius form. In addition, an unsteady state population model is represented to predict the changes in size distribution of bed materials during fluidization. The unsteady state population model was verified experimentally and the solid size distribution predicted by the model agreed well with the corresponding experimental size distributions. The model may be applicable for the batch and continuous operations of fluidized beds in which the solids size reduction is predominantly resulted from attritions and elutriations. Such significance of the mechanical attrition and elutriation is frequently seen in a fast fluidized bed as well as in a circulating fluidized bed.« less

First order sea-level cycles and supercontinent break up

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

Heller, P.L.; Angevine, C.L.

1985-01-01

The authors have developed a model that successfully predicts the approximate magnitude and timing of long term sea-level change without relying on short term increases in global spreading rates. The model involves the following key assumptions. (1) Ocean basins have two types of area/age distributions; Pacific ocean basins are rimmed by subduction zones and have triangular distributions; and Atlantic ocean basins which open at constant rates, have no subduction, and so have rectangular distributions. (2) The total area of the global ocean is constant so that the Pacific basin must close as the Atlantic opens. These assumptions approximate modern globalmore » ocean basin conditions. The model begins with supercontinent break up. As the Atlantic begins to open, the mean age of the global ocean decreases, the mean depth of the sea floor shallows, and sea level, therefore, rises. Once the Atlantic occupies more than 8 to 10% of the global ocean area, the mean age and depth of the ocean floor increases resulting in a sea-level fall. The model can be applied to the mid-Cretaceous sea-level high stand which followed break up of Pangea by 80 to 100 Ma. Based on average Atlantic opening rates, sea level rises to a peak of 44 m at 80 Ma after opening began and then falls by 84 m to the present. Thus the model is capable of explaining approximately half of the total magnitude of the post-mid-Cretaceous eustatic fall without invoking short-term changes in global spreading rates. In addition, the model predicts the observed time lag between supercontinent break up and sea-level high stand for both Mesozoic as well as early Paleozoic time.« less

Kinetics and mechanism of the oxidation of S(IV) by ozone in aqueous solution with particular reference to SO2 conversion in nonurban tropospheric clouds

NASA Technical Reports Server (NTRS)

Maahs, H. G.

1983-01-01

Results are presented from a laboratory study of the kinetics of the S(IV)-O3 reaction in aqueous solution, including measurements of the effects of UV radiation, dissolved transition metals, and an antioxidant (hydroquinone) on the rate. On the basis of the results, relative rates of S(IV) conversion by O3 in tropospheric cloud water are compared with those predicted for H2O2 and for O2. The reaction mechanism is discussed, with an outline given of the elements of a possible reaction scheme. Application of the rate constants obtained to SO2 conversion in cloud water predicts conversion rates by ozone to be competitive with those by H2O2 at pH above about 4.5 and to dominate at pH above about 5.5. It is pointed out that since these pH's are typical for nonurban tropospheric cloud water, ozone is a potentially important contributor to the overall oxidative conversion of SO2 to sulfate in the nonurban troposphere.

Computational Prediction of Excited-State Carbon Tunneling in the Two Steps of Triplet Zimmerman Di-π-Methane Rearrangement.

PubMed

Li, Xin; Liao, Tao; Chung, Lung Wa

2017-11-22

The photoinduced Zimmerman di-π-methane (DPM) rearrangement of polycyclic molecules to form synthetically useful cyclopropane derivatives was found experimentally to proceed in a triplet excited state. We have applied state-of-the-art quantum mechanical methods, including M06-2X, DLPNO-CCSD(T) and variational transition-state theory with multidimensional tunneling corrections, to an investigation of the reaction rates of the two steps in the triplet DPM rearrangement of dibenzobarrelene, benzobarrelene and barrelene. This study predicts a high probability of carbon tunneling in regions around the two consecutive transition states at 200-300 K, and an enhancement in the rates by 104-276/35-67% with carbon tunneling at 200/300 K. The Arrhenius plots of the rate constants were found to be curved at low temperatures. Moreover, the computed 12 C/ 13 C kinetic isotope effects were affected significantly by carbon tunneling and temperature. Our predictions of electronically excited-state carbon tunneling and two consecutive carbon tunneling are unprecedented. Heavy-atom tunneling in some photoinduced reactions with reactive intermediates and narrow barriers can be potentially observed at relatively low temperature in experiments.

Direct numerical simulation of turbulent H2-O2 combustion using reduced chemistry

NASA Technical Reports Server (NTRS)

Montgomery, Christopher J.; Kosaly, George; Riley, James J.

1993-01-01

Results of direct numerical simulations of hydrogen-oxygen combustion using a partial-equilibrium chemistry scheme in constant density, decaying, isotropic turbulence are reported. The simulations qualitatively reproduce many features of experimental results, such as superequilibrium radical species mole fractions, with temperature and major species mole fractions closer to chemical equilibrium. It was also observed that the peak reaction rates occur in narrow zones where the stoichiometric surface intersects regions of high scalar dissipation, as might be expected for combustion conditions close to chemical equilibrium. Another finding was that high OH mole fraction correspond more closely to the stoichiometric surface than to areas of high reaction rate for conditions of the simulations. Simulation results were compared to predictions of the Conditional Moment Closure model. This model was found to give good results for all quantities of interest when the conditionally averaged scalar dissipation was used in the prediction. When the nonconditioned average dissipation was used, the predictions compared well to the simulations for most of the species and temperature, but not for the reaction rate. The comparison would be expected to improve for higher Reynolds number flows, however.

Rate Constants and Mechanisms of Protein–Ligand Binding

PubMed Central

Pang, Xiaodong; Zhou, Huan-Xiang

2017-01-01

Whereas protein–ligand binding affinities have long-established prominence, binding rate constants and binding mechanisms have gained increasing attention in recent years. Both new computational methods and new experimental techniques have been developed to characterize the latter properties. It is now realized that binding mechanisms, like binding rate constants, can and should be quantitatively determined. In this review, we summarize studies and synthesize ideas on several topics in the hope of providing a coherent picture of and physical insight into binding kinetics. The topics include microscopic formulation of the kinetic problem and its reduction to simple rate equations; computation of binding rate constants; quantitative determination of binding mechanisms; and elucidation of physical factors that control binding rate constants and mechanisms. PMID:28375732

Insect density-plant density relationships: a modified view of insect responses to resource concentrations.

PubMed

Andersson, Petter; Löfstedt, Christer; Hambäck, Peter A

2013-12-01

Habitat area is an important predictor of spatial variation in animal densities. However, the area often correlates with the quantity of resources within habitats, complicating our understanding of the factors shaping animal distributions. We addressed this problem by investigating densities of insect herbivores in habitat patches with a constant area but varying numbers of plants. Using a mathematical model, predictions of scale-dependent immigration and emigration rates for insects into patches with different densities of host plants were derived. Moreover, a field experiment was conducted where the scaling properties of odour-mediated attraction in relation to the number of odour sources were estimated, in order to derive a prediction of immigration rates of olfactory searchers. The theoretical model predicted that we should expect immigration rates of contact and visual searchers to be determined by patch area, with a steep scaling coefficient, μ = -1. The field experiment suggested that olfactory searchers should show a less steep scaling coefficient, with μ ≈ -0.5. A parameter estimation and analysis of published data revealed a correspondence between observations and predictions, and density-variation among groups could largely be explained by search behaviour. Aphids showed scaling coefficients corresponding to the prediction for contact/visual searchers, whereas moths, flies and beetles corresponded to the prediction for olfactory searchers. As density responses varied considerably among groups, and variation could be explained by a certain trait, we conclude that a general theory of insect responses to habitat heterogeneity should be based on shared traits, rather than a general prediction for all species.

Predicting heterocyclic ring coupling constants through a conformational search of tetra-O-methyl-(+)-catechin

Treesearch

Fred L. Tobiason; Richard W. Hemingway

1994-01-01

A GMMX conformational search routine gives a family of conformations that reflects the Boltzmann-averaged heterocyclic ring conformation as evidenced by accurate prediction of all three coupling constants observed for tetra-O-methyl-(+)-catechin.

Predicting heterocyclic ring coupling constants through a conformational search of tetra-o-methyl-(+)-catechin

Treesearch

Fred L. Tobiason; Richard w. Hemingway

1994-01-01

A GMMXe conformational search routine gives a family a conformations that reflects the boltzmann-averaged heterocyclic ring conformation as evidence by accurate prediction of all three coupling constants observed for tetra-O-methyl-(+)-catechin.

Rate Constant and Temperature Dependence for the Reaction of Hydroxyl Radicals with 2-Flouropropane (FC-281ea) and Comparison with an Estimated Rate Constant

NASA Technical Reports Server (NTRS)

DeMore, W.; Wilson, E., Jr.

1998-01-01

Relative rate experiments were used to measure the rate constant and temperature dependence of the reaction of OH radicals with 2-fluoropropane (HFC-281ea), using ethane, propane, ethyl chloride as reference standards.

Kinetic Analysis of Haloacetonitrile Stability in Drinking Waters.

PubMed

Yu, Yun; Reckhow, David A

2015-09-15

Haloacetonitriles (HANs) are an important class of drinking water disinfection byproducts (DBPs) that are reactive and can undergo considerable transformation on time scales relevant to system distribution (i.e., from a few hours to a week or more). The stability of seven mono-, di-, and trihaloacetonitriles was examined under a variety of conditions including different pH levels and disinfectant doses that are typical of drinking water distribution systems. Results indicated that hydroxide, hypochlorite, and their protonated forms could react with HANs via nucleophilic attack on the nitrile carbon, forming the corresponding haloacetamides (HAMs) and haloacetic acids (HAAs) as major reaction intermediates and end products. Other stable intermediate products, such as the N-chloro-haloacetamides (N-chloro-HAMs), may form during the course of HAN chlorination. A scheme of pathways for the HAN reactions was proposed, and the rate constants for individual reactions were estimated. Under slightly basic conditions, hydroxide and hypochlorite are primary reactants and their associated second-order reaction rate constants were estimated to be 6 to 9 orders of magnitude higher than those of their protonated conjugates (i.e., neutral water and hypochlorous acid), which are much weaker but more predominant nucleophiles at neutral and acidic pHs. Developed using the estimated reaction rate constants, the linear free energy relationships (LFERs) summarized the nucleophilic nature of HAN reactions and demonstrated an activating effect of the electron withdrawing halogens on nitrile reactivity, leading to decreasing HAN stability with increasing degree of halogenation of the substituents, while subsequent shift from chlorine to bromine atoms has a contrary stabilizing effect on HANs. The chemical kinetic model together with the reaction rate constants that were determined in this work can be used for quantitative predictions of HAN concentrations depending on pH and free chlorine contact times (CTs), which can be applied as an informative tool by drinking water treatment and system management engineers to better control these emerging nitrogenous DBPs, and can also be significant in making regulatory decisions.

Computational study of chain transfer to monomer reactions in high-temperature polymerization of alkyl acrylates.

PubMed

Moghadam, Nazanin; Liu, Shi; Srinivasan, Sriraj; Grady, Michael C; Soroush, Masoud; Rappe, Andrew M

2013-03-28

This article presents a computational study of chain transfer to monomer (CTM) reactions in self-initiated high-temperature homopolymerization of alkyl acrylates (methyl, ethyl, and n-butyl acrylate). Several mechanisms of CTM are studied. The effects of the length of live polymer chains and the type of monoradical that initiated the live polymer chains on the energy barriers and rate constants of the involved reaction steps are investigated theoretically. All calculations are carried out using density functional theory. Three types of hybrid functionals (B3LYP, X3LYP, and M06-2X) and four basis sets (6-31G(d), 6-31G(d,p), 6-311G(d), and 6-311G(d,p)) are applied to predict the molecular geometries of the reactants, products and transition sates, and energy barriers. Transition state theory is used to estimate rate constants. The results indicate that abstraction of a hydrogen atom (by live polymer chains) from the methyl group in methyl acrylate, the methylene group in ethyl acrylate, and methylene groups in n-butyl acrylate are the most likely mechanisms of CTM. Also, the rate constants of CTM reactions calculated using M06-2X are in good agreement with those estimated from polymer sample measurements using macroscopic mechanistic models. The rate constant values do not change significantly with the length of live polymer chains. Abstraction of a hydrogen atom by a tertiary radical has a higher energy barrier than abstraction by a secondary radical, which agrees with experimental findings. The calculated and experimental NMR spectra of dead polymer chains produced by CTM reactions are comparable. This theoretical/computational study reveals that CTM occurs most likely via hydrogen abstraction by live polymer chains from the methyl group of methyl acrylate and methylene group(s) of ethyl (n-butyl) acrylate.

Kinetics and Thermodynamics of the Reaction between the (•)OH Radical and Adenine: A Theoretical Investigation.

PubMed

Milhøj, Birgitte O; Sauer, Stephan P A

2015-06-18

The accessibility of all possible reaction paths for the reaction between the nucleobase adenine and the (•)OH radical is investigated through quantum chemical calculations of barrier heights and rate constants at the ωB97X-D/6-311++G(2df,2pd) level with Eckart tunneling corrections. First the computational method is validated by considering the hydrogen abstraction from the heterocyclic N9 nitrogen in adenine as a test system. Geometries for all molecules in the reaction are optimized with four different DFT exchange-correlation functionals (B3LYP, BHandHLYP, M06-2X, and ωB97X-D), in combination with Pople and Dunning basis sets, all of which have been employed in similar investigations in the literature. Improved energies are obtained through single point calculations with CCSD(T) and the same basis sets, and reaction rate constants are calculated for all methods both without tunneling corrections and with the Wigner, Bell, and Eckart corrections. In comparison to CCSD(T)//BHandHLYP/aug-cc-pVTZ reference results, the ωB97X-D/6-311++G(2df,2pd) method combined with Eckart tunneling corrections provides a sensible compromise between accuracy and time. Using this method, all subreactions of the reaction between adenine and the (•)OH radical are investigated. The total rate constants for hydrogen abstraction and addition for adenine are predicted with this method to be 1.06 × 10(-12) and 1.10 × 10(-12) cm(3) molecules(-1) s(-1), respectively. Abstractions of H61 and H62 contribute the most, while only addition to the C8 carbon is found to be of any significance, in contrast to previous claims that addition is the dominant reaction pathway. The overall rate constant for the complete reaction is found to be 2.17 × 10(-12) cm(3) molecules(-1) s(-1), which agrees exceptionally well with experimental results.

Comparisons between thermodynamic and one-dimensional combustion models of spark-ignition engines

NASA Technical Reports Server (NTRS)

Ramos, J. I.

1986-01-01

Results from a one-dimensional combustion model employing a constant eddy diffusivity and a one-step chemical reaction are compared with those of one-zone and two-zone thermodynamic models to study the flame propagation in a spark-ignition engine. One-dimensional model predictions are found to be very sensitive to the eddy diffusivity and reaction rate data. The average mixing temperature found using the one-zone thermodynamic model is higher than those of the two-zone and one-dimensional models during the compression stroke, and that of the one-dimensional model is higher than those predicted by both thermodynamic models during the expansion stroke. The one-dimensional model is shown to predict an accelerating flame even when the front approaches the cold cylinder wall.

Rapid estimation of glucosinolate thermal degradation rate constants in leaves of Chinese kale and broccoli (Brassica oleracea) in two seasons.

PubMed

Hennig, Kristin; Verkerk, Ruud; Bonnema, Guusje; Dekker, Matthijs

2012-08-15

Kinetic modeling was used as a tool to quantitatively estimate glucosinolate thermal degradation rate constants. Literature shows that thermal degradation rates differ in different vegetables. Well-characterized plant material, leaves of broccoli and Chinese kale plants grown in two seasons, was used in the study. It was shown that a first-order reaction is appropriate to model glucosinolate degradation independent from the season. No difference in degradation rate constants of structurally identical glucosinolates was found between broccoli and Chinese kale leaves when grown in the same season. However, glucosinolate degradation rate constants were highly affected by the season (20-80% increase in spring compared to autumn). These results suggest that differences in glucosinolate degradation rate constants can be due to variation in environmental as well as genetic factors. Furthermore, a methodology to estimate rate constants rapidly is provided to enable the analysis of high sample numbers for future studies.

Aqueous reactions of triplet excited states with allylic compounds

NASA Astrophysics Data System (ADS)

Kaur, R.; Anastasio, C.; Hudson, B. M.; Tantillo, D. J.

2016-12-01

Triplet excited states of dissolved organic matter react with several classes of aromatic organics such as phenols, anilines, sulfonamide antibiotics and phenylurea herbicides. Aqueous triplets appear to be among the most important oxidants for atmospheric phenols in regions with biomass burning, with phenol lifetimes on the order of a few hours to a day. However, little is known of the reactions of triplets with other classes of organic compounds. Recent work from our group shows that triplets react rapidly with several biogenic volatile organic compounds (BVOCs), such as methyl jasmonate, cis-3-hexenyl acetate, and cis-3-hexen-1-ol. However, there are only a few rate constants for aqueous reactions between alkenes such as these and triplet excited states. For our work, we refer to these and similar alkenes which have hydrogen(s) attached to a carbon adjacent to the double bond, as allylic compounds. To better assess the importance of triplets as aqueous oxidants, we measured second-order rate constants (kAC+3BP*) for a number of allylic compounds (ACs) with the triplet state of benzophenone; then established a quantitative structure-activity relationship (QSAR) between kAC+3BP* and computed oxidation potential of the ACs (R2 =0.65). Using the QSAR, we estimated the rate constants for triplets with some allylic isoprene and limonene oxidation products that have high Henry's law constants (KH>103 M atm-1). Hydroxylated limonene products and the delta-isomers of isoprene hydroxyhydroperoxides (δ4ISOPOOH) and hydroxynitrates (δ4ISONO2) were faster with predicted kAC+3BP* values ranging between (0.5-3.5) x 109 M-1-s-1 whereas the beta-isomers of ISOPOOH and ISONO2 were slower (kAC+3BP* < 0.5 x 109 M-1s-1). We scaled the predicted kAC+3BP* to represent less reactive atmospheric triplets that have been measured in fog drops, and compared to gas and aqueous hydroxyl radical and ozone, triplets in fog could account for up to 20 % of the measured loss of these compounds in the atmosphere. We are currently evaluating the importance of triplets in particulate matter (PM) which can have much higher concentrations of triplet precursors than fog. Our results show that as oxidants of unsaturated organic compounds, triplet excited states are of modest significance in fog/cloud drops but could be very significant in PM.

Application of ADM1 for modeling of biogas production from anaerobic digestion of Hydrilla verticillata.

PubMed

Chen, Xiaojuan; Chen, Zhihua; Wang, Xun; Huo, Chan; Hu, Zhiquan; Xiao, Bo; Hu, Mian

2016-07-01

The present study focused on the application of anaerobic digestion model no. 1 (ADM1) to simulate biogas production from Hydrilla verticillata. Model simulation was carried out by implementing ADM1 in AQUASIM 2.0 software. Sensitivity analysis was used to select the most sensitive parameters for estimation using the absolute-relative sensitivity function. Among all the kinetic parameters, disintegration constant (kdis), hydrolysis constant of protein (khyd_pr), Monod maximum specific substrate uptake rate (km_aa, km_ac, km_h2) and half-saturation constants (Ks_aa, Ks_ac) affect biogas production significantly, which were optimized by fitting of the model equations to the data obtained from batch experiments. The ADM1 model after parameter estimation was able to well predict the experimental results of daily biogas production and biogas composition. The simulation results of evolution of organic acids, bacteria concentrations and inhibition effects also helped to get insight into the reaction mechanisms. Copyright © 2016. Published by Elsevier Ltd.

Developmental Times of Chrysomya megacephala (Fabricius) (Diptera: Calliphoridae) at Constant Temperatures and Applications in Forensic Entomology.

PubMed

Yang, Yong-Qiang; Li, Xue-Bo; Shao, Ru-Yue; Lyu, Zhou; Li, Hong-Wei; Li, Gen-Ping; Xu, Lyu-Zi; Wan, Li-Hua

2016-09-01

The characteristic life stages of infesting blowflies (Calliphoridae) such as Chrysomya megacephala (Fabricius) are powerful evidence for estimating the death time of a corpse, but an established reference of developmental times for local blowfly species is required. We determined the developmental rates of C. megacephala from southwest China at seven constant temperatures (16-34°C). Isomegalen and isomorphen diagrams were constructed based on the larval length and time for each developmental event (first ecdysis, second ecdysis, wandering, pupariation, and eclosion), at each temperature. A thermal summation model was constructed by estimating the developmental threshold temperature D0 and the thermal summation constant K. The thermal summation model indicated that, for complete development from egg hatching to eclosion, D0 = 9.07 ± 0.54°C and K = 3991.07 ± 187.26 h °C. This reference can increase the accuracy of estimations of postmortem intervals in China by predicting the growth of C. megacephala. © 2016 American Academy of Forensic Sciences.

Methane steam reforming rates over Pt, Rh and Ni(111) accounting for H tunneling and for metal lattice vibrations

NASA Astrophysics Data System (ADS)

German, Ernst D.; Sheintuch, Moshe

2017-02-01

Microkinetic models of methane steam reforming (MSR) over bare platinum and rhodium (111) surfaces are analyzed in present work using calculated rate constants. The individual rate constants are classified into three different sets: (i) rate constants of adsorption and desorption steps of CH4, H2O, CO and of H2; (ii) rate constants of dissociation and formation of A-H bonds (A = C, O, and H), and (iii) rate constants of dissociation and formation of C-O bond. The rate constants of sets (i) and (iii) are calculated using transition state theory and published thermochemical data. The rate constants of H-dissociation reactions (set (ii)) are calculated in terms of a previously-developed approach that accounts for thermal metal lattice vibrations and for H tunneling through a potential barrier of height which depends on distance of AH from a surface. Pre-exponential factors of several group (ii) steps were calculated to be usually lower than the traditional kBT/h due to tunneling effect. Surface composition and overall MSR rates over platinum and rhodium surfaces are compared with those over nickel surface showing that operating conditions strongly affect on the activity order of the catalysts.

Toward Theoretical Foundations of Resistive Force Theory of Granular-Structural Interaction, with Expansions to Flexible Locomotors

DTIC Science & Technology

2015-05-07

the proper depth-dependent pressure distribution before intruder motion begins. We model the intruder as a rigid surface within the granular body by...assigning corresponding planar nodes to move as a rigid body at a constant rate. This resembles a fully rough surface due to the no-slip condition, no...Stokesian fluids. Despite its remarkable capability to predict experimental locomotion and force distributions on mobile bodies in granular media, there is

Fatigue damage mechanics of notched graphite-epoxy laminates

NASA Astrophysics Data System (ADS)

Spearing, Mark; Beaumont, Peter W. R.; Ashby, Michael F.

A modeling approach is presented that recognizes that the residual properties of composite laminates after any form of loading depend on the damage state. Therefore, in the case of cyclic loading, it is necessary to first derive a damage growth law and then relate the residual properties to the accumulated damage. The propagation of fatigue damage in notched laminates is investigated. A power law relationship between damage growth and the strain energy release rate is developed. The material constants used in the model have been determined in independent experiments and are invariant for all the layups investigated. The strain energy release rates are calculated using a simple finite element representation of the damaged specimen. The model is used to predict the effect of tension-tension cyclic loading on laminates of the T300/914C carbon-fiber epoxy system. The extent of damage propagation is successfully predicted in a number of cross-ply laminates.

Recovery from nonlinear creep provides a window into physics of polymer glasses

NASA Astrophysics Data System (ADS)

Caruthers, James; Medvedev, Grigori

Creep under constant applied stress is one of the most basic mechanical experiments, where it exhibits extremely rich relaxation behavior for polymer glasses. As many as five distinct stages of nonlinear creep are observed, where the rate of creep dramatically slows down, accelerates and then slows down again. Modeling efforts to-date has primarily focused on predicting the intricacies of the nonlinear creep curve. We argue that as much attention should be paid to the creep recovery response, when the stress is removed. The experimental creep recovery curve is smooth, where the rate of recovery is initially quite rapid and then progressively decreases. In contrast, the majority of the traditional constitutive models predict recovery curves that are much too abrupt. A recently developed stochastic constitutive model that takes into account the dynamic heterogeneity of glasses produces a smooth creep recovery response that is consistent with experiment.

How to deal with the Poisson-gamma model to forecast patients' recruitment in clinical trials when there are pauses in recruitment dynamic?

PubMed

Minois, Nathan; Savy, Stéphanie; Lauwers-Cances, Valérie; Andrieu, Sandrine; Savy, Nicolas

2017-03-01

Recruiting patients is a crucial step of a clinical trial. Estimation of the trial duration is a question of paramount interest. Most techniques are based on deterministic models and various ad hoc methods neglecting the variability in the recruitment process. To overpass this difficulty the so-called Poisson-gamma model has been introduced involving, for each centre, a recruitment process modelled by a Poisson process whose rate is assumed constant in time and gamma-distributed. The relevancy of this model has been widely investigated. In practice, rates are rarely constant in time, there are breaks in recruitment (for instance week-ends or holidays). Such information can be collected and included in a model considering piecewise constant rate functions yielding to an inhomogeneous Cox model. The estimation of the trial duration is much more difficult. Three strategies of computation of the expected trial duration are proposed considering all the breaks, considering only large breaks and without considering breaks. The bias of these estimations procedure are assessed by means of simulation studies considering three scenarios of breaks simulation. These strategies yield to estimations with a very small bias. Moreover, the strategy with the best performances in terms of prediction and with the smallest bias is the one which does not take into account of breaks. This result is important as, in practice, collecting breaks data is pretty hard to manage.

Implication of surface modified NZVI particle retention in the porous media: Assessment with the help of 1-D transport model

NASA Astrophysics Data System (ADS)

Raychoudhury, Trishikhi; Surasani, Vikranth Kumar

2017-06-01

Retention of surface-modified nanoscale zero-valent iron (NZVI) particles in the porous media near the point of injection has been reported in the recent studies. Retention of excess particles in porous media can alter the media properties. The main objectives of this study are, therefore, to evaluate the effect of particle retention on the porous media properties and its implication on further NZVI particle transport under different flow conditions. To achieve the objectives, a one-dimensional transport model is developed by considering particle deposition, detachment, and straining mechanisms along with the effect of changes in porosity resulting from retention of NZVI particles. Two different flow conditions are considered for simulations. The first is a constant Darcy's flow rate condition, which assumes a change in porosity, causes a change in pore water velocity and the second, is a constant head condition, which assumes the change in porosity, influence the permeability and hydraulic conductivity (thus Darcy's flow rate). Overall a rapid decrease in porosity was observed as a result of high particle retention near the injection points resulting in a spatial distribution of deposition rate coefficient. In the case of constant head condition, the spatial distribution of Darcy's velocities is predicted due to variation in porosity and hydraulic conductivity. The simulation results are compared with the data reported from the field studies; which suggests straining is likely to happen in the real field condition.

Detection of the YORP effect in asteroid (161989) Cacus

NASA Astrophysics Data System (ADS)

Durech, Josef; Vokrouhlicky, David; Pravec, Petr; Hanus, Josef; Kusnirak, Peter; Hornoch, Kamil; Galad, Adrian; Masi, Gianluca

2016-10-01

The rotation state of small asteroids is affected by the thermal Yarkovsky-O'Keefe-Radzievski-Paddack (YORP) torque. The directly observable consequence of YORP is the secular change of the asteroid's rotational period in time. We carried out new photometric observations of asteroid (161989) Cacus during its apparitions in 2014-2016. Using the new lightcurves together with archived data going back to 1978, we were able to detect a tiny deviation from the constant-period rotation. This deviation caused an observable shift between the observed lightcurves and those predicted by the best constant-period model. We used the lightcurve inversion method to derive a shape/spin solution that fitted the data at best. We assumed that the rotation rate evolved linearly in time and derived the acceleration of the rotation rate dω/dt = (1.9 +/- 0.3) × 10-8 rad/day2. The accelerating model provides a significantly better fit than the constant-period model. By applying a thermophysical model on WISE thermal infrared data, we estimated the thermal inertia of the surface to Γ = 250-2000 J m-2 s-0.5 K-1 and the volume-equivalent diameter to 0.8-1.2 km (1σ intervals). The value of dω/dt derived from observations is in agreement with the theoretical value computed numerically from the lightcurve inversion shape model and its spin axis orientation. Cacus has become the sixth asteroid with YORP detection. Surprisingly, for all six cases the rotation rate accelerates.

Diurnal Temperature Variations Affect Development of a Herbivorous Arthropod Pest and its Predators

PubMed Central

Vangansbeke, Dominiek; Audenaert, Joachim; Nguyen, Duc Tung; Verhoeven, Ruth; Gobin, Bruno; Tirry, Luc; De Clercq, Patrick

2015-01-01

The impact of daily temperature variations on arthropod life history remains woefully understudied compared to the large body of research that has been carried out on the effects of constant temperatures. However, diurnal varying temperature regimes more commonly represent the environment in which most organisms thrive. Such varying temperature regimes have been demonstrated to substantially affect development and reproduction of ectothermic organisms, generally in accordance with Jensen’s inequality. In the present study we evaluated the impact of temperature alternations at 4 amplitudes (DTR0, +5, +10 and +15°C) on the developmental rate of the predatory mites Phytoseiulus persimilis Athias-Henriot and Neoseiulus californicus McGregor (Acari: Phytoseiidae) and their natural prey, the two-spotted spider mite Tetranychus urticae Koch (Acari: Tetranychidae). We have modelled their developmental rates as a function of temperature using both linear and nonlinear models. Diurnally alternating temperatures resulted in a faster development in the lower temperature range as compared to their corresponding mean constant temperatures, whereas the opposite was observed in the higher temperature range. Our results indicate that Jensen’s inequality does not suffice to fully explain the differences in developmental rates at constant and alternating temperatures, suggesting additional physiological responses play a role. It is concluded that diurnal temperature range should not be ignored and should be incorporated in predictive models on the phenology of arthropod pests and their natural enemies and their performance in biological control programmes. PMID:25874697

Ab initio chemical kinetic study on Cl + ClO and related reverse processes.

PubMed

Xu, Z F; Lin, M C

2010-11-04

The reaction of ClO with Cl and its related reverse processes have been studied theoretically by ab initio quantum chemical and statistical mechanical calculations. The geometric parameters of the reactants, products, and transition states are optimized by both UMPW1PW91 and unrestricted coupled-cluster single and double excitation (UCCSD) methods with the 6-311+G(3df) basis set. The potential energy surface has been further refined (with triple excitations, T) at the UCCSD(T)/6-311+G(3df) level of theory. The results show that Cl(2) and O ((3)P) can be produced by chlorine atom abstraction via a tight transition state, while ClOCl ((1)A(1)) and ClClO ((1)A') can be formed by barrierless association processes with exothermicities of 31.8 and 16.0 kcal/mol, respectively. In principle the O ((1)D) atom can be generated with a large endothermicity of 56.9 kcal/mol; on the other hand, its barrierless reaction with Cl(2) can readily form ClClO ((1)A'), which fragments rapidly to give ClO + Cl. The rate constants of both forward and reverse processes have been predicted at 150-2000 K by the microcanonical variational transition state theory (VTST)/Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The predicted rate constants are in good agreement with available experimental data within reported errors.

Flows of dioxins and furans in coastal food webs: inverse modeling, sensitivity analysis, and applications of linear system theory.

PubMed

Saloranta, Tuomo M; Andersen, Tom; Naes, Kristoffer

2006-01-01

Rate constant bioaccumulation models are applied to simulate the flow of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the coastal marine food web of Frierfjorden, a contaminated fjord in southern Norway. We apply two different ways to parameterize the rate constants in the model, global sensitivity analysis of the models using Extended Fourier Amplitude Sensitivity Test (Extended FAST) method, as well as results from general linear system theory, in order to obtain a more thorough insight to the system's behavior and to the flow pathways of the PCDD/Fs. We calibrate our models against observed body concentrations of PCDD/Fs in the food web of Frierfjorden. Differences between the predictions from the two models (using the same forcing and parameter values) are of the same magnitude as their individual deviations from observations, and the models can be said to perform about equally well in our case. Sensitivity analysis indicates that the success or failure of the models in predicting the PCDD/F concentrations in the food web organisms highly depends on the adequate estimation of the truly dissolved concentrations in water and sediment pore water. We discuss the pros and cons of such models in understanding and estimating the present and future concentrations and bioaccumulation of persistent organic pollutants in aquatic food webs.

Fiber-Supported Droplet Combustion. Experiment 32

NASA Technical Reports Server (NTRS)

Dietrich, Daniel L.; Haggard, John B., Jr.; Nayagam, Vedha; Dryer, Frederick L.; Williams, Forman A.; Shaw, Ben D.

1998-01-01

Individual droplets with diameters ranging from about 2 mm to 5 mm were burned under microgravity conditions in air at 1 bar with an ambient temperature of 300 K. Each droplet was tethered by a silicon carbide fiber of 80 mm or 150 mm diameter to keep it in view of video recording, and, in some tests, a forced air flow was applied in a direction parallel to the fiber axis. Methanol, two methanol-water mixtures, two methanol-dodecanol mixtures, and two heptane-hexadecane mixtures were the fuels. Droplet diameters were measured as functions of time and compared with existing theoretical predictions. The prediction that methanol droplets extinguish at diameters that increase with increasing initial droplet diameter is verified by these experiments. In addition, the quasi-steady burning rate constant of the heptane-hexadecane mixtures appears to decrease with increasing droplet diameter; obscuration consistent with very heavy sooting, but without the formation of soot shells, is observed for the largest of these droplets. Forced convective flow around methanol droplets was found to increase the burning rate and to produce a ratio of downstream-to-upstream flame radius that remained constant as the droplet size decreased, a trend in agreement with earlier results obtained at higher convective velocities for smaller droplets having larger flame standoff ratios. There are a number of implications of the experimental results regarding droplet-combustion theory.

High Throughput pharmacokinetic modeling using computationally predicted parameter values: dissociation constants (TDS)

EPA Science Inventory

Estimates of the ionization association and dissociation constant (pKa) are vital to modeling the pharmacokinetic behavior of chemicals in vivo. Methodologies for the prediction of compound sequestration in specific tissues using partition coefficients require a parameter that ch...

Microcomputer-Based Programs for Pharmacokinetic Simulations.

ERIC Educational Resources Information Center

Li, Ronald C.; And Others

1995-01-01

Microcomputer software that simulates drug-concentration time profiles based on user-assigned pharmacokinetic parameters such as central volume of distribution, elimination rate constant, absorption rate constant, dosing regimens, and compartmental transfer rate constants is described. The software is recommended for use in undergraduate…

MOlecular MAterials Property Prediction Package (MOMAP) 1.0: a software package for predicting the luminescent properties and mobility of organic functional materials

NASA Astrophysics Data System (ADS)

Niu, Yingli; Li, Wenqiang; Peng, Qian; Geng, Hua; Yi, Yuanping; Wang, Linjun; Nan, Guangjun; Wang, Dong; Shuai, Zhigang

2018-04-01

MOlecular MAterials Property Prediction Package (MOMAP) is a software toolkit for molecular materials property prediction. It focuses on luminescent properties and charge mobility properties. This article contains a brief descriptive introduction of key features, theoretical models and algorithms of the software, together with examples that illustrate the performance. First, we present the theoretical models and algorithms for molecular luminescent properties calculation, which includes the excited-state radiative/non-radiative decay rate constant and the optical spectra. Then, a multi-scale simulation approach and its algorithm for the molecular charge mobility are described. This approach is based on hopping model and combines with Kinetic Monte Carlo and molecular dynamics simulations, and it is especially applicable for describing a large category of organic semiconductors, whose inter-molecular electronic coupling is much smaller than intra-molecular charge reorganisation energy.

Model comparison for Escherichia coli growth in pouched food.

PubMed

Fujikawa, Hiroshi; Yano, Kazuyoshi; Morozumi, Satoshi

2006-06-01

We recently studied the growth characteristics of Escherichia coli cells in pouched mashed potatoes (Fujikawa et al., J. Food Hyg. Soc. Japan, 47, 95-98 (2006)). Using those experimental data, in the present study, we compared a logistic model newly developed by us with the modified Gompertz and the Baranyi models, which are used as growth models worldwide. Bacterial growth curves at constant temperatures in the range of 12 to 34 degrees C were successfully described with the new logistic model, as well as with the other models. The Baranyi gave the least error in cell number and our model gave the least error in the rate constant and the lag period. For dynamic temperature, our model successfully predicted the bacterial growth, whereas the Baranyi model considerably overestimated it. Also, there was a discrepancy between the growth curves described with the differential equations of the Baranyi model and those obtained with DMfit, a software program for Baranyi model fitting. These results indicate that the new logistic model can be used to predict bacterial growth in pouched food.

Effect of increasing dialysate flow rate on diffusive mass transfer of urea, phosphate and β2-microglobulin during clinical haemodialysis

PubMed Central

Bhimani, Jai P.; Ouseph, Rosemary; Ward, Richard A.

2010-01-01

Background. Diffusive clearance depends on blood and dialysate flow rates and the overall mass transfer area coefficient (KoA) of the dialyzer. Although KoA should be constant for a given dialyzer, urea KoA has been reported to vary with dialysate flow rate possibly because of improvements in flow distribution. This study examined the dependence of KoA for urea, phosphate and β2-microglobulin on dialysate flow rate in dialyzers containing undulating fibers to promote flow distribution and two different fiber packing densities. Methods. Twelve stable haemodialysis patients underwent dialysis with four different dialyzers, each used with a blood flow rate of 400 mL/min and dialysate flow rates of 350, 500 and 800 mL/min. Clearances of urea, phosphate and β2-microglobulin were measured and KoA values calculated. Results. Clearances of urea and phosphate, but not β2-microglobulin, increased significantly with increasing dialysate flow rate. However, increasing dialysate flow rate had no significant effect on KoA or Ko for any of the three solutes examined, although Ko for urea and phosphate increased significantly as the average flow velocity in the dialysate compartment increased. Conclusions. For dialyzers with features that promote good dialysate flow distribution, increasing dialysate flow rate beyond 600 mL/min at a blood flow rate of 400 mL/min is likely to have only a modest impact on dialyzer performance, limited to the theoretical increase predicted for a constant KoA. PMID:20543211

Effect of bacterial growth rate on bacteriophage population growth rate.

PubMed

Nabergoj, Dominik; Modic, Petra; Podgornik, Aleš

2018-04-01

It is important to understand how physiological state of the host influence propagation of bacteriophages (phages), due to the potential higher phage production needs in the future. In our study, we tried to elucidate the effect of bacterial growth rate on adsorption constant (δ), latent period (L), burst size (b), and bacteriophage population growth rate (λ). As a model system, a well-studied phage T4 and Escherichia coli K-12 as a host was used. Bacteria were grown in a continuous culture operating at dilution rates in the range between 0.06 and 0.98 hr -1 . It was found that the burst size increases linearly from 8 PFU·cell -1 to 89 PFU·cell -1 with increase in bacteria growth rate. On the other hand, adsorption constant and latent period were both decreasing from 2.6∙10 -9  ml·min -1 and 80 min to reach limiting values of 0.5 × 10 -9  ml·min -1 and 27 min at higher growth rates, respectively. Both trends were mathematically described with Michaelis-Menten based type of equation and reasons for such form are discussed. By applying selected equations, a mathematical equation for prediction of bacteriophage population growth rate as a function of dilution rate was derived, reaching values around 8 hr -1 at highest dilution rate. Interestingly, almost identical description can be obtained using much simpler Monod type equation and possible reasons for this finding are discussed. © 2017 The Authors. MicrobiologyOpen published by John Wiley & Sons Ltd.

Pronounced non-Arrhenius behaviour of hydrogen-abstractions from toluene and derivatives by phthalimide-N-oxyl radicals: a theoretical study.

PubMed

Hermans, Ive; Jacobs, Pierre; Peeters, Jozef

2008-02-28

Abstraction of hydrogen atoms by pthalimide-N-oxyl radicals is an important step in the N-hydroxyphthalimide catalyzed autoxidation of hydrocarbons. In this contribution, the temperature dependency of this reaction is evaluated by a detailed transition state theory based kinetic analysis for the case of toluene. Tunneling was found to play a very important role, enhancing the rate constant by a factor of 20 at room temperature. As a result, tunneling, in combination with the existence of two distinct rotamers of the transition state, causes a pronounced temperature dependency of the pre-exponential frequency factor, and, as a consequence, marked curvature of the Arrhenius plot. This explains why earlier experimental studies over a limited temperature range around 300 K found formal Arrhenius activation energies and pre-factors that are 4 kcal mol(-1) and three orders of magnitude smaller than the actual energy barrier and the corresponding frequency factor, respectively. Also as a consequence of tunneling, substitution of a deuterium atom for a hydrogen atom causes a large decrease in the rate constant, in agreement with the measured kinetic isotope effects. The present theoretical analysis, complementary to the experimental rate coefficient data, allows for a reliable prediction of the rate coefficient at higher temperatures, relevant for actual autoxidation processes.

Effect of misalignment on mechanical behavior of metals in creep. [computer programs

NASA Technical Reports Server (NTRS)

Wu, H. C.

1979-01-01

Application of the endochronic theory of viscoplasticity to creep, creep recovery, and stress relaxation at the small strain and short time range produced the following results: (1) The governing constitutive equations for constant-strain-rate stress-strain behavior, creep, creep recovery, and stress relaxation were derived by imposing appropriate constraints on the general constitutive equation of the endochronic theory. (2) A set of material constants was found which correlate strain-hardening, creep, creep recovery, and stress relaxation. (3) The theory predicts with reasonable accuracy the creep and creep recovery behaviors at short time. (4) The initial strain history prior to the creep stage affects the subsequent creep significantly. (5) A critical stress was established for creep recovery. A computer program, written for the misalignment problem is reported.

Dynamic ground-effect measurements on the F-15 STOL and Maneuver Technology Demonstrator (S/MTD) configuration

NASA Technical Reports Server (NTRS)

Kemmerly, Guy T.

1990-01-01

A moving-model ground-effect testing method was used to study the influence of rate-of-descent on the aerodynamic characteristics for the F-15 STOL and Maneuver Technology Demonstrator (S/MTD) configuration for both the approach and roll-out phases of landing. The approach phase was modeled for three rates of descent, and the results were compared to the predictions from the F-15 S/MTD simulation data base (prediction based on data obtained in a wind tunnel with zero rate of descent). This comparison showed significant differences due both to the rate of descent in the moving-model test and to the presence of the ground boundary layer in the wind tunnel test. Relative to the simulation data base predictions, the moving-model test showed substantially less lift increase in ground effect, less nose-down pitching moment, and less increase in drag. These differences became more prominent at the larger thrust vector angles. Over the small range of rates of descent tested using the moving-model technique, the effect of rate of descent on longitudinal aerodynamics was relatively constant. The results of this investigation indicate no safety-of-flight problems with the lower jets vectored up to 80 deg on approach. The results also indicate that this configuration could employ a nozzle concept using lower reverser vector angles up to 110 deg on approach if a no-flare approach procedure were adopted and if inlet reingestion does not pose a problem.

A Comparative Analysis of Reynolds-Averaged Navier-Stokes Model Predictions for Rayleigh-Taylor Instability and Mixing with Constant and Complex Accelerations

NASA Astrophysics Data System (ADS)

Schilling, Oleg

2016-11-01

Two-, three- and four-equation, single-velocity, multicomponent Reynolds-averaged Navier-Stokes (RANS) models, based on the turbulent kinetic energy dissipation rate or lengthscale, are used to simulate At = 0 . 5 Rayleigh-Taylor turbulent mixing with constant and complex accelerations. The constant acceleration case is inspired by the Cabot and Cook (2006) DNS, and the complex acceleration cases are inspired by the unstable/stable and unstable/neutral cases simulated using DNS (Livescu, Wei & Petersen 2011) and the unstable/stable/unstable case simulated using ILES (Ramaprabhu, Karkhanis & Lawrie 2013). The four-equation models couple equations for the mass flux a and negative density-specific volume correlation b to the K- ɛ or K- L equations, while the three-equation models use a two-fluid algebraic closure for b. The lengthscale-based models are also applied with no buoyancy production in the L equation to explore the consequences of neglecting this term. Predicted mixing widths, turbulence statistics, fields, and turbulent transport equation budgets are compared among these models to identify similarities and differences in the turbulence production, dissipation and diffusion physics represented by the closures used in these models. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Dynamic Characteristics of The DSI-Type Constant-Flow Valves

NASA Astrophysics Data System (ADS)

Kang, Yuan; Hu, Sheng-Yan; Chou, Hsien-Chin; Lee, Hsing-Han

Constant flow valves have been presented in industrial applications or academic studies, which compensate recess pressures of a hydrostatic bearing to resist load fluctuating. The flow rate of constant-flow valves can be constant in spite of the pressure changes in recesses, however the design parameters must be specified. This paper analyzes the dynamic responses of DSI-type constant-flow valves that is designed as double pistons on both ends of a spool with single feedback of working pressure and regulating restriction at inlet. In this study the static analysis presents the specific relationships among design parameters for constant flow rate and the dynamic analyses give the variations around the constant flow rate as the working pressure fluctuates.

A Green's function method for simulation of time-dependent solute transport and reaction in realistic microvascular geometries

PubMed Central

Secomb, Timothy W.

2016-01-01

A novel theoretical method is presented for simulating the spatially resolved convective and diffusive transport of reacting solutes between microvascular networks and the surrounding tissues. The method allows for efficient computational solution of problems involving convection and non-linear binding of solutes in blood flowing through microvascular networks with realistic 3D geometries, coupled with transvascular exchange and diffusion and reaction in the surrounding tissue space. The method is based on a Green's function approach, in which the solute concentration distribution in the tissue is expressed as a sum of fields generated by time-varying distributions of discrete sources and sinks. As an example of the application of the method, the washout of an inert diffusible tracer substance from a tissue region perfused by a network of microvessels is simulated, showing its dependence on the solute's transvascular permeability and tissue diffusivity. Exponential decay of the washout concentration is predicted, with rate constants that are about 10–30% lower than the rate constants for a tissue cylinder model with the same vessel length, vessel surface area and blood flow rate per tissue volume. PMID:26443811

Uptake dynamics of inorganic mercury and methylmercury by the earthworm Pheretima guillemi.

PubMed

Dang, Fei; Zhao, Jie; Zhou, Dongmei

2016-02-01

Mercury uptake dynamics in the earthworm Pheretima guillemi, including the dissolved uptake rate constant (ku) from pore-water and assimilation efficiencies (AEs) from mercury-contaminated soil, was quantified in this study. Dissolved uptake rate constants were 0.087 and 0.553 L g(-1) d(-1) for inorganic mercury (IHg) and methylmercury (MeHg), respectively. Assimilation efficiency of IHg in field-contaminated soil was 7.2%, lower than 15.4% of spiked soil. In contrast, MeHg exhibited comparable AEs for both field-contaminated and spiked soil (82.4-87.2%). Within the framework of biodynamic model, we further modelled the exposure pathways (dissolved exposure vs soil ingestion) to source the accumulated mercury in Pheretima guillemi. The model showed that the relative importance of soil ingestion to mercury bioaccumulation depended largely on mercury partitioning coefficients (K(d)), and was also influenced by soil ingestion rate of earthworms. In the examined field-contaminated soil, almost (>99%) accumulated IHg and MeHg was predicted to derive from soil ingestion. Therefore, soil ingestion should be carefully considered when assessing mercury exposure risk to earthworms. Copyright © 2015 Elsevier Ltd. All rights reserved.

Calculating tracer currents through narrow ion channels: Beyond the independent particle model.

PubMed

Coalson, Rob D; Jasnow, David

2018-06-01

Discrete state models of single-file ion permeation through a narrow ion channel pore are employed to analyze the ratio of forward to backward tracer current. Conditions under which the well-known Ussing formula for this ratio hold are explored in systems where ions do not move independently through the channel. Building detailed balance into the rate constants for the model in such a way that under equilibrium conditions (equal rate of forward vs. backward permeation events) the Nernst Equation is satisfied, it is found that in a model where only one ion can occupy the channel at a time, the Ussing formula is always obeyed for any number of binding sites, reservoir concentrations of the ions and electric potential difference across the membrane which the ion channel spans, independent of the internal details of the permeation pathway. However, numerical analysis demonstrates that when multiple ions can occupy the channel at once, the nonequilibrium forward/backward tracer flux ratio deviates from the prediction of the Ussing model. Assuming an appropriate effective potential experienced by ions in the channel, we provide explicit formulae for the rate constants in these models. © 2018 IOP Publishing Ltd.

Vapor condensation on liquid surface due to laminar jet-induced mixing: The effects of system parameters

NASA Technical Reports Server (NTRS)

Lin, Chin-Shun; Hasan, Mohammad M.

1989-01-01

The effects of system parameters on the interface condensation rate in a laminar jet induced mixing tank are numerically studied. The physical system consists of a partially filled cylindrical tank with a slightly subcooled jet discharged from the center of the tank bottom toward the liquid-vapor interface which is at a saturation temperature corresponding to the constant tank pressure. Liquid is also withdrawn from the outer part of the tank bottom to maintain the constant liquid level. The jet velocity is selected to be low enough such that the free surface is approximately flat. The effect of vapor superheat is assumed to be negligible. Therefore, the interface condensation rate can be determined from the resulting temperature field in the liquid region alone. The nondimensional form of the steady state conservation equations are solved by a finite difference method for various system parameters including liquid height to tank diameter ratio, tank to jet diameter ratio, liquid inflow to outflow area ratio, and a heat leak parameter which characterizes the uniform wall heat flux. Detailed analyses based on the numerical solutions are performed and simplified equations are suggested for the prediction of condensation rate.

Predicting functional divergence in protein evolution by site-specific rate shifts

NASA Technical Reports Server (NTRS)

Gaucher, Eric A.; Gu, Xun; Miyamoto, Michael M.; Benner, Steven A.

2002-01-01

Most modern tools that analyze protein evolution allow individual sites to mutate at constant rates over the history of the protein family. However, Walter Fitch observed in the 1970s that, if a protein changes its function, the mutability of individual sites might also change. This observation is captured in the "non-homogeneous gamma model", which extracts functional information from gene families by examining the different rates at which individual sites evolve. This model has recently been coupled with structural and molecular biology to identify sites that are likely to be involved in changing function within the gene family. Applying this to multiple gene families highlights the widespread divergence of functional behavior among proteins to generate paralogs and orthologs.

A Complex-Valued Firing-Rate Model That Approximates the Dynamics of Spiking Networks

PubMed Central

Schaffer, Evan S.; Ostojic, Srdjan; Abbott, L. F.

2013-01-01

Firing-rate models provide an attractive approach for studying large neural networks because they can be simulated rapidly and are amenable to mathematical analysis. Traditional firing-rate models assume a simple form in which the dynamics are governed by a single time constant. These models fail to replicate certain dynamic features of populations of spiking neurons, especially those involving synchronization. We present a complex-valued firing-rate model derived from an eigenfunction expansion of the Fokker-Planck equation and apply it to the linear, quadratic and exponential integrate-and-fire models. Despite being almost as simple as a traditional firing-rate description, this model can reproduce firing-rate dynamics due to partial synchronization of the action potentials in a spiking model, and it successfully predicts the transition to spike synchronization in networks of coupled excitatory and inhibitory neurons. PMID:24204236

Creep fatigue life prediction for engine hot section materials (isotropic)

NASA Technical Reports Server (NTRS)

Moreno, V.

1983-01-01

The Hot Section Technology (HOST) program, creep fatigue life prediction for engine hot section materials (isotropic), is reviewed. The program is aimed at improving the high temperature crack initiation life prediction technology for gas turbine hot section components. Significant results include: (1) cast B1900 and wrought IN 718 selected as the base and alternative materials respectively; (2) fatigue test specimens indicated that measurable surface cracks appear early in the specimen lives, i.e., 15% of total life at 871 C and 50% of life at 538 c; (3) observed crack initiation sites are all surface initiated and are associated with either grain boundary carbides or local porosity, transgrannular cracking is observed at the initiation site for all conditions tested; and (4) an initial evaluation of two life prediction models, representative of macroscopic (Coffin-Mason) and more microscopic (damage rate) approaches, was conducted using limited data generated at 871 C and 538 C. It is found that the microscopic approach provides a more accurate regression of the data used to determine crack initiation model constants, but overpredicts the effect of strain rate on crack initiation life for the conditions tested.

Circular Functions Based Comprehensive Analysis of Plastic Creep Deformations in the Fiber Reinforced Composites

NASA Astrophysics Data System (ADS)

Monfared, Vahid

2016-12-01

Analytically based model is presented for behavioral analysis of the plastic deformations in the reinforced materials using the circular (trigonometric) functions. The analytical method is proposed to predict creep behavior of the fibrous composites based on basic and constitutive equations under a tensile axial stress. New insight of the work is to predict some important behaviors of the creeping matrix. In the present model, the prediction of the behaviors is simpler than the available methods. Principal creep strain rate behaviors are very noteworthy for designing the fibrous composites in the creeping composites. Analysis of the mentioned parameter behavior in the reinforced materials is necessary to analyze failure, fracture, and fatigue studies in the creep of the short fiber composites. Shuttles, spaceships, turbine blades and discs, and nozzle guide vanes are commonly subjected to the creep effects. Also, predicting the creep behavior is significant to design the optoelectronic and photonic advanced composites with optical fibers. As a result, the uniform behavior with constant gradient is seen in the principal creep strain rate behavior, and also creep rupture may happen at the fiber end. Finally, good agreements are found through comparing the obtained analytical and FEM results.

Estimating Energy Conversion Efficiency of Thermoelectric Materials: Constant Property Versus Average Property Models

NASA Astrophysics Data System (ADS)

Armstrong, Hannah; Boese, Matthew; Carmichael, Cody; Dimich, Hannah; Seay, Dylan; Sheppard, Nathan; Beekman, Matt

2017-01-01

Maximum thermoelectric energy conversion efficiencies are calculated using the conventional "constant property" model and the recently proposed "cumulative/average property" model (Kim et al. in Proc Natl Acad Sci USA 112:8205, 2015) for 18 high-performance thermoelectric materials. We find that the constant property model generally predicts higher energy conversion efficiency for nearly all materials and temperature differences studied. Although significant deviations are observed in some cases, on average the constant property model predicts an efficiency that is a factor of 1.16 larger than that predicted by the average property model, with even lower deviations for temperature differences typical of energy harvesting applications. Based on our analysis, we conclude that the conventional dimensionless figure of merit ZT obtained from the constant property model, while not applicable for some materials with strongly temperature-dependent thermoelectric properties, remains a simple yet useful metric for initial evaluation and/or comparison of thermoelectric materials, provided the ZT at the average temperature of projected operation, not the peak ZT, is used.

Fluid dynamics of the unsteady two phase processes leading to DDT in granular solid propellants

NASA Technical Reports Server (NTRS)

Krier, H.; Butler, P. B.; Lembeck, M. F.

1980-01-01

Deflagration to Detonation (DDT) was predicted to occur in porous beds of high-energy solid propellants by solving the unsteady fluid mechanical convective heat transfer from hot gas products, obtained from the rapid burning at high pressures, provides the impetus to develop a narrow combustion zone and a resulting strong shock. A parametric study clearly indicates that DDT occurs only when a combination of the solids loading fraction, the burning rate constants, the propellant chemical energy, and the particle size provide for critical energy and gas release to support a detonation wave. Predictions for the run-up length to detonation as a function of these parameters are presented.

Prediction of pathogen growth on iceberg lettuce under real temperature history during distribution from farm to table.

PubMed

Koseki, Shigenobu; Isobe, Seiichiro

2005-10-25

The growth of pathogenic bacteria Escherichia coli O157:H7, Salmonella spp., and Listeria monocytogenes on iceberg lettuce under constant and fluctuating temperatures was modelled in order to estimate the microbial safety of this vegetable during distribution from the farm to the table. Firstly, we examined pathogen growth on lettuce at constant temperatures, ranging from 5 to 25 degrees C, and then we obtained the growth kinetic parameters (lag time, maximum growth rate (micro(max)), and maximum population density (MPD)) using the Baranyi primary growth model. The parameters were similar to those predicted by the pathogen modelling program (PMP), with the exception of MPD. The MPD of each pathogen on lettuce was 2-4 log(10) CFU/g lower than that predicted by PMP. Furthermore, the MPD of pathogens decreased with decreasing temperature. The relationship between mu(max) and temperature was linear in accordance with Ratkowsky secondary model as was the relationship between the MPD and temperature. Predictions of pathogen growth under fluctuating temperature used the Baranyi primary microbial growth model along with the Ratkowsky secondary model and MPD equation. The fluctuating temperature profile used in this study was the real temperature history measured during distribution from the field at harvesting to the retail store. Overall predictions for each pathogen agreed well with observed viable counts in most cases. The bias and root mean square error (RMSE) of the prediction were small. The prediction in which mu(max) was based on PMP showed a trend of overestimation relative to prediction based on lettuce. However, the prediction concerning E. coli O157:H7 and Salmonella spp. on lettuce greatly overestimated growth in the case of a temperature history starting relatively high, such as 25 degrees C for 5 h. In contrast, the overall prediction of L. monocytogenes under the same circumstances agreed with the observed data.

Prediction of contaminant persistence in aqueous phase: a quantum chemical approach.

PubMed

Blotevogel, Jens; Mayeno, Arthur N; Sale, Tom C; Borch, Thomas

2011-03-15

At contaminated field sites where active remediation measures are not feasible, monitored natural attenuation is sometimes the only alternative for surface water or groundwater decontamination. However, due to slow degradation rates of some contaminants under natural conditions, attenuation processes and their performance assessment can take several years to decades to complete. Here, we apply quantum chemical calculations to predict contaminant persistence in the aqueous phase. For the test compound hexamethylphosphoramide (HMPA), P-N bond hydrolysis is the only thermodynamically favorable reaction that may lead to its degradation under reducing conditions. Through calculation of aqueous Gibbs free energies of activation for all potential reaction mechanisms, it is predicted that HMPA hydrolyzes via an acid-catalyzed mechanism at pH < 8.2, and an uncatalyzed mechanism at pH 8.2-8.5. The estimated half-lives of thousands to hundreds of thousands of years over the groundwater-typical pH range of 6.0 to 8.5 indicate that HMPA will be persistent in the absence of suitable oxidants. At pH 0, where the hydrolysis reaction is rapid enough to enable measurement, the experimentally determined rate constant and half-life are in excellent agreement with the predicted values. Since the quantum chemical methodology described herein can be applied to virtually any contaminant or reaction of interest, it is especially valuable for the prediction of persistence when slow reaction rates impede experimental investigations and appropriate QSARs are unavailable.

Papain hydrolysis of X-phenyl-N-methanesulfonyl glycinates: a quantitative structure-activity relationship and molecular graphics analysis.

PubMed

Carotti, A; Smith, R N; Wong, S; Hansch, C; Blaney, J M; Langridge, R

1984-02-15

The hydrolysis of 32 X-phenyl-N-methanesulfonyl glycinates by papain was investigated. It was found that the variation in the Michaelis constants could be rationalized by the following correlation equation: log 1/Km = 0.61 pi '3 + 0.46 MR4 + 0.55 sigma + 2.00 with a correlation coefficient of 0.945. In this expression, pi '3 is the hydrophobic constant for the more lipophilic of the two possible meta substituents, MR4 is the molar refractivity of 4-substituents, and sigma is the Hammett constant summed for all substituents. Using this equation, we designed, synthesized, and successfully predicted Km for a new congener intended to maximize binding (1/Km). The interactions involved in enzyme-substrate binding, as characterized by the correlation equation, are interpreted using a computer-constructed color three-dimensional-graphics molecular model of the enzyme active site. The nonenzymatic hydrolysis (both acid and basic) of phenyl hippurates yield rate constants which are well correlated by Hammett equations; however, log k for both acid and alkaline hydrolysis are not linearly related to log 1/Km or log kcat/Km.

Thermal niche estimators and the capability of poor dispersal species to cope with climate change

PubMed Central

Sánchez-Fernández, David; Rizzo, Valeria; Cieslak, Alexandra; Faille, Arnaud; Fresneda, Javier; Ribera, Ignacio

2016-01-01

For management strategies in the context of global warming, accurate predictions of species response are mandatory. However, to date most predictions are based on niche (bioclimatic) models that usually overlook biotic interactions, behavioral adjustments or adaptive evolution, and assume that species can disperse freely without constraints. The deep subterranean environment minimises these uncertainties, as it is simple, homogeneous and with constant environmental conditions. It is thus an ideal model system to study the effect of global change in species with poor dispersal capabilities. We assess the potential fate of a lineage of troglobitic beetles under global change predictions using different approaches to estimate their thermal niche: bioclimatic models, rates of thermal niche change estimated from a molecular phylogeny, and data from physiological studies. Using bioclimatic models, at most 60% of the species were predicted to have suitable conditions in 2080. Considering the rates of thermal niche change did not improve this prediction. However, physiological data suggest that subterranean species have a broad thermal tolerance, allowing them to stand temperatures never experienced through their evolutionary history. These results stress the need of experimental approaches to assess the capability of poor dispersal species to cope with temperatures outside those they currently experience. PMID:26983802

Chemical Action of Halogenated Agents in Fire Extinguishing

NASA Technical Reports Server (NTRS)

Belles, Frank E.

1955-01-01

The action of halogenated agents in preventing flame propagation in fuel-air mixtures in laboratory tests is discussed in terms of a possible chemical mechanism. The mechanism chosen is that of chain-breaking reactions between agent and active particles (hydrogen and oxygen atoms and hydroxyl radicsls). Data from the literature on the flammability peaks of n-heptane agent-air mixtures are treated. Ratings of agent effectiveness in terms of the fuel equivalent of the agent, based on both fuel and agent concentrations at the peak, are proposed as preferable to ratings in terms of agent concentration alone. These fuel-equivalent ratings are roughly correlated by reactivities assigned to halogen and hydrogen atoms in the agent molecules. It is concluded that the presence of hydrogen in agent need not reduce its fire-fighting ability, provided there is enough halogen to make the agent nonflammable. A method is presented for estimating from quenching-distance data a rate constant for the reaction of agent with active particles. A quantitative result is obtained for methyl bromide. This rate constant predicts the observed peak concentration of methyl bromide quite well. However, more data are needed to prove the validity of the method. The assumption that hal.ogenatedagents act mainly by chain-bresking reactions with active particles is consistent with the experimental facts and should help guide the selection of agents for further tests.

Ionic strength dependence of the oxidation of SO2 by H2O2 in sodium chloride particles

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

Ali, Hashim M.; Iedema, Martin J.; Yu, Xiao-Ying

The reaction of sulfur dioxide and hydrogen peroxide in the presence of deliquesced (>75% RH) sodium particles was studied by utilizing a crossflow-mini reactor. The reaction kinetics was followed by observing chloride depletion in particles by computer-controlled scanning electron microscope with energy dispersive X-ray analysis, namely SEM/EDX. The reactions take place in concentrated mixed salt brine aerosols, for which no complete kinetic equilibrium data previously existed. We measured the Henry’s law solubility of H2O2 to close that gap. We also calculated the reaction rate as the particle transforms continuously from concentrated NaCl brine to eventually a mixed NaHSO4 plus H2SO4more » brine solution. The reaction rate of the SO2 oxidation by H2O2 was found to be influenced by the change in ionic strength as the particle undergoes compositional transformation, following closely the dependence of the third order rate constant on ionic strength as predicted rates using previously established rate equations. This is the first study that has measured the ionic strength dependence of sulfate formation (in non-aqueous media) from oxidation of mixed salt brine aerosols in the presence of H2O2. It also gives the first report of the Henry’s law constant of H2O2 dependence on ionic strength.« less

Pulsed Power Discharges in Water

NASA Astrophysics Data System (ADS)

Kratel, Axel Wolf Hendrik

An Electrohydraulic Discharge Process (EHD) for the treatment of hazardous chemical wastes in water has been developed. Liquid waste in a 4 L EHD reactor is directly exposed to high-energy pulsed electrical discharges between two submerged electrodes. The high-temperature (> 14,000 K) plasma channel created by an EHD discharge emits ultraviolet radiation, and produces an intense shock wave as it expands against the surrounding water. A simulation of the EHD process is presented along with experimental results. The simulation assumes a uniform plasma channel with a plasma that obeys the ideal gas law and the Spitzer conductivity law. The results agree with previously published data. The simulation is used to predict the total energy efficiency, energy partitioning, maximum plasma channel temperature and pressure for the Caltech Pulsed Power Facility (CPPF). The simulation shows that capacitance, initial voltage and gap length can be used to control the efficiency of the discharge. The oxidative degradation of 4-chlorophenol (4 -CP), 3,4-dichloroaniline (3,4-DCA), and 2,4,6 trinitrotoluene (TNT) in an EHD reactor was explored. The initial rates of degradation for the three substrates are described by a first-order rate equation, where k_{ it 0/} is the zero-order rate constant that accounts for direct photolysis; and k_ {it 1/} is the first-order term that accounts for oxidation in the plasma channel region. For 4-CP in the 4.0 L reactor, the values of these two rate constants are k_{it 0/} = 0.73 +/- 0.08 mu M, and k_{ it 1/} =(9.4 +/- 1.4) times 10^{-4}. For a 200 mu M 4-CP solution this corresponds to an overall intrinsic zero-order rate constant of 0.022 M s^{it -1/} , and a G-value of 4.45 times 10^{-3}. Ozone increases the rate and extent of degradation of the substrates in the EHD reactor. Combined EHD/ozone treatment of a 160 mu M TNT solution resulted in the complete degradation of TNT, and a 34% reduction of the total organic carbon (TOC). The intrinsic initial rate constant of TNT degradation was 0.024 M s^{it -1/} . The results of these experiments demonstrate the potential application of the EHD process for the treatment of hazardous wastes.

Multiaxial Fatigue Damage Parameter and Life Prediction without Any Additional Material Constants

PubMed Central

Yu, Zheng-Yong; Liu, Qiang; Liu, Yunhan

2017-01-01

Based on the critical plane approach, a simple and efficient multiaxial fatigue damage parameter with no additional material constants is proposed for life prediction under uniaxial/multiaxial proportional and/or non-proportional loadings for titanium alloy TC4 and nickel-based superalloy GH4169. Moreover, two modified Ince-Glinka fatigue damage parameters are put forward and evaluated under different load paths. Results show that the generalized strain amplitude model provides less accurate life predictions in the high cycle life regime and is better for life prediction in the low cycle life regime; however, the generalized strain energy model is relatively better for high cycle life prediction and is conservative for low cycle life prediction under multiaxial loadings. In addition, the Fatemi–Socie model is introduced for model comparison and its additional material parameter k is found to not be a constant and its usage is discussed. Finally, model comparison and prediction error analysis are used to illustrate the superiority of the proposed damage parameter in multiaxial fatigue life prediction of the two aviation alloys under various loadings. PMID:28792487

Multiaxial Fatigue Damage Parameter and Life Prediction without Any Additional Material Constants.

PubMed

Yu, Zheng-Yong; Zhu, Shun-Peng; Liu, Qiang; Liu, Yunhan

2017-08-09

Based on the critical plane approach, a simple and efficient multiaxial fatigue damage parameter with no additional material constants is proposed for life prediction under uniaxial/multiaxial proportional and/or non-proportional loadings for titanium alloy TC4 and nickel-based superalloy GH4169. Moreover, two modified Ince-Glinka fatigue damage parameters are put forward and evaluated under different load paths. Results show that the generalized strain amplitude model provides less accurate life predictions in the high cycle life regime and is better for life prediction in the low cycle life regime; however, the generalized strain energy model is relatively better for high cycle life prediction and is conservative for low cycle life prediction under multiaxial loadings. In addition, the Fatemi-Socie model is introduced for model comparison and its additional material parameter k is found to not be a constant and its usage is discussed. Finally, model comparison and prediction error analysis are used to illustrate the superiority of the proposed damage parameter in multiaxial fatigue life prediction of the two aviation alloys under various loadings.

[Effect of SO2 volume fraction in flue gas on the adsorption behaviors adsorbed by ZL50 activated carbon and kinetic analysis].

PubMed

Gao, Ji-xian; Wang, Tie-feng; Wang, Jin-fu

2010-05-01

The influence of SO2 dynamic adsorption behaviors using ZL50 activated carbon for flue gas desulphurization and denitrification under different SO2 volume fraction was investigated experimentally, and the kinetic analysis was conducted by kinetic models. With the increase of SO2 volume fraction in flue gas, the SO2 removal ratio and the activity ratio of ZL50 activated carbon decreased, respectively, and SO2 adsorption rate and capacity increased correspondingly. The calculated results indicate that Bangham model has the best prediction effect, the chemisorption processes of SO2 was significantly affected by catalytic oxidative reaction. The adsorption rate constant of Lagergren's pseudo first order model increased with the increase of inlet SO, volume fraction, which indicated that catalytic oxidative reaction of SO2 adsorbed by ZL50 activated carbon may be the rate controlling step in earlier adsorption stage. The Lagergren's and Bangham's initial adsorption rate were deduced and defined, respectively. The Ho's and Elovich's initial adsorption rate were also deduced in this paper. The Bangham's initial adsorption rate values were defined in good agreement with those of experiments. The defined Bangham's adsorptive reaction kinetic model can describe the SO2 dynamic adsorption rate well. The studied results indicated that the SO2 partial order of initial reaction rate was one or adjacent to one, while the O2 and water vapor partial order of initial reaction rate were constants ranging from 0.15-0.20 and 0.45-0.50, respectively.

Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

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

Soudackov, Alexander V.; Hammes-Schiffer, Sharon

2015-11-21

Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at highmore » temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes.« less

High-temperature langatate elastic constants and experimental validation up to 900 degrees C.

PubMed

Davulis, Peter M; da Cunha, Mauricio Pereira

2010-01-01

This paper reports on a set of langatate (LGT) elastic constants extracted from room temperature to 1100 degrees C using resonant ultrasound spectroscopy techniques and an accompanying assessment of these constants at high temperature. The evaluation of the constants employed SAW device measurements from room temperature to 900 degrees C along 6 different LGT wafer orientations. Langatate parallelepipeds and wafers were aligned, cut, ground, and polished, and acoustic wave devices were fabricated at the University of Maine facilities along specific orientations for elastic constant extraction and validation. SAW delay lines were fabricated on LGT wafers prepared at the University of Maine using 100-nm platinumrhodium- zirconia electrodes capable of withstanding temperatures up to 1000 degrees C. The numerical predictions based on the resonant ultrasound spectroscopy high-temperature constants were compared with SAW phase velocity, fractional frequency variation, and temperature coefficients of delay extracted from SAW delay line frequency response measurements. In particular, the difference between measured and predicted fractional frequency variation is less than 2% over the 25 degrees C to 900 degrees C temperature range and within the calculated and measured discrepancies. Multiple temperature-compensated orientations at high temperature were predicted and verified in this paper: 4 of the measured orientations had turnover temperatures (temperature coefficient of delay = 0) between 200 and 420 degrees C, and 2 had turnover temperatures below 100 degrees C. In summary, this work reports on extracted high-temperature elastic constants for LGT up to 1100 degrees C, confirmed the validity of those constants by high-temperature SAW device measurements up to 900 degrees C, and predicted and identified temperature-compensated LGT orientations at high temperature.

Ab Initio Kinetics of Hydrogen Abstraction from Methyl Acetate by Hydrogen, Methyl, Oxygen, Hydroxyl, and Hydroperoxy Radicals.

PubMed

Tan, Ting; Yang, Xueliang; Krauter, Caroline M; Ju, Yiguang; Carter, Emily A

2015-06-18

The kinetics of hydrogen abstraction by five radicals (H, O((3)P), OH, CH3, and HO2) from methyl acetate (MA) is investigated theoretically in order to gain further understanding of certain aspects of the combustion chemistry of biodiesels, such as the effect of the ester moiety. We employ ab initio quantum chemistry methods, coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) and multireference averaged coupled pair functional theory (MRACPF2), to predict chemically accurate reaction energetics. Overall, MRACPF2 predicts slightly higher barrier heights than CCSD(T) for MA + H/CH3/O/OH, but slightly lower barrier heights for hydrogen abstraction by HO2. Based on the obtained reaction energies, we also report high-pressure-limit rate constants using transition state theory (TST) in conjunction with the separable-hindered-rotor approximation, the variable reaction coordinate TST, and the multi-structure all-structure approach. The fitted modified Arrhenius expressions are provided over a temperature range of 250 to 2000 K. The predictions are in good agreement with available experimental results. Abstractions from both of the methyl groups in MA are expected to contribute to consumption of the fuel as they exhibit similar rate coefficients. The reactions involving the OH radical are predicted to have the highest rates among the five abstracting radicals, while those initiated by HO2 are expected to be the lowest.

Predicting gaseous reaction rates of short chain chlorinated paraffins with ·OH: overcoming the difficulty in experimental determination.

PubMed

Li, Chao; Xie, Hong-Bin; Chen, Jingwen; Yang, Xianhai; Zhang, Yifei; Qiao, Xianliang

2014-12-02

Short chain chlorinated paraffins (SCCPs) are under evaluation for inclusion in the Stockholm Convention on persistent organic pollutants. However, information on their reaction rate constants with gaseous ·OH (kOH) is unavailable, limiting the evaluation of their persistence in the atmosphere. Experimental determination of kOH is confined by the unavailability of authentic chemical standards for some SCCP congeners. In this study, we evaluated and selected density functional theory (DFT) methods to predict kOH of SCCPs, by comparing the experimental kOH values of six polychlorinated alkanes (PCAs) with those calculated by the different theoretical methods. We found that the M06-2X/6-311+G(3df,2pd)//B3LYP/6-311 +G(d,p) method is time-effective and can be used to predict kOH of PCAs. Moreover, based on the calculated kOH of nine SCCPs and available experimental kOH values of 22 PCAs with low carbon chain, a quantitative structure-activity relationship (QSAR) model was developed. The molecular structural characteristics determining the ·OH reaction rate were discussed. logkOH was found to negatively correlate with the percentage of chlorine substitutions (Cl%). The DFT calculation method and the QSAR model are important alternatives to the conventional experimental determination of kOH for SCCPs, and are prospective in predicting their persistence in the atmosphere.

Molecular model for the diffusion of associating telechelic polymer networks

NASA Astrophysics Data System (ADS)

Ramirez, Jorge; Dursch, Thomas; Olsen, Bradley

Understanding the mechanisms of motion and stress relaxation of associating polymers at the molecular level is critical for advanced technological applications such as enhanced oil-recovery, self-healing materials or drug delivery. In associating polymers, the strength and rates of association/dissociation of the reversible physical crosslinks govern the dynamics of the network and therefore all the macroscopic properties, like self-diffusion and rheology. Recently, by means of forced Rayleigh scattering experiments, we have proved that associating polymers of different architectures show super-diffusive behavior when the free motion of single molecular species is slowed down by association/dissociation kinetics. Here we discuss a new molecular picture for unentangled associating telechelic polymers that considers concentration, molecular weight, number of arms of the molecules and equilibrium and rate constants of association/dissociation. The model predicts super-diffusive behavior under the right combination of values of the parameters. We discuss some of the predictions of the model using scaling arguments, show detailed results from Brownian dynamics simulations of the FRS experiments, and attempt to compare the predictions of the model to experimental data.

Unsteady Thermocapillary Migration of Isolated Drops in Creeping Flow

NASA Technical Reports Server (NTRS)

Dill, Loren H.; Balasubramaniam, R.

1992-01-01

The problem of an isolated immiscible drop that slowly migrates due to unsteady thermocapillary stresses is considered. All physical properties except for interfacial tension are assumed constant for the two Newtonian fluids. Explicit expressions are found for the migration rate and stream functions in the Laplace domain. The resulting microgravity theory is useful, e.g., in predicting the distance a drop will migrate due to an impulsive interfacial temperature gradient as well as the time required to attain steady flow conditions from an initially resting state.

Computational Prediction of Kinetic Rate Constants

DTIC Science & Technology

2009-02-01

best experimental estimates are in kcal/mol. RMcdoo l> Uil. . 1 -.In 1 1 II. lei ,. »rrsnn • emu rtvm . « snfi. !>ii K.IIHlMi’ \\i . St"WTi H...straightforward extensions the HF energy and gradient expressions. For example, the energy and the gradient HF-DFT ’ dE designated as E r-IIF DF1 and...8217’ Coulomb Electron Electron «P Hartr » . pBecke-LYP I ^Hartree-Fock \\7 n ’ Exchange correlation \\H ’ r llarlree-Fock Contract

Development of a Novel Approach for Fatigue Life Prediction of Structural Materials

DTIC Science & Technology

2008-12-01

applied when the crack length was 8.45 mm and 14.96 mm, respectively, on these two specimens. A third specimen was subjected to a constant amplitude...The crack growth rate at the middle point (the third point) was determined from the derivative of the parabola. The stress intensity factor for...minimum load was identical in the two loading steps (Fig. 32(b)). The third specimen experienced two-step loading with identical /?-ratio in the two

Informed Materials Discovery: Designing New Engineering Polymer Systems Using High Throughput Modeling Techniques

DTIC Science & Technology

2016-10-27

and molecu- lar physical structure into the prediction of the macroscopic constitutive properties and behaviour of the polymers. GIM uses a mean field...Cβ and Cg are related to the loss of DOFs over beta and glass transitions, where R is the molar gas constant and C is defined by: (2) C = NR (6.7T θ1...The compression yield behaviour of polymethyl methacrylate over a wide range of temperatures and strain-rates, Journal of Materials Science 8 (7

(210)Pb and compositional data of sediments from Rondonian lakes, Madeira River basin, Brazil.

PubMed

Bonotto, Daniel Marcos; Vergotti, Marcelo

2015-05-01

Gold exploration has been intensive in Brazilian Amazon over the last 40 years, where the use of mercury as an amalgam has caused abnormal Hg concentrations in water bodies. Special attention has been directed to Madeira River due to fact it is a major tributary of Amazon River and that since 1986, gold exploration has been officially permitted along a 350km sector of the river. The (21)(0)Pb method has been used to date sediments taken from nine lakes situated in Madeira River basin, Rondônia State, and to verify where anthropogenic Hg might exist due to gold exploitation in Madeira River. Activity profiles of excess (21)(0)Pb determined in the sediment cores provided a means to evaluate the sedimentation rates using a Constant Flux: Constant Sedimentation (CF:CS) and Constant Rate of Supply (CRS) of unsupported/excess (21)(0)Pb models. A significant relationship was found between the CF:CS sedimentation rates and the mean values of the CRS sedimentation rates (Pearson correlation coefficient r=0.59). Chemical data were also determined in the sediments for identifying possible relationships with Hg occurring in the area. Significant values were found in statistical correlation tests realized among the Hg, major oxides and Total Organic Carbon (TOC) content in the sediments. The TOC increased in the sediment cores accompanied by a loss on ignition (LOI) increment, whereas silica decreased following a specific surface area raising associated to the TOC increase. The CRS model always provided ages within the permitted range of the (21)(0)Pb-method in the studied lakes, whereas the CF:CS model predicted two values above 140 years. Copyright © 2015 Elsevier Ltd. All rights reserved.

Gas Phase Molecular Spectroscopy: Electronic Spectroscopy of Combustion Intermediates, Chlorine Azide kinetics, and Rovibrational Energy Transfer in Acetylene

NASA Astrophysics Data System (ADS)

Freel, Keith A.

This dissertation is composed of three sections. The first deals with the electronic spectroscopy of combustion intermediates that are related to the formation of polycyclic aromatic hydrocarbons. Absorption spectra for phenyl, phenoxy, benzyl, and phenyl peroxy radicals were recorded using the technique of cavity ring-down spectroscopy. When possible, molecular constants, vibrational frequencies, and excited state lifetimes for these radicals were derived from these data. The results were supported by theoretical predictions. The second section presents a study of electron attachment to chlorine azide (ClN3) using a flowing-afterglow Langmuir-probe apparatus. Electron attachment rates were measured to be 3.5x10-8 and 4.5x10-8 cm3s-1 at 298 and 400 K respectively. The reactions of ClN3 with eighteen cations and seventeen anions were characterized. Rate constants were measured using a selected ion flow tube. The ionization energy (>9.6eV), proton affinity (713+/-41 kJ mol-1), and electron affinity (2.48+/-0.2 eV) for ClN 3 were determined from these data. The third section demonstrates the use of double resonance spectroscopy to observe state-selected rovibrational energy transfer from the first overtone asymmetric stretch of acetylene. The total population removal rate constants from various rotational levels of the (1,0,1,00,00) vibrational state were determined to be in the range of (9-17) x 10 -10 cm3s-1. Rotational energy transfer accounted for approximately 90% of the total removal rate from each state. Therefore, the upper limit of vibrational energy transfer from the (1,0,1,0 0,00) state was 10%.

GROUND WATER ISSUE - CALCULATION AND USE OF FIRST-ORDER RATE CONSTANTS FOR MONITORED NATURAL ATTENUATION STUDIES

EPA Science Inventory

This issue paper explains when and how to apply first-order attenuation rate constant calculations in monitored natural attenuation (MNA) studies. First-order attenuation rate constant calculations can be an important tool for evaluating natural attenuation processes at ground-wa...

Trends in electron-ion dissociative recombination of benzene analogs with functional group substitutions: Negative Hammett σpara values

NASA Astrophysics Data System (ADS)

Osborne, David; Lawson, Patrick Andrew; Adams, Nigel; Dotan, Itzhak

2014-06-01

An in-depth study of the effects of functional group substitution on benzene's electron-ion dissociative recombination (e-IDR) rate constant has been conducted. The e-IDR rate constants for benzene, biphenyl, toluene, ethylbenzene, anisole, phenol, and aniline have been measured using a Flowing Afterglow equipped with an electrostatic Langmuir probe (FALP). These measurements have been made over a series of temperatures from 300 to 550 K. A relationship between the Hammett σpara values for each compound and rate constant has indicated a trend in the e-IDR rate constants and possibly in their temperature dependence data. The Hammett σpara value is a method to describe the effect a functional group substituted to a benzene ring has upon the reaction rate constant.

Rate constants of hydroxyl radical oxidation of polychlorinated biphenyls in the gas phase: A single-descriptor based QSAR and DFT study.

PubMed

Yang, Zhihui; Luo, Shuang; Wei, Zongsu; Ye, Tiantian; Spinney, Richard; Chen, Dong; Xiao, Ruiyang

2016-04-01

The second-order rate constants (k) of hydroxyl radical (·OH) with polychlorinated biphenyls (PCBs) in the gas phase are of scientific and regulatory importance for assessing their global distribution and fate in the atmosphere. Due to the limited number of measured k values, there is a need to model the k values for unknown PCBs congeners. In the present study, we developed a quantitative structure-activity relationship (QSAR) model with quantum chemical descriptors using a sequential approach, including correlation analysis, principal component analysis, multi-linear regression, validation, and estimation of applicability domain. The result indicates that the single descriptor, polarizability (α), plays an important role in determining the reactivity with a global standardized function of lnk = -0.054 × α ‒ 19.49 at 298 K. In order to validate the QSAR predicted k values and expand the current k value database for PCBs congeners, an independent method, density functional theory (DFT), was employed to calculate the kinetics and thermodynamics of the gas-phase ·OH oxidation of 2,4',5-trichlorobiphenyl (PCB31), 2,2',4,4'-tetrachlorobiphenyl (PCB47), 2,3,4,5,6-pentachlorobiphenyl (PCB116), 3,3',4,4',5,5'-hexachlorobiphenyl (PCB169), and 2,3,3',4,5,5',6-heptachlorobiphenyl (PCB192) at 298 K at B3LYP/6-311++G**//B3LYP/6-31 + G** level of theory. The QSAR predicted and DFT calculated k values for ·OH oxidation of these PCB congeners exhibit excellent agreement with the experimental k values, indicating the robustness and predictive power of the single-descriptor based QSAR model we developed. Copyright © 2015 Elsevier Ltd. All rights reserved.

Population pharmacokinetic analysis of carboxyhaemoglobin concentrations in adult cigarette smokers.

PubMed

Cronenberger, Carol; Mould, Diane R; Roethig, Hans-Juergen; Sarkar, Mohamadi

2008-01-01

To develop a population-based model to describe and predict the pharmacokinetics of carboxyhaemoglobin (COHb) in adult smokers. Data from smokers of different conventional cigarettes (CC) in three open-label, randomized studies were analysed using NONMEM (version V, Level 1.1). COHb concentrations were determined at baseline for two cigarettes [Federal Trade Commission (FTC) tar 11 mg; CC1, or FTC tar 6 mg; CC2]. On day 1, subjects were randomized to continue smoking their original cigarettes, switch to a different cigarette (FTC tar 1 mg; CC3), or stop smoking. COHb concentrations were measured at baseline and on days 3 and 8 after randomization. Each cigarette was treated as a unit dose assuming a linear relationship between the number of cigarettes smoked and measured COHb percent saturation. Model building used standard methods. Model performance was evaluated using nonparametric bootstrapping and predictive checks. The data were described by a two-compartment model with zero-order input and first-order elimination with endogenous COHb. Model parameters included elimination rate constant (k(10)), central volume of distribution (Vc/F), rate constants between central and peripheral compartments (k(12) and k(21)), baseline COHb concentrations (c0), and relative fraction of carbon monoxide absorbed (F1). The median (range) COHb half-lives were 1.6 h (0.680-2.76) and 30.9 h (7.13-367) (alpha and beta phases, respectively). F1 increased with increasing cigarette tar content and age, whereas k(12) increased with ideal body weight. A robust model was developed to predict COHb concentrations in adult smokers and to determine optimum COHb sampling times in future studies.

Modeling of Fume Formation from Shielded Metal Arc Welding Process

NASA Astrophysics Data System (ADS)

Sivapirakasam, S. P.; Mohan, Sreejith; Santhosh Kumar, M. C.; Surianarayanan, M.

2017-04-01

In this study, a semi-empirical model of fume formation rate (FFR) from a shielded metal arc welding (SMAW) process has been developed. The model was developed for a DC electrode positive (DCEP) operation and involves the calculations of droplet temperature, surface area of the droplet, and partial vapor pressures of the constituents of the droplet to predict the FFR. The model was further extended for predicting FFR from nano-coated electrodes. The model estimates the FFR for Fe and Mn assuming constant proportion of other elements in the electrode. Fe FFR was overestimated, while Mn FFR was underestimated. The contribution of spatters and other mechanism in the arc responsible for fume formation were neglected. A good positive correlation was obtained between the predicted and experimental FFR values which highlighted the usefulness of the model.

Equilibrium muscle cross-bridge behavior. Theoretical considerations.

PubMed Central

Schoenberg, M

1985-01-01

We have developed a model for the equilibrium attachment and detachment of myosin cross-bridges to actin that takes into account the possibility that a given cross-bridge can bind to one of a number of actin monomers, as seems likely, rather than to a site on only a single actin monomer, as is often assumed. The behavior of this multiple site model in response to constant velocity, as well as instantaneous stretches, was studied and the influence of system parameters on the force response explored. It was found that in the multiple site model the detachment rate constant has considerably greater influence on the mechanical response than the attachment rate constant. It is shown that one can obtain information about the detachment rate constants either by examining the relationship between the apparent stiffness and duration of stretch for constant velocity stretches or by examining the force-decay rate constants following an instantaneous stretch. The main effect of the attachment rate constant is to scale the mechanical response by influencing the number of attached cross-bridges. The significance of the modeling for the interpretation of experimental results is discussed. PMID:4041539

Electron-ion dissociative recombination rate constants relevant to the Titan atmosphere and the Interstellar Medium

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

Osborne, David; Lawson, Patrick; Adams, Nigel, E-mail: ngadams@uga.edu

Following the arrival of Cassini at Titan in 2004, the Titan atmosphere has been shown to contain large complex polycyclic-aromatic hydrocarbons. Since Cassini has provided a great deal of data, there exists a need for kinetic rate data to help with modeling this atmosphere. One type of kinetic data needed is electron-ion dissociative recombination (e-IDR) rate constants. These data are not readily available for larger compounds, such as naphthalene, or oxygen containing compounds, such as 1,4 dioxane or furan. Here, the rate constants for naphthalene, 1,4 dioxane, and furan have been measured and their temperature dependencies are determined when possible,more » using the University of Georgia's Variable Temperature Flowing Afterglow. The rate constants are compared with those previously published for other compounds; these show trends which illustrate the effects which multi-rings and oxygen heteroatoms substitutions have upon e-IDR rate constants.« less

Electron-ion dissociative recombination rate constants relevant to the Titan atmosphere and the Interstellar Medium

NASA Astrophysics Data System (ADS)

Osborne, David; Lawson, Patrick; Adams, Nigel

2014-01-01

Following the arrival of Cassini at Titan in 2004, the Titan atmosphere has been shown to contain large complex polycyclic-aromatic hydrocarbons. Since Cassini has provided a great deal of data, there exists a need for kinetic rate data to help with modeling this atmosphere. One type of kinetic data needed is electron-ion dissociative recombination (e-IDR) rate constants. These data are not readily available for larger compounds, such as naphthalene, or oxygen containing compounds, such as 1,4 dioxane or furan. Here, the rate constants for naphthalene, 1,4 dioxane, and furan have been measured and their temperature dependencies are determined when possible, using the University of Georgia's Variable Temperature Flowing Afterglow. The rate constants are compared with those previously published for other compounds; these show trends which illustrate the effects which multi-rings and oxygen heteroatoms substitutions have upon e-IDR rate constants.

Well hydraulics in pumping tests with exponentially decayed rates of abstraction in confined aquifers

NASA Astrophysics Data System (ADS)

Wen, Zhang; Zhan, Hongbin; Wang, Quanrong; Liang, Xing; Ma, Teng; Chen, Chen

2017-05-01

Actual field pumping tests often involve variable pumping rates which cannot be handled by the classical constant-rate or constant-head test models, and often require a convolution process to interpret the test data. In this study, we proposed a semi-analytical model considering an exponentially decreasing pumping rate started at a certain (higher) rate and eventually stabilized at a certain (lower) rate for cases with or without wellbore storage. A striking new feature of the pumping test with an exponentially decayed rate is that the drawdowns will decrease over a certain period of time during intermediate pumping stage, which has never been seen before in constant-rate or constant-head pumping tests. It was found that the drawdown-time curve associated with an exponentially decayed pumping rate function was bounded by two asymptotic curves of the constant-rate tests with rates equaling to the starting and stabilizing rates, respectively. The wellbore storage must be considered for a pumping test without an observation well (single-well test). Based on such characteristics of the time-drawdown curve, we developed a new method to estimate the aquifer parameters by using the genetic algorithm.

Impact of uncertainties in inorganic chemical rate constants on tropospheric composition and ozone radiative forcing

NASA Astrophysics Data System (ADS)

Newsome, Ben; Evans, Mat

2017-12-01

Chemical rate constants determine the composition of the atmosphere and how this composition has changed over time. They are central to our understanding of climate change and air quality degradation. Atmospheric chemistry models, whether online or offline, box, regional or global, use these rate constants. Expert panels evaluate laboratory measurements, making recommendations for the rate constants that should be used. This results in very similar or identical rate constants being used by all models. The inherent uncertainties in these recommendations are, in general, therefore ignored. We explore the impact of these uncertainties on the composition of the troposphere using the GEOS-Chem chemistry transport model. Based on the Jet Propulsion Laboratory (JPL) and International Union of Pure and Applied Chemistry (IUPAC) evaluations we assess the influence of 50 mainly inorganic rate constants and 10 photolysis rates on tropospheric composition through the use of the GEOS-Chem chemistry transport model. We assess the impact on four standard metrics: annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime. Uncertainty in the rate constants for NO2 + OH →M HNO3 and O3 + NO → NO2 + O2 are the two largest sources of uncertainty in these metrics. The absolute magnitude of the change in the metrics is similar if rate constants are increased or decreased by their σ values. We investigate two methods of assessing these uncertainties, addition in quadrature and a Monte Carlo approach, and conclude they give similar outcomes. Combining the uncertainties across the 60 reactions gives overall uncertainties on the annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime of 10, 11, 16 and 16 %, respectively. These are larger than the spread between models in recent model intercomparisons. Remote regions such as the tropics, poles and upper troposphere are most uncertain. This chemical uncertainty is sufficiently large to suggest that rate constant uncertainty should be considered alongside other processes when model results disagree with measurement. Calculations for the pre-industrial simulation allow a tropospheric ozone radiative forcing to be calculated of 0.412 ± 0.062 W m-2. This uncertainty (13 %) is comparable to the inter-model spread in ozone radiative forcing found in previous model-model intercomparison studies where the rate constants used in the models are all identical or very similar. Thus, the uncertainty of tropospheric ozone radiative forcing should expanded to include this additional source of uncertainty. These rate constant uncertainties are significant and suggest that refinement of supposedly well-known chemical rate constants should be considered alongside other improvements to enhance our understanding of atmospheric processes.

Effects of Variable Inflationary Conditions on AN Inventory Model with Inflation-Proportional Demand Rate

NASA Astrophysics Data System (ADS)

Mirzazadeh, Abolfazl

2009-08-01

The inflation rate in the most of the previous researches has been considered constant and well-known over the time horizon, although the future rate of inflation is inherently uncertain and unstable, and is difficult to predict it accurately. Therefore, A time varying inventory model for deteriorating items with allowable shortages is developed in this paper. The inflation rates (internal and external) are time-dependent and demand rate is inflation-proportional. The inventory level is described by differential equations over the time horizon and present value method is used. The numerical example is given to explain the results. Some particular cases, which follow the main problem, will discuss and the results will compare with the main model by using the numerical examples. It has been achieved which shortages increases considerably in comparison with the case of without variable inflationary conditions.