Sample records for zero-order rate constant

  1. A comparison of zero-order, first-order, and monod biotransformation models

    USGS Publications Warehouse

    Bekins, B.A.; Warren, E.; Godsy, E.M.

    1998-01-01

    Under some conditions, a first-order kinetic model is a poor representation of biodegradation in contaminated aquifers. Although it is well known that the assumption of first-order kinetics is valid only when substrate concentration, S, is much less than the half-saturation constant, K(s), this assumption is often made without verification of this condition. We present a formal error analysis showing that the relative error in the first-order approximation is S/K(S) and in the zero-order approximation the error is K(s)/S. We then examine the problems that arise when the first-order approximation is used outside the range for which it is valid. A series of numerical simulations comparing results of first- and zero-order rate approximations to Monod kinetics for a real data set illustrates that if concentrations observed in the field are higher than K(s), it may better to model degradation using a zero-order rate expression. Compared with Monod kinetics, extrapolation of a first-order rate to lower concentrations under-predicts the biotransformation potential, while extrapolation to higher concentrations may grossly over-predict the transformation rate. A summary of solubilities and Monod parameters for aerobic benzene, toluene, and xylene (BTX) degradation shows that the a priori assumption of first-order degradation kinetics at sites contaminated with these compounds is not valid. In particular, out of six published values of KS for toluene, only one is greater than 2 mg/L, indicating that when toluene is present in concentrations greater than about a part per million, the assumption of first-order kinetics may be invalid. Finally, we apply an existing analytical solution for steady-state one-dimensional advective transport with Monod degradation kinetics to a field data set.A formal error analysis is presented showing that the relative error in the first-order approximation is S/KS and in the zero-order approximation the error is KS/S where S is the substrate

  2. Computer Calculation of First-Order Rate Constants

    ERIC Educational Resources Information Center

    Williams, Robert C.; Taylor, James W.

    1970-01-01

    Discusses the computer program used to calculate first-order rate constants. Discussion includes data preparation, weighting options, comparison techniques, infinity point adjustment, least-square fit, Guggenheim calculation, and printed outputs. Exemplifies the utility of the computer program by two experiments: (1) the thermal decomposition of…

  3. 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...

  4. Impact of transverse and longitudinal dispersion on first-order degradation rate constant estimation

    NASA Astrophysics Data System (ADS)

    Stenback, Greg A.; Ong, Say Kee; Rogers, Shane W.; Kjartanson, Bruce H.

    2004-09-01

    A two-dimensional analytical model is employed for estimating the first-order degradation rate constant of hydrophobic organic compounds (HOCs) in contaminated groundwater under steady-state conditions. The model may utilize all aqueous concentration data collected downgradient of a source area, but does not require that any data be collected along the plume centerline. Using a least squares fit of the model to aqueous concentrations measured in monitoring wells, degradation rate constants were estimated at a former manufactured gas plant (FMGP) site in the Midwest U.S. The estimated degradation rate constants are 0.0014, 0.0034, 0.0031, 0.0019, and 0.0053 day -1 for acenaphthene, naphthalene, benzene, ethylbenzene, and toluene, respectively. These estimated rate constants were as low as one-half those estimated with the one-dimensional (centerline) approach of Buscheck and Alcantar [Buscheck, T.E., Alcantar, C.M., 1995. Regression techniques and analytical solutions to demonstrate intrinsic bioremediation. In: Hinchee, R.E., Wilson, J.T., Downey, D.C. (Eds.), Intrinsic Bioremediation, Battelle Press, Columbus, OH, pp. 109-116] which does not account for transverse dispersivity. Varying the transverse and longitudinal dispersivity values over one order of magnitude for toluene data obtained from the FMGP site resulted in nearly a threefold variation in the estimated degradation rate constant—highlighting the importance of reliable estimates of the dispersion coefficients for obtaining reasonable estimates of the degradation rate constants. These results have significant implications for decision making and site management where overestimation of a degradation rate may result in remediation times and bioconversion factors that exceed expectations. For a complex source area or non-steady-state plume, a superposition of analytical models that incorporate longitudinal and transverse dispersion and time may be used at sites where the centerline method would not be

  5. 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.

  6. Determination of rate constants and branching ratios for TCE degradation by zero-valent iron using a chain decay multispecies model.

    PubMed

    Hwang, Hyoun-Tae; Jeen, Sung-Wook; Sudicky, Edward A; Illman, Walter A

    2015-01-01

    The applicability of a newly-developed chain-decay multispecies model (CMM) was validated by obtaining kinetic rate constants and branching ratios along the reaction pathways of trichloroethene (TCE) reduction by zero-valent iron (ZVI) from column experiments. Changes in rate constants and branching ratios for individual reactions for degradation products over time for two columns under different geochemical conditions were examined to provide ranges of those parameters expected over the long-term. As compared to the column receiving deionized water, the column receiving dissolved CaCO3 showed higher mean degradation rates for TCE and all of its degradation products. However, the column experienced faster reactivity loss toward TCE degradation due to precipitation of secondary carbonate minerals, as indicated by a higher value for the ratio of maximum to minimum TCE degradation rate observed over time. From the calculated branching ratios, it was found that TCE and cis-dichloroethene (cis-DCE) were dominantly dechlorinated to chloroacetylene and acetylene, respectively, through reductive elimination for both columns. The CMM model, validated by the column test data in this study, provides a convenient tool to determine simultaneously the critical design parameters for permeable reactive barriers and natural attenuation such as rate constants and branching ratios. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Development and validation of different methods manipulating zero order and first order spectra for determination of the partially overlapped mixture benazepril and amlodipine: A comparative study

    NASA Astrophysics Data System (ADS)

    Hemdan, A.

    2016-07-01

    Three simple, selective, and accurate spectrophotometric methods have been developed and then validated for the analysis of Benazepril (BENZ) and Amlodipine (AML) in bulk powder and pharmaceutical dosage form. The first method is the absorption factor (AF) for zero order and amplitude factor (P-F) for first order spectrum, where both BENZ and AML can be measured from their resolved zero order spectra at 238 nm or from their first order spectra at 253 nm. The second method is the constant multiplication coupled with constant subtraction (CM-CS) for zero order and successive derivative subtraction-constant multiplication (SDS-CM) for first order spectrum, where both BENZ and AML can be measured from their resolved zero order spectra at 240 nm and 238 nm, respectively, or from their first order spectra at 214 nm and 253 nm for Benazepril and Amlodipine respectively. The third method is the novel constant multiplication coupled with derivative zero crossing (CM-DZC) which is a stability indicating assay method for determination of Benazepril and Amlodipine in presence of the main degradation product of Benazepril which is Benazeprilate (BENZT). The three methods were validated as per the ICH guidelines and the standard curves were found to be linear in the range of 5-60 μg/mL for Benazepril and 5-30 for Amlodipine, with well accepted mean correlation coefficient for each analyte. The intra-day and inter-day precision and accuracy results were well within the acceptable limits.

  8. Biotransformation of trace organic chemicals during groundwater recharge: How useful are first-order rate constants?

    PubMed

    Regnery, J; Wing, A D; Alidina, M; Drewes, J E

    2015-08-01

    This study developed relationships between the attenuation of emerging trace organic chemicals (TOrC) during managed aquifer recharge (MAR) as a function of retention time, system characteristics, and operating conditions using controlled laboratory-scale soil column experiments simulating MAR. The results revealed that MAR performance in terms of TOrC attenuation is primarily determined by key environmental parameters (i.e., redox, primary substrate). Soil columns with suboxic and anoxic conditions performed poorly (i.e., less than 30% attenuation of moderately degradable TOrC) in comparison to oxic conditions (on average between 70-100% attenuation for the same compounds) within a residence time of three days. Given this dependency on redox conditions, it was investigated if key parameter-dependent rate constants are more suitable for contaminant transport modeling to properly capture the dynamic TOrC attenuation under field-scale conditions. Laboratory-derived first-order removal kinetics were determined for 19 TOrC under three different redox conditions and rate constants were applied to MAR field data. Our findings suggest that simplified first-order rate constants will most likely not provide any meaningful results if the target compounds exhibit redox dependent biotransformation behavior or if the intention is to exactly capture the decline in concentration over time and distance at field-scale MAR. However, if the intention is to calculate the percent removal after an extended time period and subsurface travel distance, simplified first-order rate constants seem to be sufficient to provide a first estimate on TOrC attenuation during MAR. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Development and validation of different methods manipulating zero order and first order spectra for determination of the partially overlapped mixture benazepril and amlodipine: A comparative study.

    PubMed

    Hemdan, A

    2016-07-05

    Three simple, selective, and accurate spectrophotometric methods have been developed and then validated for the analysis of Benazepril (BENZ) and Amlodipine (AML) in bulk powder and pharmaceutical dosage form. The first method is the absorption factor (AF) for zero order and amplitude factor (P-F) for first order spectrum, where both BENZ and AML can be measured from their resolved zero order spectra at 238nm or from their first order spectra at 253nm. The second method is the constant multiplication coupled with constant subtraction (CM-CS) for zero order and successive derivative subtraction-constant multiplication (SDS-CM) for first order spectrum, where both BENZ and AML can be measured from their resolved zero order spectra at 240nm and 238nm, respectively, or from their first order spectra at 214nm and 253nm for Benazepril and Amlodipine respectively. The third method is the novel constant multiplication coupled with derivative zero crossing (CM-DZC) which is a stability indicating assay method for determination of Benazepril and Amlodipine in presence of the main degradation product of Benazepril which is Benazeprilate (BENZT). The three methods were validated as per the ICH guidelines and the standard curves were found to be linear in the range of 5-60μg/mL for Benazepril and 5-30 for Amlodipine, with well accepted mean correlation coefficient for each analyte. The intra-day and inter-day precision and accuracy results were well within the acceptable limits. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. 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.

  11. On the ambiguity of the reaction rate constants in multivariate curve resolution for reversible first-order reaction systems.

    PubMed

    Schröder, Henning; Sawall, Mathias; Kubis, Christoph; Selent, Detlef; Hess, Dieter; Franke, Robert; Börner, Armin; Neymeyr, Klaus

    2016-07-13

    If for a chemical reaction with a known reaction mechanism the concentration profiles are accessible only for certain species, e.g. only for the main product, then often the reaction rate constants cannot uniquely be determined from the concentration data. This is a well-known fact which includes the so-called slow-fast ambiguity. This work combines the question of unique or non-unique reaction rate constants with factor analytic methods of chemometrics. The idea is to reduce the rotational ambiguity of pure component factorizations by considering only those concentration factors which are possible solutions of the kinetic equations for a properly adapted set of reaction rate constants. The resulting set of reaction rate constants corresponds to those solutions of the rate equations which appear as feasible factors in a pure component factorization. The new analysis of the ambiguity of reaction rate constants extends recent research activities on the Area of Feasible Solutions (AFS). The consistency with a given chemical reaction scheme is shown to be a valuable tool in order to reduce the AFS. The new methods are applied to model and experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. 78 FR 63176 - Notice Announcing Workshop; Zero Rate Reactive Power Rate Schedules

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-10-23

    ... DEPARTMENT OF ENERGY Federal Energy Regulatory Commission [Docket No. AD14-1-000] Notice Announcing Workshop; Zero Rate Reactive Power Rate Schedules Concurrent with this notice, the Commission is issuing an order in Chehalis Power Generating, L.P., Docket No. ER05-1056-007 clarifying its policy...

  13. Three dielectric constants and orientation order parameters in nematic mesophases

    NASA Astrophysics Data System (ADS)

    Yoon, Hyung Guen; Jeong, Seung Yeon; Kumar, Satyendra; Park, Min Sang; Park, Jung Ok; Srinivasarao, M.; Shin, Sung Tae

    2011-03-01

    Temperature dependence of the three components ɛ1 , ɛ2 , and ɛ3 of dielectric constant and orientation order parameters in the nematic phase of mesogens with rod, banana, and zero-order dendritic shape were measured using the in-plane and vertical switching geometries, and micro-Raman technique. Results on the well-known uniaxial (Nu) nematogens, E7 and 5CB, revealed two components ɛ1 = ~ɛ| | and ɛ2 = ~ɛ3 = ~ɛ⊥ , as expected. The three dielectric constants were different for two azo substituted (A131 and A103) and an oxadiazole based (ODBP-Ph-C12) bent core mesogens, and a Ge core tetrapode. In some cases, two of the components became the same indicating a loss of biaxiality at temperatures coinciding with the previously reported Nu to biaxial nematic transition. This interpretation is substantiated by micro-Raman measurements of the uniaxial and biaxial nematic order parameters. Supported by the US Department of Energy, Basic Energy Sciences grant ER46572 and by Samsung Electronics Corporation.

  14. Applying constraints on model-based methods: Estimation of rate constants in a second order consecutive reaction

    NASA Astrophysics Data System (ADS)

    Kompany-Zareh, Mohsen; Khoshkam, Maryam

    2013-02-01

    This paper describes estimation of reaction rate constants and pure ultraviolet/visible (UV-vis) spectra of the component involved in a second order consecutive reaction between Ortho-Amino benzoeic acid (o-ABA) and Diazoniom ions (DIAZO), with one intermediate. In the described system, o-ABA was not absorbing in the visible region of interest and thus, closure rank deficiency problem did not exist. Concentration profiles were determined by solving differential equations of the corresponding kinetic model. In that sense, three types of model-based procedures were applied to estimate the rate constants of the kinetic system, according to Levenberg/Marquardt (NGL/M) algorithm. Original data-based, Score-based and concentration-based objective functions were included in these nonlinear fitting procedures. Results showed that when there is error in initial concentrations, accuracy of estimated rate constants strongly depends on the type of applied objective function in fitting procedure. Moreover, flexibility in application of different constraints and optimization of the initial concentrations estimation during the fitting procedure were investigated. Results showed a considerable decrease in ambiguity of obtained parameters by applying appropriate constraints and adjustable initial concentrations of reagents.

  15. Regularized learning of linear ordered-statistic constant false alarm rate filters (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Havens, Timothy C.; Cummings, Ian; Botts, Jonathan; Summers, Jason E.

    2017-05-01

    The linear ordered statistic (LOS) is a parameterized ordered statistic (OS) that is a weighted average of a rank-ordered sample. LOS operators are useful generalizations of aggregation as they can represent any linear aggregation, from minimum to maximum, including conventional aggregations, such as mean and median. In the fuzzy logic field, these aggregations are called ordered weighted averages (OWAs). Here, we present a method for learning LOS operators from training data, viz., data for which you know the output of the desired LOS. We then extend the learning process with regularization, such that a lower complexity or sparse LOS can be learned. Hence, we discuss what 'lower complexity' means in this context and how to represent that in the optimization procedure. Finally, we apply our learning methods to the well-known constant-false-alarm-rate (CFAR) detection problem, specifically for the case of background levels modeled by long-tailed distributions, such as the K-distribution. These backgrounds arise in several pertinent imaging problems, including the modeling of clutter in synthetic aperture radar and sonar (SAR and SAS) and in wireless communications.

  16. Determination of acidity constants of curcumin in aqueous solution and apparent rate constant of its decomposition

    NASA Astrophysics Data System (ADS)

    Bernabé-Pineda, Margarita; Ramírez-Silva, María. Teresa; Romero-Romo, Mario; González-Vergara, Enrique; Rojas-Hernández, Alberto

    2004-04-01

    The stability of curcumin (H 3Cur) in aqueous media is improved when the systems in which it is present are at high pH values (higher than 11.7), fitting a model describable by a pseudo-zero order with a rate constant k' for the disappearance of the Cur 3- species of 1.39 (10 -9) M min -1. There were three acidity constants measured for the curcumin as follows: p KA3=10.51±0.01 corresponding to the equilibrium HCur 2-=Cur 3-+H +, a p KA2=9.88±0.02 corresponding to the equilibrium H 2Cur -=HCur -2+H +. These p KA values were attributed to the hydrogen of the phenol part of the curcumin, while the p KA1=8.38±0.04 corresponds to the equilibrium H 3Cur=H 2Cur -+H + and is attributed the acetylacetone type group. Formation of quinoid structures play an important role in the tautomeric forms of the curcumin in aqueous media, which makes the experimental values differ from the theoretically calculated ones, depending on the conditions adopted in the study.

  17. Development of near zero-order release dosage forms using three-dimensional printing (3-DP) technology.

    PubMed

    Wang, Chen-Chao; Tejwani Motwani, Monica R; Roach, Willie J; Kay, Jennifer L; Yoo, Jaedeok; Surprenant, Henry L; Monkhouse, Donald C; Pryor, Timothy J

    2006-03-01

    Three near zero-order controlled-release pseudoephedrine hydrochloride (PEH) formulations demonstrating proportional release rates were developed using 3-Dimensional Printing (3-DP) technology. Mixtures of Kollidon SR and hydroxypropylmethyl cellulose (HPMC) were used as drug carriers. The release rates were adjusted by varying the Kollidon SR-HPMC ratio while keeping fabrication parameters constant. The dosage forms were composed of an immediate release core and a release rate regulating shell, fabricated with an aqueous PEH and an ethanolic triethyl citrate (TEC) binder, respectively. The dosage form design called for the drug to be released via diffusional pathways formed by HPMC in the shell matrix. The release rate was shown to increase correspondingly with the fraction of HPMC contained in the polymer blend. The designed formulations resulted in dosage forms that were insensitive to changes in pH of the dissolution medium, paddle stirring rate, and the presence/absence of a sinker. The near zero-order release properties were unchanged regardless of the dissolution test being performed on either single cubes or on a group of eight cubes encased within a gelatin capsule shell. The chemical and dissolution properties of the three formulations remained unchanged following 1 month's exposure to 25 degrees C/60% RH or 40 degrees C/75% RH environment under open container condition. The in vivo performance of the three formulations was evaluated using a single-dose, randomized, open-label, four-way crossover clinical study composed of 10 fasted healthy volunteers. The pharmacokinetic parameters were analyzed using a noncompartmental model. Qualitative rank order linear correlations between in vivo absorption profiles and in vitro dissolution parameters (with slope and intercept close to unity and origin, respectively) were obtained for all three formulations, indicating good support for a Level A in vivo/in vitro correlation.

  18. Inflation with a constant rate of roll

    NASA Astrophysics Data System (ADS)

    Motohashi, Hayato; Starobinsky, Alexei A.; Yokoyama, Jun'ichi

    2015-09-01

    We consider an inflationary scenario where the rate of inflaton roll defined by ̈phi/H dot phi remains constant. The rate of roll is small for slow-roll inflation, while a generic rate of roll leads to the interesting case of 'constant-roll' inflation. We find a general exact solution for the inflaton potential required for such inflaton behaviour. In this model, due to non-slow evolution of background, the would-be decaying mode of linear scalar (curvature) perturbations may not be neglected. It can even grow for some values of the model parameter, while the other mode always remains constant. However, this always occurs for unstable solutions which are not attractors for the given potential. The most interesting particular cases of constant-roll inflation remaining viable with the most recent observational data are quadratic hilltop inflation (with cutoff) and natural inflation (with an additional negative cosmological constant). In these cases even-order slow-roll parameters approach non-negligible constants while the odd ones are asymptotically vanishing in the quasi-de Sitter regime.

  19. Inflation with a constant rate of roll

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

    Motohashi, Hayato; Starobinsky, Alexei A.; Yokoyama, Jun'ichi, E-mail: motohashi@kicp.uchicago.edu, E-mail: alstar@landau.ac.ru, E-mail: yokoyama@resceu.s.u-tokyo.ac.jp

    2015-09-01

    We consider an inflationary scenario where the rate of inflaton roll defined by {sup ··}φ/H φ-dot remains constant. The rate of roll is small for slow-roll inflation, while a generic rate of roll leads to the interesting case of 'constant-roll' inflation. We find a general exact solution for the inflaton potential required for such inflaton behaviour. In this model, due to non-slow evolution of background, the would-be decaying mode of linear scalar (curvature) perturbations may not be neglected. It can even grow for some values of the model parameter, while the other mode always remains constant. However, this always occurs formore » unstable solutions which are not attractors for the given potential. The most interesting particular cases of constant-roll inflation remaining viable with the most recent observational data are quadratic hilltop inflation (with cutoff) and natural inflation (with an additional negative cosmological constant). In these cases even-order slow-roll parameters approach non-negligible constants while the odd ones are asymptotically vanishing in the quasi-de Sitter regime.« less

  20. Zero-order metoprolol pharmacokinetics after therapeutic doses: severe toxicity and cardiogenic shock.

    PubMed

    Isbister, Geoffrey K; Ang, Karyn; Gorman, Kieron; Cooper, Joyce; Mostafa, Ahmed; Roberts, Michael S

    2016-11-01

    Acute beta-blocker overdose can cause severe cardiac dysfunction. Chronic toxicity is rare but potentially severe. We report therapeutic dosing of metoprolol resulting in unusual pharmacokinetics and toxicity, given high-dose insulin therapy for treatment. A 90-year-old female presented with hypotension, tachycardia and severe cardiac dysfunction after commencing a rapidly increasing metoprolol dose of 250 mg split daily. She was admitted to intensive care and given high-dose insulin therapy (10 U/kg/h), noradrenaline, adrenaline and dobutamine for severe cardiac dysfunction (cardiac index, 0.76 L/min/m 2 ). She developed acute renal failure, ischaemic hepatitis and disseminated intravascular coagulopathy. Inotropes and high-dose insulin were weaned over four days with complete recovery. Metoprolol was quantified with liquid chromatography-tandem mass spectrometry and concentration-time data were analysed using MONOLIX ® vs 4.3 ( www.lixoft.com ). Admission metoprolol concentration was 2.39 μg/mL (therapeutic reference range: 0.035-0.5 μg/mL). Data best fitted a one compartmental model with Michaelis-Menten kinetics and zero order elimination at high concentrations. Final parameter estimates were V, 63.4 L, maximum rate [V m ], 9.57 mg h -1 , Michaelis constant [K m ], 1.97 mg L -1 . Predicted elimination half-life decreased from 20 h over time until there was first order elimination with a half-life 9 h. The time course of cardiac dysfunction was longer than acute overdose but consistent with prolonged zero order elimination of metoprolol, suggesting the patient was a poor CYP2D6 metaboliser. High-dose insulin euglycaemia appeared to be effective in combination with vasoconstrictors/inotropes.

  1. Zero-order drug delivery system: theory and preliminary testing.

    PubMed

    Brooke, D; Washkuhn, R J

    1977-02-01

    A new approach to zero-order drug delivery that includes geometric factors is described. An experimental device based on the theory was tested by following the release of stearic acid into ethanol. Three separate trials indicated that the solid was released via a zero-order process in a reproducible manner.

  2. Analytical model for advective-dispersive transport involving flexible boundary inputs, initial distributions and zero-order productions

    NASA Astrophysics Data System (ADS)

    Chen, Jui-Sheng; Li, Loretta Y.; Lai, Keng-Hsin; Liang, Ching-Ping

    2017-11-01

    A novel solution method is presented which leads to an analytical model for the advective-dispersive transport in a semi-infinite domain involving a wide spectrum of boundary inputs, initial distributions, and zero-order productions. The novel solution method applies the Laplace transform in combination with the generalized integral transform technique (GITT) to obtain the generalized analytical solution. Based on this generalized analytical expression, we derive a comprehensive set of special-case solutions for some time-dependent boundary distributions and zero-order productions, described by the Dirac delta, constant, Heaviside, exponentially-decaying, or periodically sinusoidal functions as well as some position-dependent initial conditions and zero-order productions specified by the Dirac delta, constant, Heaviside, or exponentially-decaying functions. The developed solutions are tested against an analytical solution from the literature. The excellent agreement between the analytical solutions confirms that the new model can serve as an effective tool for investigating transport behaviors under different scenarios. Several examples of applications, are given to explore transport behaviors which are rarely noted in the literature. The results show that the concentration waves resulting from the periodically sinusoidal input are sensitive to dispersion coefficient. The implication of this new finding is that a tracer test with a periodic input may provide additional information when for identifying the dispersion coefficients. Moreover, the solution strategy presented in this study can be extended to derive analytical models for handling more complicated problems of solute transport in multi-dimensional media subjected to sequential decay chain reactions, for which analytical solutions are not currently available.

  3. Numerical ordering of zero in honey bees.

    PubMed

    Howard, Scarlett R; Avarguès-Weber, Aurore; Garcia, Jair E; Greentree, Andrew D; Dyer, Adrian G

    2018-06-08

    Some vertebrates demonstrate complex numerosity concepts-including addition, sequential ordering of numbers, or even the concept of zero-but whether an insect can develop an understanding for such concepts remains unknown. We trained individual honey bees to the numerical concepts of "greater than" or "less than" using stimuli containing one to six elemental features. Bees could subsequently extrapolate the concept of less than to order zero numerosity at the lower end of the numerical continuum. Bees demonstrated an understanding that parallels animals such as the African grey parrot, nonhuman primates, and even preschool children. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

  4. Continuous fractional-order Zero Phase Error Tracking Control.

    PubMed

    Liu, Lu; Tian, Siyuan; Xue, Dingyu; Zhang, Tao; Chen, YangQuan

    2018-04-01

    A continuous time fractional-order feedforward control algorithm for tracking desired time varying input signals is proposed in this paper. The presented controller cancels the phase shift caused by the zeros and poles of controlled closed-loop fractional-order system, so it is called Fractional-Order Zero Phase Tracking Controller (FZPETC). The controlled systems are divided into two categories i.e. with and without non-cancellable (non-minimum-phase) zeros which stand in unstable region or on stability boundary. Each kinds of systems has a targeted FZPETC design control strategy. The improved tracking performance has been evaluated successfully by applying the proposed controller to three different kinds of fractional-order controlled systems. Besides, a modified quasi-perfect tracking scheme is presented for those systems which may not have available future tracking trajectory information or have problem in high frequency disturbance rejection if the perfect tracking algorithm is applied. A simulation comparison and a hardware-in-the-loop thermal peltier platform are shown to validate the practicality of the proposed quasi-perfect control algorithm. Copyright © 2018 ISA. Published by Elsevier Ltd. All rights reserved.

  5. In Vitro and In Vivo Sustained Zero-Order Delivery of Rapamycin (Sirolimus) From a Biodegradable Intraocular Device.

    PubMed

    Lance, Kevin D; Good, Samuel D; Mendes, Thaís S; Ishikiriyama, Mynna; Chew, Patrick; Estes, Laurel S; Yamada, Kazuhito; Mudumba, Sri; Bhisitkul, Robert B; Desai, Tejal A

    2015-11-01

    We created implantable intraocular devices capable of constant and continuous rapamycin release on the scale of months to years. Polycaprolactone (PCL) thin films were used to encapsulate rapamycin to create implantable and biodegradable intraocular devices. Different film devices were studied by modifying the size, thickness, and porosity of the PCL films. In vitro release of rapamycin was observed to be constant (zero-order) through 14 weeks of study. Release rates were tunable by altering PCL film porosity and thickness. In vivo release of rapamycin was observed out through 16 weeks with concentrations in the retina-choroid in the therapeutic range. Rapamycin concentration in the blood was below the lower limit of quantification. The drug remaining in the device was chemically stable in vitro and in vivo, and was sufficient to last for upwards of 2 years of total release. The mechanism of release is related to the dissolution kinetics of crystalline rapamycin. Microporous PCL thin film devices demonstrate good ocular compatibility and the ability to release rapamycin locally to the eye over the course of many weeks.

  6. In Vitro and In Vivo Sustained Zero-Order Delivery of Rapamycin (Sirolimus) From a Biodegradable Intraocular Device

    PubMed Central

    Lance, Kevin D.; Good, Samuel D.; Mendes, Thaís S.; Ishikiriyama, Mynna; Chew, Patrick; Estes, Laurel S.; Yamada, Kazuhito; Mudumba, Sri; Bhisitkul, Robert B.; Desai, Tejal A.

    2015-01-01

    Purpose We created implantable intraocular devices capable of constant and continuous rapamycin release on the scale of months to years. Methods Polycaprolactone (PCL) thin films were used to encapsulate rapamycin to create implantable and biodegradable intraocular devices. Different film devices were studied by modifying the size, thickness, and porosity of the PCL films. Results In vitro release of rapamycin was observed to be constant (zero-order) through 14 weeks of study. Release rates were tunable by altering PCL film porosity and thickness. In vivo release of rapamycin was observed out through 16 weeks with concentrations in the retina–choroid in the therapeutic range. Rapamycin concentration in the blood was below the lower limit of quantification. The drug remaining in the device was chemically stable in vitro and in vivo, and was sufficient to last for upwards of 2 years of total release. The mechanism of release is related to the dissolution kinetics of crystalline rapamycin. Conclusions Microporous PCL thin film devices demonstrate good ocular compatibility and the ability to release rapamycin locally to the eye over the course of many weeks. PMID:26559479

  7. Unidimensional factor models imply weaker partial correlations than zero-order correlations.

    PubMed

    van Bork, Riet; Grasman, Raoul P P P; Waldorp, Lourens J

    2018-06-01

    In this paper we present a new implication of the unidimensional factor model. We prove that the partial correlation between two observed variables that load on one factor given any subset of other observed variables that load on this factor lies between zero and the zero-order correlation between these two observed variables. We implement this result in an empirical bootstrap test that rejects the unidimensional factor model when partial correlations are identified that are either stronger than the zero-order correlation or have a different sign than the zero-order correlation. We demonstrate the use of the test in an empirical data example with data consisting of fourteen items that measure extraversion.

  8. On the Henry constant and isosteric heat at zero loading in gas phase adsorption.

    PubMed

    Do, D D; Nicholson, D; Do, H D

    2008-08-01

    The Henry constant and the isosteric heat of adsorption at zero loading are commonly used as indicators of the strength of the affinity of an adsorbate for a solid adsorbent. It is assumed that (i) they are observable in practice, (ii) the Van Hoff's plot of the logarithm of the Henry constant versus the inverse of temperature is always linear and the slope is equal to the heat of adsorption, and (iii) the isosteric heat of adsorption at zero loading is either constant or weakly dependent on temperature. We show in this paper that none of these three points is necessarily correct, first because these variables might not be observable since they are outside the range of measurability; second that the linearity of the Van Hoff plot breaks down at very high temperature, and third that the isosteric heat versus loading is a strong function of temperature. We demonstrate these points using Monte Carlo integration and Monte Carlo simulation of adsorption of various gases on a graphite surface. Another issue concerning the Henry constant is related to the way the adsorption excess is defined. The most commonly used equation is the one that assumes that the void volume is the volume extended all the way to a boundary passing through the centres of the outermost solid atoms. With this definition the Henry constant can become negative at high temperatures. Although adsorption at these temperatures may not be practical because of the very low value of the Henry constant, it is more useful to define the Henry constant in such a way that it is always positive at all temperatures. Here we propose the use of the accessible volume; the volume probed by the adsorbate when it is in nonpositive regions of the potential, to calculate the Henry constant.

  9. MICROBIAL TRANSFORMATION RATE CONSTANTS OF STRUCTURALLY DIVERSE MAN-MADE CHEMICALS

    EPA Science Inventory

    To assist in estimating microbially mediated transformation rates of man-made chemicals from their chemical structures, all second order rate constants that have been measured under conditions that make the values comparable have been extracted from the literature and combined wi...

  10. Analysis of gas absorption to a thin liquid film in the presence of a zero-order chemical reaction

    NASA Technical Reports Server (NTRS)

    Rajagopalan, S.; Rahman, M. M.

    1995-01-01

    The paper presents a detailed theoretical analysis of the process of gas absorption to a thin liquid film adjacent to a horizontal rotating disk. The film is formed by the impingement of a controlled liquid jet at the center of the disk and subsequent radial spreading of liquid along the disk. The chemical reaction between the gas and the liquid film can be expressed as a zero-order homogeneous reaction. The process was modeled by establishing equations for the conservation of mass, momentum, and species concentration and solving them analytically. A scaling analysis was used to determine dominant transport processes. Appropriate boundary conditions were used to solve these equations to develop expressions for the local concentration of gas across the thickness of the film and distributions of film height, bulk concentration, and Sherwood number along the radius of the disk. The partial differential equation for species concentration was solved using the separation of variables technique along with the Duhamel's theorem and the final analytical solution was expressed using confluent hypergeometric functions. Tables for eigenvalues and eigenfunctions are presented for a number of reaction rate constants. A parametric study was performed using Reynolds number, Ekman number, and dimensionless reaction rate as parameters. At all radial locations, Sherwood number increased with Reynolds number (flow rate) as well as Ekman number (rate of rotation). The enhancement of mass transfer due to chemical reaction was found to be small when compared to the case of no reaction (pure absorption), but the enhancement factor was very significant when compared to pure absorption in a stagnant liquid film. The zero-order reaction processes considered in the present investigation included the absorption of oxygen in aqueous alkaline solutions of sodiumdithionite and rhodium complex catalyzed carbonylation of methanol. Present analytical results were compared to previous theoretical

  11. Drug Delivery and Transport into the Central Circulation: An Example of Zero-Order In vivo Absorption of Rotigotine from a Transdermal Patch Formulation.

    PubMed

    Cawello, Willi; Braun, Marina; Andreas, Jens-Otto

    2018-01-13

    Pharmacokinetic studies using deconvolution methods and non-compartmental analysis to model clinical absorption of drugs are not well represented in the literature. The purpose of this research was (1) to define the system of equations for description of rotigotine (a dopamine receptor agonist delivered via a transdermal patch) absorption based on a pharmacokinetic model and (2) to describe the kinetics of rotigotine disposition after single and multiple dosing. The kinetics of drug disposition was evaluated based on rotigotine plasma concentration data from three phase 1 trials. In two trials, rotigotine was administered via a single patch over 24 h in healthy subjects. In a third trial, rotigotine was administered once daily over 1 month in subjects with early-stage Parkinson's disease (PD). A pharmacokinetic model utilizing deconvolution methods was developed to describe the relationship between drug release from the patch and plasma concentrations. Plasma-concentration over time profiles were modeled based on a one-compartment model with a time lag, a zero-order input (describing a constant absorption via skin into central circulation) and first-order elimination. Corresponding mathematical models for single- and multiple-dose administration were developed. After single-dose administration of rotigotine patches (using 2, 4 or 8 mg/day) in healthy subjects, a constant in vivo absorption was present after a minor time lag (2-3 h). On days 27 and 30 of the multiple-dose study in patients with PD, absorption was constant during patch-on periods and resembled zero-order kinetics. Deconvolution based on rotigotine pharmacokinetic profiles after single- or multiple-dose administration of the once-daily patch demonstrated that in vivo absorption of rotigotine showed constant input through the skin into the central circulation (resembling zero-order kinetics). Continuous absorption through the skin is a basis for stable drug exposure.

  12. A robust nanofluidic membrane with tunable zero-order release for implantable dose specific drug delivery.

    PubMed

    Fine, Daniel; Grattoni, Alessandro; Hosali, Sharath; Ziemys, Arturas; De Rosa, Enrica; Gill, Jaskaran; Medema, Ryan; Hudson, Lee; Kojic, Milos; Milosevic, Miljan; Brousseau Iii, Louis; Goodall, Randy; Ferrari, Mauro; Liu, Xuewu

    2010-11-21

    This manuscript demonstrates a mechanically robust implantable nanofluidic membrane capable of tunable long-term zero-order release of therapeutic agents in ranges relevant for clinical applications. The membrane, with nanochannels as small as 5 nm, allows for the independent control of both dosage and mechanical strength through the integration of high-density short nanochannels parallel to the membrane surface with perpendicular micro- and macrochannels for interfacing with the ambient solutions. These nanofluidic membranes are created using precision silicon fabrication techniques on silicon-on-insulator substrates enabling exquisite control over the monodispersed nanochannel dimensions and surface roughness. Zero-order release of analytes is achieved by exploiting molecule to surface interactions which dominate diffusive transport when fluids are confined to the nanoscale. In this study we investigate the nanofluidic membrane performance using custom diffusion and gas testing apparatuses to quantify molecular release rate and process uniformity as well as mechanical strength using a gas based burst test. The kinetics of the constrained zero-order release is probed with molecules presenting a range of sizes, charge states, and structural conformations. Finally, an optimal ratio of the molecular hydrodynamic diameter to the nanochannel dimension is determined to assure zero-order release for each tested molecule.

  13. 78 FR 72673 - Zero Rate Reactive Power Rate Schedules; Notice of Staff Workshop

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-12-03

    ... DEPARTMENT OF ENERGY Federal Energy Regulatory Commission [Docket No. AD14-1-000] Zero Rate Reactive Power Rate Schedules; Notice of Staff Workshop This notice establishes the location and date for... located at: https://www.ferc.gov/whats-new/registration/zero-rate-12-11-13-form.asp . The workshop will...

  14. Arrhenius Rate: constant volume burn

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

    Menikoff, Ralph

    A constant volume burn occurs for an idealized initial state in which a large volume of reactants at rest is suddenly raised to a high temperature and begins to burn. Due to the uniform spatial state, there is no fluid motion and no heat conduction. This reduces the time evolu tion to an ODE for the reaction progress variable. With an Arrhenius reaction rate, two characteristics of thermal ignition are illustrated: induction time and thermal runaway. The Frank-Kamenetskii approximation then leads to a simple expression for the adiabatic induction time. For a first order reaction, the analytic solution is derivedmore » and used to illustrate the effect of varying the activation temperature; in particular, on the induction time. In general, the ODE can be solved numerically. This is used to illustrate the effect of varying the reaction order. We note that for a first order reaction, the time evolution of the reaction progress variable has an exponential tail. In contrast, for a reaction order less than one, the reaction completes in a nite time. The reaction order also affects the induction time.« less

  15. Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

    PubMed

    Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

    2017-07-06

    The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

  16. Calculated third order rate constants for interpreting the mechanisms of hydrolyses of chloroformates, carboxylic Acid halides, sulfonyl chlorides and phosphorochloridates.

    PubMed

    Bentley, T William

    2015-05-08

    Hydrolyses of acid derivatives (e.g., carboxylic acid chlorides and fluorides, fluoro- and chloroformates, sulfonyl chlorides, phosphorochloridates, anhydrides) exhibit pseudo-first order kinetics. Reaction mechanisms vary from those involving a cationic intermediate (SN1) to concerted SN2 processes, and further to third order reactions, in which one solvent molecule acts as the attacking nucleophile and a second molecule acts as a general base catalyst. A unified framework is discussed, in which there are two reaction channels-an SN1-SN2 spectrum and an SN2-SN3 spectrum. Third order rate constants (k3) are calculated for solvolytic reactions in a wide range of compositions of acetone-water mixtures, and are shown to be either approximately constant or correlated with the Grunwald-Winstein Y parameter. These data and kinetic solvent isotope effects, provide the experimental evidence for the SN2-SN3 spectrum (e.g., for chloro- and fluoroformates, chloroacetyl chloride, p-nitrobenzoyl p-toluenesulfonate, sulfonyl chlorides). Deviations from linearity lead to U- or V-shaped plots, which assist in the identification of the point at which the reaction channel changes from SN2-SN3 to SN1-SN2 (e.g., for benzoyl chloride).

  17. A theorem regarding roots of the zero-order Bessel function of the first kind

    NASA Technical Reports Server (NTRS)

    Lin, X.-A.; Agrawal, O. P.

    1993-01-01

    This paper investigates a problem on the steady-state, conduction-convection heat transfer process in cylindrical porous heat exchangers. The governing partial differential equations for the system are obtained using the energy conservation law. Solution of these equations and the concept of enthalpy lead to a new approach to prove a theorem that the sum of inverse squares of all the positive roots of the zero order Bessel function of the first kind equals to one-forth. As a corollary, it is shown that the sum of one over pth power (p greater than or equal to 2) of the roots converges to some constant.

  18. Generalized characteristic ratios assignment for commensurate fractional order systems with one zero.

    PubMed

    Tabatabaei, Mohammad

    2017-07-01

    In this paper, a new method for determination of the desired characteristic equation and zero location of commensurate fractional order systems is presented. The concept of the characteristic ratio is extended for zero-including commensurate fractional order systems. The generalized version of characteristic ratios is defined such that the time-scaling property of characteristic ratios is also preserved. The monotonicity of the magnitude frequency response is employed to assign the generalized characteristic ratios for commensurate fractional order transfer functions with one zero. A simple pattern for characteristic ratios is proposed to reach a non-overshooting step response. Then, the proposed pattern is revisited to reach a low overshoot (say for example 2%) step response. Finally, zero-including controllers such as fractional order PI or lag (lead) controllers are designed using generalized characteristic ratios assignment method. Numerical simulations are provided to show the efficiency of the so designed controllers. Copyright © 2017 ISA. Published by Elsevier Ltd. All rights reserved.

  19. Zero-order bows in radially inhomogeneous spheres: direct and inverse problems.

    PubMed

    Adam, John A

    2011-10-01

    Zero-order ray paths are examined in radially inhomogeneous spheres with differentiable refractive index profiles. It is demonstrated that zero-order and sometimes twin zero-order bows can exist when the gradient of refractive index is sufficiently negative. Abel inversion is used to "recover" the refractive index profiles; it is therefore possible in principle to specify the nature and type of bows and determine the refractive index profile that induces them. This may be of interest in the field of rainbow refractometry and optical fiber studies. This ray-theoretic analysis has direct similarities with the phenomenon of "orbiting" and other phenomena in scattering theory and also in seismological, surface gravity wave, and gravitational "lensing" studies. For completeness these topics are briefly discussed in the appendixes; they may also be of pedagogic interest.

  20. Calculated Third Order Rate Constants for Interpreting the Mechanisms of Hydrolyses of Chloroformates, Carboxylic Acid Halides, Sulfonyl Chlorides and Phosphorochloridates

    PubMed Central

    Bentley, T. William

    2015-01-01

    Hydrolyses of acid derivatives (e.g., carboxylic acid chlorides and fluorides, fluoro- and chloroformates, sulfonyl chlorides, phosphorochloridates, anhydrides) exhibit pseudo-first order kinetics. Reaction mechanisms vary from those involving a cationic intermediate (SN1) to concerted SN2 processes, and further to third order reactions, in which one solvent molecule acts as the attacking nucleophile and a second molecule acts as a general base catalyst. A unified framework is discussed, in which there are two reaction channels—an SN1-SN2 spectrum and an SN2-SN3 spectrum. Third order rate constants (k3) are calculated for solvolytic reactions in a wide range of compositions of acetone-water mixtures, and are shown to be either approximately constant or correlated with the Grunwald-Winstein Y parameter. These data and kinetic solvent isotope effects, provide the experimental evidence for the SN2-SN3 spectrum (e.g., for chloro- and fluoroformates, chloroacetyl chloride, p-nitrobenzoyl p-toluenesulfonate, sulfonyl chlorides). Deviations from linearity lead to U- or V-shaped plots, which assist in the identification of the point at which the reaction channel changes from SN2-SN3 to SN1-SN2 (e.g., for benzoyl chloride). PMID:26006228

  1. A new approach using coagulation rate constant for evaluation of turbidity removal

    NASA Astrophysics Data System (ADS)

    Al-Sameraiy, Mukheled

    2017-06-01

    Coagulation-flocculation-sedimentation processes for treating three levels of bentonite synthetic turbid water using date seeds (DS) and alum (A) coagulants were investigated in the previous research work. In the current research, the same experimental results were used to adopt a new approach on a basis of using coagulation rate constant as an investigating parameter to identify optimum doses of these coagulants. Moreover, the performance of these coagulants to meet (WHO) turbidity standard was assessed by introducing a new evaluating criterion in terms of critical coagulation rate constant (kc). Coagulation rate constants (k2) were mathematically calculated in second order form of coagulation process for each coagulant. The maximum (k2) values corresponded to doses, which were obviously to be considered as optimum doses. The proposed criterion to assess the performance of coagulation process of these coagulants was based on the mathematical representation of (WHO) turbidity guidelines in second order form of coagulation process stated that (k2) for each coagulant should be ≥ (kc) for each level of synthetic turbid water. For all tested turbid water, DS coagulant could not satisfy it. While, A coagulant could satisfy it. The results obtained in the present research are exactly in agreement with the previous published results in terms of finding optimum doses for each coagulant and assessing their performances. On the whole, it is recommended considering coagulation rate constant to be a new approach as an indicator for investigating optimum doses and critical coagulation rate constant to be a new evaluating criterion to assess coagulants' performance.

  2. 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.

  3. Henry constant and isosteric heat at zero-loading for gas adsorption in carbon nanotubes.

    PubMed

    Do, D D; Do, H D; Wongkoblap, A; Nicholson, D

    2008-12-28

    The Henry constant and the isosteric heat of adsorption at zero loading in a carbon nanotube bundle are studied with Monte Carlo integration for the adsorption of gases over a range of temperatures. The spacing between nanotubes in a bundle is determined from the minimization of potential energy of interaction between these tubes. We study different tube configurations with bundles of 2, 3, 4 and 7 tubes. Depending on the configuration it is found that the spacing is of between 0.31 to 0.333 nm, and this falls within the range reported in the literature. The Henry constant has been carefully defined so that it will not become negative at high temperatures. This is done with the aid of accessible volume, rather than the usual absolute void volume. We show that linearity of the van't Hoff plot for the Henry constant is not strictly followed. Furthermore the slope of this plot is not equal to the isosteric heat of adsorption at zero loading, which is found to be a strong function of temperature. From the results we find that the Henry constant and the heat of adsorption depend on the tube configuration. In general the adsorption in the cusp interstices is strongest followed by that inside the tube and finally on the outer surface. However for very small tubes adsorption occurs inside the tube first. For molecules with orientation, the behaviour is even more interesting and the shape of the isosteric heat versus temperature depends on the degree of orientation, tube configuration and the domain of adsorption (interstices, inside the tube and on the outer surface).

  4. Comparison of ventilator-associated pneumonia (VAP) rates between different ICUs: Implications of a zero VAP rate.

    PubMed

    Sundar, Krishna M; Nielsen, David; Sperry, Paul

    2012-02-01

    Ventilator-associated pneumonia (VAP) is associated with significant morbidity and mortality. Measures to reduce the incidence of VAP have resulted in institutions reporting a zero or near-zero VAP rates. The implications of zero VAP rates are unclear. This study was done to compare outcomes between two intensive care units (ICU) with one of them reporting a zero VAP rate. This study retrospectively compared VAP rates between two ICUs: Utah Valley Regional Medical Center (UVRMC) with 25 ICU beds and American Fork Hospital (AFH) with 9 ICU beds. Both facilities are under the same management and attended by a single group of intensivists. Both ICUs have similar nursing and respiratory staffing patterns. Both ICUs use the same intensive care program for reduction of VAP rates. ICU outcomes between AFH (reporting zero VAP rate) and UVRMC (VAP rate of 2.41/1000 ventilator days) were compared for the years 2007-2008. UVRMC VAP rates during 2007 and 2008 were 2.31/1000 ventilator days and 2.5/1000 ventilator days respectively compared to a zero VAP rate at AFH. The total days of ventilation, mean days of ventilation per patient and mean duration of ICU stay per patient was higher in the UVRMC group as compared to AFH ICU group. There was no significant difference in mean age and APACHE II score between ICU patients at UVRMC and AFH. There was no statistical difference in rates of VAP and mortality between UVRMC and AFH. During comparisons of VAP rate between institutions, a zero VAP rate needs to be considered in the context of overall ventilator days, mean durations of ventilator stay and ICU mortality. Copyright © 2012 Elsevier Inc. All rights reserved.

  5. 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

  6. Optimal decay rate for the wave equation on a square with constant damping on a strip

    NASA Astrophysics Data System (ADS)

    Stahn, Reinhard

    2017-04-01

    We consider the damped wave equation with Dirichlet boundary conditions on the unit square parametrized by Cartesian coordinates x and y. We assume the damping a to be strictly positive and constant for x<σ and zero for x>σ . We prove the exact t^{-4/3}-decay rate for the energy of classical solutions. Our main result (Theorem 1) answers question (1) of Anantharaman and Léautaud (Anal PDE 7(1):159-214, 2014, Section 2C).

  7. On determining dose rate constants spectroscopically.

    PubMed

    Rodriguez, M; Rogers, D W O

    2013-01-01

    To investigate several aspects of the Chen and Nath spectroscopic method of determining the dose rate constants of (125)I and (103)Pd seeds [Z. Chen and R. Nath, Phys. Med. Biol. 55, 6089-6104 (2010)] including the accuracy of using a line or dual-point source approximation as done in their method, and the accuracy of ignoring the effects of the scattered photons in the spectra. Additionally, the authors investigate the accuracy of the literature's many different spectra for bare, i.e., unencapsulated (125)I and (103)Pd sources. Spectra generated by 14 (125)I and 6 (103)Pd seeds were calculated in vacuo at 10 cm from the source in a 2.7 × 2.7 × 0.05 cm(3) voxel using the EGSnrc BrachyDose Monte Carlo code. Calculated spectra used the initial photon spectra recommended by AAPM's TG-43U1 and NCRP (National Council of Radiation Protection and Measurements) Report 58 for the (125)I seeds, or TG-43U1 and NNDC(2000) (National Nuclear Data Center, 2000) for (103)Pd seeds. The emitted spectra were treated as coming from a line or dual-point source in a Monte Carlo simulation to calculate the dose rate constant. The TG-43U1 definition of the dose rate constant was used. These calculations were performed using the full spectrum including scattered photons or using only the main peaks in the spectrum as done experimentally. Statistical uncertainties on the air kerma/history and the dose rate/history were ≤0.2%. The dose rate constants were also calculated using Monte Carlo simulations of the full seed model. The ratio of the intensity of the 31 keV line relative to that of the main peak in (125)I spectra is, on average, 6.8% higher when calculated with the NCRP Report 58 initial spectrum vs that calculated with TG-43U1 initial spectrum. The (103)Pd spectra exhibit an average 6.2% decrease in the 22.9 keV line relative to the main peak when calculated with the TG-43U1 rather than the NNDC(2000) initial spectrum. The measured values from three different investigations are

  8. Dynamical approach to the cosmological constant.

    PubMed

    Mukohyama, Shinji; Randall, Lisa

    2004-05-28

    We consider a dynamical approach to the cosmological constant. There is a scalar field with a potential whose minimum occurs at a generic, but negative, value for the vacuum energy, and it has a nonstandard kinetic term whose coefficient diverges at zero curvature as well as the standard kinetic term. Because of the divergent coefficient of the kinetic term, the lowest energy state is never achieved. Instead, the cosmological constant automatically stalls at or near zero. The merit of this model is that it is stable under radiative corrections and leads to stable dynamics, despite the singular kinetic term. The model is not complete, however, in that some reheating is required. Nonetheless, our approach can at the very least reduce fine-tuning by 60 orders of magnitude or provide a new mechanism for sampling possible cosmological constants and implementing the anthropic principle.

  9. Quantitative Prediction of Rate Constants for Aqueous Racemization To Avoid Pointless Stereoselective Syntheses

    PubMed Central

    Ballard, Andrew; Ahmad, Hiwa O.; Narduolo, Stefania; Rosa, Lucy; Chand, Nikki; Cosgrove, David A.; Varkonyi, Peter; Asaad, Nabil; Tomasi, Simone

    2017-01-01

    Abstract Racemization has a large impact upon the biological properties of molecules but the chemical scope of compounds with known rate constants for racemization in aqueous conditions was hitherto limited. To address this remarkable blind spot, we have measured the kinetics for racemization of 28 compounds using circular dichroism and 1H NMR spectroscopy. We show that rate constants for racemization (measured by ourselves and others) correlate well with deprotonation energies from quantum mechanical (QM) and group contribution calculations. Such calculations thus provide predictions of the second‐order rate constants for general‐base‐catalyzed racemization that are usefully accurate. When applied to recent publications describing the stereoselective synthesis of compounds of purported biological value, the calculations reveal that racemization would be sufficiently fast to render these expensive syntheses pointless. PMID:29072355

  10. Comparison of TID Effects in Space-Like Variable Dose Rates and Constant Dose Rates

    NASA Technical Reports Server (NTRS)

    Harris, Richard D.; McClure, Steven S.; Rax, Bernard G.; Evans, Robin W.; Jun, Insoo

    2008-01-01

    The degradation of the LM193 dual voltage comparator has been studied at different TID dose rate profiles, including several different constant dose rates and a variable dose rate that simulates the behavior of a solar flare. A comparison of results following constant dose rate vs. variable dose rates is made to explore how well the constant dose rates used for typical part testing predict the performance during a simulated space-like mission. Testing at a constant dose rate equal to the lowest dose rate seen during the simulated flare provides an extremely conservative estimate of the overall amount of degradation. A constant dose rate equal to the average dose rate is also more conservative than the variable rate. It appears that, for this part, weighting the dose rates by the amount of total dose received at each rate (rather than the amount of time at each dose rate) results in an average rate that produces an amount of degradation that is a reasonable approximation to that received by the variable rate.

  11. On determining dose rate constants spectroscopically

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

    Rodriguez, M.; Rogers, D. W. O.

    2013-01-15

    Purpose: To investigate several aspects of the Chen and Nath spectroscopic method of determining the dose rate constants of {sup 125}I and {sup 103}Pd seeds [Z. Chen and R. Nath, Phys. Med. Biol. 55, 6089-6104 (2010)] including the accuracy of using a line or dual-point source approximation as done in their method, and the accuracy of ignoring the effects of the scattered photons in the spectra. Additionally, the authors investigate the accuracy of the literature's many different spectra for bare, i.e., unencapsulated {sup 125}I and {sup 103}Pd sources. Methods: Spectra generated by 14 {sup 125}I and 6 {sup 103}Pd seedsmore » were calculated in vacuo at 10 cm from the source in a 2.7 Multiplication-Sign 2.7 Multiplication-Sign 0.05 cm{sup 3} voxel using the EGSnrc BrachyDose Monte Carlo code. Calculated spectra used the initial photon spectra recommended by AAPM's TG-43U1 and NCRP (National Council of Radiation Protection and Measurements) Report 58 for the {sup 125}I seeds, or TG-43U1 and NNDC(2000) (National Nuclear Data Center, 2000) for {sup 103}Pd seeds. The emitted spectra were treated as coming from a line or dual-point source in a Monte Carlo simulation to calculate the dose rate constant. The TG-43U1 definition of the dose rate constant was used. These calculations were performed using the full spectrum including scattered photons or using only the main peaks in the spectrum as done experimentally. Statistical uncertainties on the air kerma/history and the dose rate/history were Less-Than-Or-Slanted-Equal-To 0.2%. The dose rate constants were also calculated using Monte Carlo simulations of the full seed model. Results: The ratio of the intensity of the 31 keV line relative to that of the main peak in {sup 125}I spectra is, on average, 6.8% higher when calculated with the NCRP Report 58 initial spectrum vs that calculated with TG-43U1 initial spectrum. The {sup 103}Pd spectra exhibit an average 6.2% decrease in the 22.9 keV line relative to the main peak

  12. Zero-point corrections and temperature dependence of HD spin-spin coupling constants of heavy metal hydride and dihydrogen complexes calculated by vibrational averaging.

    PubMed

    Mort, Brendan C; Autschbach, Jochen

    2006-08-09

    Vibrational corrections (zero-point and temperature dependent) of the H-D spin-spin coupling constant J(HD) for six transition metal hydride and dihydrogen complexes have been computed from a vibrational average of J(HD) as a function of temperature. Effective (vibrationally averaged) H-D distances have also been determined. The very strong temperature dependence of J(HD) for one of the complexes, [Ir(dmpm)Cp*H2]2 + (dmpm = bis(dimethylphosphino)methane) can be modeled simply by the Boltzmann average of the zero-point vibrationally averaged JHD of two isomers. For this complex and four others, the vibrational corrections to JHD are shown to be highly significant and lead to improved agreement between theory and experiment in most cases. The zero-point vibrational correction is important for all complexes. Depending on the shape of the potential energy and J-coupling surfaces, for some of the complexes higher vibrationally excited states can also contribute to the vibrational corrections at temperatures above 0 K and lead to a temperature dependence. We identify different classes of complexes where a significant temperature dependence of J(HD) may or may not occur for different reasons. A method is outlined by which the temperature dependence of the HD spin-spin coupling constant can be determined with standard quantum chemistry software. Comparisons are made with experimental data and previously calculated values where applicable. We also discuss an example where a low-order expansion around the minimum of a complicated potential energy surface appears not to be sufficient for reproducing the experimentally observed temperature dependence.

  13. Bessel Plasmon-Polaritons at the Boundaries of Metamaterials with Near-Zero Dielectric Constants

    NASA Astrophysics Data System (ADS)

    Kurilkina, S. N.; Belyi, V. N.; Kazak, N. S.; Binhussain, M. A.

    2015-07-01

    The conditions for and features of the excitation of Bessel plasmon-polaritons (BPP) are examined at the boundary of a hyperbolic metamaterial with a near-zero dielectric constant made of a dielectric matrix with metal nanorods embedded in it normal to its surface. This material is compared with BPP that have traditional surface plasmons. The effect of the absorption of the metamaterial on the excitation of BPP is studied. The possibility of changes in the direction of the radial energy fl ows in BPP excited at the surface of an isotropic medium, a hyperbolic metamaterial, is demonstrated and the conditions for these changes are determined.

  14. The elimination of zero-order diffraction of 10.6 μm infrared digital holography

    NASA Astrophysics Data System (ADS)

    Liu, Ning; Yang, Chao

    2017-05-01

    A new method of eliminating the zero-order diffraction in infrared digital holography has been raised in this paper. Usually in the reconstruction of digital holography, the spatial frequency of the infrared thermal imager, such as microbolometer, cannot be compared to the common visible CCD or CMOS devices. The infrared imager suffers the problems of large pixel size and low spatial resolution, which cause the zero-order diffraction a severe influence of the reconstruction process of digital holograms. The zero-order diffraction has very large energy and occupies the central region in the spectrum domain. In this paper, we design a new filtering strategy to overcome this problem. This filtering strategy contains two kinds of filtering process which are the Gaussian low-frequency filter and the high-pass phase averaging filter. With the correct set of the calculating parameters, these filtering strategies can work effectively on the holograms and fully eliminate the zero-order diffraction, as well as the two crossover bars shown in the spectrum domain. Detailed explanation and discussion about the new method have been proposed in this paper, and the experiment results are also demonstrated to prove the performance of this method.

  15. Can compactifications solve the cosmological constant problem?

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

    Hertzberg, Mark P.; Center for Theoretical Physics, Department of Physics,Massachusetts Institute of Technology,77 Massachusetts Ave, Cambridge, MA 02139; Masoumi, Ali

    2016-06-30

    Recently, there have been claims in the literature that the cosmological constant problem can be dynamically solved by specific compactifications of gravity from higher-dimensional toy models. These models have the novel feature that in the four-dimensional theory, the cosmological constant Λ is much smaller than the Planck density and in fact accumulates at Λ=0. Here we show that while these are very interesting models, they do not properly address the real cosmological constant problem. As we explain, the real problem is not simply to obtain Λ that is small in Planck units in a toy model, but to explain whymore » Λ is much smaller than other mass scales (and combinations of scales) in the theory. Instead, in these toy models, all other particle mass scales have been either removed or sent to zero, thus ignoring the real problem. To this end, we provide a general argument that the included moduli masses are generically of order Hubble, so sending them to zero trivially sends the cosmological constant to zero. We also show that the fundamental Planck mass is being sent to zero, and so the central problem is trivially avoided by removing high energy physics altogether. On the other hand, by including various large mass scales from particle physics with a high fundamental Planck mass, one is faced with a real problem, whose only known solution involves accidental cancellations in a landscape.« less

  16. Balancing specificity, sensitivity, and speed of ligand discrimination by zero-order ultraspecificity

    NASA Astrophysics Data System (ADS)

    Kajita, Masashi K.; Aihara, Kazuyuki; Kobayashi, Tetsuya J.

    2017-07-01

    Specific interactions between receptors and their target ligands in the presence of nontarget ligands are crucial for biological processes such as T cell ligand discrimination. To discriminate between the target and nontarget ligands, cells have to increase specificity to the target ligands by amplifying the small differences in affinity among ligands. In addition, sensitivity to the ligand concentration and quick discrimination are also important to detect low amounts of target ligands and facilitate fast cellular decision making after ligand recognition. In this work we propose a mechanism for nonlinear specificity amplification (ultraspecificity) based on zero-order saturating reactions, which was originally proposed to explain nonlinear sensitivity amplification (ultrasensitivity) to the ligand concentration. In contrast to the previously proposed proofreading mechanisms that amplify the specificity by a multistep reaction, our model can produce an optimal balance of specificity, sensitivity, and quick discrimination. Furthermore, we show that a model for insensitivity to a large number of nontarget ligands can be naturally derived from a model with the zero-order ultraspecificity. The zero-order ultraspecificity, therefore, may provide an alternative way to understand ligand discrimination from the viewpoint of nonlinear properties in biochemical reactions.

  17. Vegetation-environment relationships in zero-order basins in coastal Oregon.

    Treesearch

    Chris D. Sheridan; Thomas A. Spies

    2005-01-01

    Zero-order basins, where hillslope topography converges to form drainages, are common in steep, forested landscapes but we know little about their ecological structure. We used indirect gradient analysis to characterize gradients in plant species composition and cluster analysis to characterize groups of plant species associated with specific geomorphic areas. We...

  18. The Rate Constant for Fluorescence Quenching

    ERIC Educational Resources Information Center

    Legenza, Michael W.; Marzzacco, Charles J.

    1977-01-01

    Describes an experiment that utilizes fluorescence intensity measurements from a Spectronic 20 to determine the rate constant for the fluorescence quenching of various aromatic hydrocarbons by carbon tetrachloride in an ethanol solvent. (MLH)

  19. Rate Constant and Reaction Coordinate of Trp-Cage Folding in Explicit Water

    PubMed Central

    Juraszek, Jarek; Bolhuis, Peter G.

    2008-01-01

    We report rate constant calculations and a reaction coordinate analysis of the rate-limiting folding and unfolding process of the Trp-cage mini-protein in explicit solvent using transition interface sampling. Previous transition path sampling simulations revealed that in this (un)folding process the protein maintains its compact configuration, while a (de)increase of secondary structure is observed. The calculated folding rate agrees reasonably with experiment, while the unfolding rate is 10 times higher. We discuss possible origins for this mismatch. We recomputed the rates with the forward flux sampling method, and found a discrepancy of four orders of magnitude, probably caused by the method's higher sensitivity to the choice of order parameter with respect to transition interface sampling. Finally, we used the previously computed transition path-sampling ensemble to screen combinations of many order parameters for the best model of the reaction coordinate by employing likelihood maximization. We found that a combination of the root mean-square deviation of the helix and of the entire protein was, of the set of tried order parameters, the one that best describes the reaction coordination. PMID:18676648

  20. Estimation of hydrolysis rate constants for carbamates ...

    EPA Pesticide Factsheets

    Cheminformatics based tools, such as the Chemical Transformation Simulator under development in EPA’s Office of Research and Development, are being increasingly used to evaluate chemicals for their potential to degrade in the environment or be transformed through metabolism. Hydrolysis represents a major environmental degradation pathway; unfortunately, only a small fraction of hydrolysis rates for about 85,000 chemicals on the Toxic Substances Control Act (TSCA) inventory are in public domain, making it critical to develop in silico approaches to estimate hydrolysis rate constants. In this presentation, we compare three complementary approaches to estimate hydrolysis rates for carbamates, an important chemical class widely used in agriculture as pesticides, herbicides and fungicides. Fragment-based Quantitative Structure Activity Relationships (QSARs) using Hammett-Taft sigma constants are widely published and implemented for relatively simple functional groups such as carboxylic acid esters, phthalate esters, and organophosphate esters, and we extend these to carbamates. We also develop a pKa based model and a quantitative structure property relationship (QSPR) model, and evaluate them against measured rate constants using R square and root mean square (RMS) error. Our work shows that for our relatively small sample size of carbamates, a Hammett-Taft based fragment model performs best, followed by a pKa and a QSPR model. This presentation compares three comp

  1. Population Heterogeneity in Mutation Rate Increases the Frequency of Higher-Order Mutants and Reduces Long-Term Mutational Load

    PubMed Central

    Alexander, Helen K.; Mayer, Stephanie I.; Bonhoeffer, Sebastian

    2017-01-01

    Abstract Mutation rate is a crucial evolutionary parameter that has typically been treated as a constant in population genetic analyses. However, the propensity to mutate is likely to vary among co-existing individuals within a population, due to genetic polymorphisms, heterogeneous environmental influences, and random physiological fluctuations. We review the evidence for mutation rate heterogeneity and explore its consequences by extending classic population genetic models to allow an arbitrary distribution of mutation rate among individuals, either with or without inheritance. With this general new framework, we rigorously establish the effects of heterogeneity at various evolutionary timescales. In a single generation, variation of mutation rate about the mean increases the probability of producing zero or many simultaneous mutations on a genome. Over multiple generations of mutation and selection, heterogeneity accelerates the appearance of both deleterious and beneficial multi-point mutants. At mutation-selection balance, higher-order mutant frequencies are likewise boosted, while lower-order mutants exhibit subtler effects; nonetheless, population mean fitness is always enhanced. We quantify the dependencies on moments of the mutation rate distribution and selection coefficients, and clarify the role of mutation rate inheritance. While typical methods of estimating mutation rate will recover only the population mean, analyses assuming mutation rate is fixed to this mean could underestimate the potential for multi-locus adaptation, including medically relevant evolution in pathogenic and cancerous populations. We discuss the potential to empirically parameterize mutation rate distributions, which have to date hardly been quantified. PMID:27836985

  2. Third-order elastic constants of diamond determined from experimental data

    DOE PAGES

    Winey, J. M.; Hmiel, A.; Gupta, Y. M.

    2016-06-01

    The pressure derivatives of the second-order elastic constants (SOECs) of diamond were determined by analyzing previous sound velocity measurements under hydrostatic stress [McSkimin and Andreatch, J. Appl. Phys. 43, 294 (1972)]. Furthermore, our analysis corrects an error in the previously reported results.We present a complete and corrected set of third-order elastic constants (TOECs) using the corrected pressure derivatives, together with published data for the nonlinear elastic response of shock compressed diamond [Lang and Gupta, Phys. Rev. Lett. 106, 125502 (2011)] and it differs significantly from TOECs published previously.

  3. First and Higher Order Effects on Zero Order Radiative Transfer Model

    NASA Astrophysics Data System (ADS)

    Neelam, M.; Mohanty, B.

    2014-12-01

    Microwave radiative transfer model are valuable tool in understanding the complex land surface interactions. Past literature has largely focused on local sensitivity analysis for factor priotization and ignoring the interactions between the variables and uncertainties around them. Since land surface interactions are largely nonlinear, there always exist uncertainties, heterogeneities and interactions thus it is important to quantify them to draw accurate conclusions. In this effort, we used global sensitivity analysis to address the issues of variable uncertainty, higher order interactions, factor priotization and factor fixing for zero-order radiative transfer (ZRT) model. With the to-be-launched Soil Moisture Active Passive (SMAP) mission of NASA, it is very important to have a complete understanding of ZRT for soil moisture retrieval to direct future research and cal/val field campaigns. This is a first attempt to use GSA technique to quantify first order and higher order effects on brightness temperature from ZRT model. Our analyses reflect conditions observed during the growing agricultural season for corn and soybeans in two different regions in - Iowa, U.S.A and Winnipeg, Canada. We found that for corn fields in Iowa, there exist significant second order interactions between soil moisture, surface roughness parameters (RMS height and correlation length) and vegetation parameters (vegetation water content, structure and scattering albedo), whereas in Winnipeg, second order interactions are mainly due to soil moisture and vegetation parameters. But for soybean fields in both Iowa and Winnipeg, we found significant interactions only to exist between soil moisture and surface roughness parameters.

  4. 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.

  5. Rate constants for the slow Mu + propane abstraction reaction at 300 K by diamagnetic RF resonance.

    PubMed

    Fleming, Donald G; Cottrell, Stephen P; McKenzie, Iain; Ghandi, Khashayar

    2015-08-14

    The study of kinetic isotope effects for H-atom abstraction rates by incident H-atoms from the homologous series of lower mass alkanes (CH4, C2H6 and, here, C3H8) provides important tests of reaction rate theory on polyatomic systems. With a mass of only 0.114 amu, the most sensitive test is provided by the rates of the Mu atom. Abstraction of H by Mu can be highly endoergic, due to the large zero-point energy shift in the MuH bond formed, which also gives rise to high activation energies from similar zero-point energy corrections at the transition state. Rates are then far too slow near 300 K to be measured by conventional TF-μSR techniques that follow the disappearance of the spin-polarised Mu atom with time. Reported here is the first measurement of a slow Mu reaction rate in the gas phase by the technique of diamagnetic radio frequency (RF) resonance, where the amplitude of the MuH product formed in the Mu + C3H8 reaction is followed with time. The measured rate constant, kMu = (6.8 ± 0.5) × 10(-16) cm(3) s(-1) at 300 K, is surprisingly only about a factor of three slower than that expected for H + C3H8, indicating a dominant contribution from quantum tunneling in the Mu reaction, consistent with elementary transition state theory calculations of the kMu/kH kinetic isotope effect.

  6. Convergence of high order memory kernels in the Nakajima-Zwanzig generalized master equation and rate constants: Case study of the spin-boson model.

    PubMed

    Xu, Meng; Yan, Yaming; Liu, Yanying; Shi, Qiang

    2018-04-28

    The Nakajima-Zwanzig generalized master equation provides a formally exact framework to simulate quantum dynamics in condensed phases. Yet, the exact memory kernel is hard to obtain and calculations based on perturbative expansions are often employed. By using the spin-boson model as an example, we assess the convergence of high order memory kernels in the Nakajima-Zwanzig generalized master equation. The exact memory kernels are calculated by combining the hierarchical equation of motion approach and the Dyson expansion of the exact memory kernel. High order expansions of the memory kernels are obtained by extending our previous work to calculate perturbative expansions of open system quantum dynamics [M. Xu et al., J. Chem. Phys. 146, 064102 (2017)]. It is found that the high order expansions do not necessarily converge in certain parameter regimes where the exact kernel show a long memory time, especially in cases of slow bath, weak system-bath coupling, and low temperature. Effectiveness of the Padé and Landau-Zener resummation approaches is tested, and the convergence of higher order rate constants beyond Fermi's golden rule is investigated.

  7. Convergence of high order memory kernels in the Nakajima-Zwanzig generalized master equation and rate constants: Case study of the spin-boson model

    NASA Astrophysics Data System (ADS)

    Xu, Meng; Yan, Yaming; Liu, Yanying; Shi, Qiang

    2018-04-01

    The Nakajima-Zwanzig generalized master equation provides a formally exact framework to simulate quantum dynamics in condensed phases. Yet, the exact memory kernel is hard to obtain and calculations based on perturbative expansions are often employed. By using the spin-boson model as an example, we assess the convergence of high order memory kernels in the Nakajima-Zwanzig generalized master equation. The exact memory kernels are calculated by combining the hierarchical equation of motion approach and the Dyson expansion of the exact memory kernel. High order expansions of the memory kernels are obtained by extending our previous work to calculate perturbative expansions of open system quantum dynamics [M. Xu et al., J. Chem. Phys. 146, 064102 (2017)]. It is found that the high order expansions do not necessarily converge in certain parameter regimes where the exact kernel show a long memory time, especially in cases of slow bath, weak system-bath coupling, and low temperature. Effectiveness of the Padé and Landau-Zener resummation approaches is tested, and the convergence of higher order rate constants beyond Fermi's golden rule is investigated.

  8. 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.

  9. Experimental determination of third-order elastic constants of diamond.

    PubMed

    Lang, J M; Gupta, Y M

    2011-03-25

    To determine the nonlinear elastic response of diamond, single crystals were shock compressed along the [100], [110], and [111] orientations to 120 GPa peak elastic stresses. Particle velocity histories and elastic wave velocities were measured by using laser interferometry. The measured elastic wave profiles were used, in combination with published acoustic measurements, to determine the complete set of third-order elastic constants. These constants represent the first experimental determination, and several differ significantly from those calculated by using theoretical models.

  10. 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.

  11. Uniform function constants of motion and their first-order perturbation

    NASA Astrophysics Data System (ADS)

    Prato, Domingo; Hamity, Victor H.

    2005-05-01

    The main purpose of this work is to present some uniform function constants of motion rather than the well-known quantities arising from spacetime symmetries. These constants are usually associated with the intrinsic characteristics of the trajectories of a particle in a central potential field. We treat two cases. The first is the Lenz vector which sometimes is found in the literature [1, 2]; the other is associated with the isotropic harmonic oscillator, of relative importance in some simple models of the classical molecular interaction. The first example is applied to describe the perturbation of the trajectories in the Rutherford scattering and the precession of the Keplerian orbit of a planet. In the other case the conserved quantity is a symmetric tensor. We find the eigenvectors and eigenvalues of that tensor while at the same time we obtain the solution to the problem of calculating the rotation rate of the orbits in first order of a perturbation parameter in the potential energy, by performing a simple coordinate transformation in the Cartesian plane. We think that the present work addresses many aspects of mechanics with a didactical interest in other physics or mathematics courses.

  12. An optimal policy for deteriorating items with time-proportional deterioration rate and constant and time-dependent linear demand rate

    NASA Astrophysics Data System (ADS)

    Singh, Trailokyanath; Mishra, Pandit Jagatananda; Pattanayak, Hadibandhu

    2017-12-01

    In this paper, an economic order quantity (EOQ) inventory model for a deteriorating item is developed with the following characteristics: (i) The demand rate is deterministic and two-staged, i.e., it is constant in first part of the cycle and linear function of time in the second part. (ii) Deterioration rate is time-proportional. (iii) Shortages are not allowed to occur. The optimal cycle time and the optimal order quantity have been derived by minimizing the total average cost. A simple solution procedure is provided to illustrate the proposed model. The article concludes with a numerical example and sensitivity analysis of various parameters as illustrations of the theoretical results.

  13. 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.

  14. Rate constant for reaction of atomic hydrogen with germane

    NASA Technical Reports Server (NTRS)

    Nava, David F.; Payne, Walter A.; Marston, George; Stief, Louis J.

    1990-01-01

    Due to the interest in the chemistry of germane in the atmospheres of Jupiter and Saturn, and because previously reported kinetic reaction rate studies at 298 K gave results differing by a factor of 200, laboratory measurements were performed to determine the reaction rate constant for H + GeH4. Results of the study at 298 K, obtained via the direct technique of flash photolysis-resonance fluorescence, yield the reaction rate constant, k = (4.08 + or - 0.22) x 10(exp -12) cu cm/s.

  15. Binding Rate Constants Reveal Distinct Features of Disordered Protein Domains.

    PubMed

    Dogan, Jakob; Jonasson, Josefin; Andersson, Eva; Jemth, Per

    2015-08-04

    Intrinsically disordered proteins (IDPs) are abundant in the proteome and involved in key cellular functions. However, experimental data about the binding kinetics of IDPs as a function of different environmental conditions are scarce. We have performed an extensive characterization of the ionic strength dependence of the interaction between the molten globular nuclear co-activator binding domain (NCBD) of CREB binding protein and five different protein ligands, including the intrinsically disordered activation domain of p160 transcriptional co-activators (SRC1, TIF2, ACTR), the p53 transactivation domain, and the folded pointed domain (PNT) of transcription factor ETS-2. Direct comparisons of the binding rate constants under identical conditions show that the association rate constant, kon, for interactions between NCBD and disordered protein domains is high at low salt concentrations (90-350 × 10(6) M(-1) s(-1) at 4 °C) but is reduced significantly (10-30-fold) with an increasing ionic strength and reaches a plateau around physiological ionic strength. In contrast, the kon for the interaction between NCBD and the folded PNT domain is only 7 × 10(6) M(-1) s(-1) (4 °C and low salt) and displays weak ionic strength dependence, which could reflect a distinctly different association that relies less on electrostatic interactions. Furthermore, the basal rate constant (in the absence of electrostatic interactions) is high for the NCBD interactions, exceeding those typically observed for folded proteins. One likely interpretation is that disordered proteins have a large number of possible collisions leading to a productive on-pathway encounter complex, while folded proteins are more restricted in terms of orientation. Our results highlight the importance of electrostatic interactions in binding involving IDPs and emphasize the significance of including ionic strength as a factor in studies that compare the binding properties of IDPs to those of ordered proteins.

  16. 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

  17. Precisely and Accurately Inferring Single-Molecule Rate Constants

    PubMed Central

    Kinz-Thompson, Colin D.; Bailey, Nevette A.; Gonzalez, Ruben L.

    2017-01-01

    The kinetics of biomolecular systems can be quantified by calculating the stochastic rate constants that govern the biomolecular state versus time trajectories (i.e., state trajectories) of individual biomolecules. To do so, the experimental signal versus time trajectories (i.e., signal trajectories) obtained from observing individual biomolecules are often idealized to generate state trajectories by methods such as thresholding or hidden Markov modeling. Here, we discuss approaches for idealizing signal trajectories and calculating stochastic rate constants from the resulting state trajectories. Importantly, we provide an analysis of how the finite length of signal trajectories restrict the precision of these approaches, and demonstrate how Bayesian inference-based versions of these approaches allow rigorous determination of this precision. Similarly, we provide an analysis of how the finite lengths and limited time resolutions of signal trajectories restrict the accuracy of these approaches, and describe methods that, by accounting for the effects of the finite length and limited time resolution of signal trajectories, substantially improve this accuracy. Collectively, therefore, the methods we consider here enable a rigorous assessment of the precision, and a significant enhancement of the accuracy, with which stochastic rate constants can be calculated from single-molecule signal trajectories. PMID:27793280

  18. Molecular and Metabolic Adaptations of Lactococcus lactis at Near-Zero Growth Rates

    PubMed Central

    Ercan, Onur; Wels, Michiel; Smid, Eddy J.

    2014-01-01

    This paper describes the molecular and metabolic adaptations of Lactococcus lactis during the transition from a growing to a near-zero growth state by using carbon-limited retentostat cultivation. Transcriptomic analyses revealed that metabolic patterns shifted between lactic- and mixed-acid fermentations during retentostat cultivation, which appeared to be controlled at the level of transcription of the corresponding pyruvate dissipation-encoding genes. During retentostat cultivation, cells continued to consume several amino acids but also produced specific amino acids, which may derive from the conversion of glycolytic intermediates. We identify a novel motif containing CTGTCAG in the upstream regions of several genes related to amino acid conversion, which we propose to be the target site for CodY in L. lactis KF147. Finally, under extremely low carbon availability, carbon catabolite repression was progressively relieved and alternative catabolic functions were found to be highly expressed, which was confirmed by enhanced initial acidification rates on various sugars in cells obtained from near-zero-growth cultures. The present integrated transcriptome and metabolite (amino acids and previously reported fermentation end products) study provides molecular understanding of the adaptation of L. lactis to conditions supporting low growth rates and expands our earlier analysis of the quantitative physiology of this bacterium at near-zero growth rates toward gene regulation patterns involved in zero-growth adaptation. PMID:25344239

  19. THz computed tomography system with zero-order Bessel beam

    NASA Astrophysics Data System (ADS)

    Niu, Liting; Wu, Qiao; Wang, Kejia; Liu, Jinsong; Yang, Zhengang

    2018-01-01

    Terahertz (THz) waves can penetrate many optically opaque dielectric materials such as plastics, ceramics and colorants. It is effective to reveal the internal structures of these materials. We have built a THz Computed Tomography (CT) system with 0.3 THz zero-order Bessel beam to improve the depth of focus of this imaging system for the non-diffraction property of Bessel beam. The THz CT system has been used to detect a paper cup with a metal rod inside. Finally, the acquired projection data have been processed by the filtered back-projection algorithm and the reconstructed image of the sample has been obtained.

  20. High-Temperature Slow Crack Growth of Silicon Carbide Determined by Constant-Stress-Rate and Constant-Stress Testing

    NASA Technical Reports Server (NTRS)

    Choi, Sung H.; Salem, J. A.; Nemeth, N. N.

    1998-01-01

    High-temperature slow-crack-growth behaviour of hot-pressed silicon carbide was determined using both constant-stress-rate ("dynamic fatigue") and constant-stress ("static fatigue") testing in flexure at 1300 C in air. Slow crack growth was found to be a governing mechanism associated with failure of the material. Four estimation methods such as the individual data, the Weibull median, the arithmetic mean and the median deviation methods were used to determine the slow crack growth parameters. The four estimation methods were in good agreement for the constant-stress-rate testing with a small variation in the slow-crack-growth parameter, n, ranging from 28 to 36. By contrast, the variation in n between the four estimation methods was significant in the constant-stress testing with a somewhat wide range of n= 16 to 32.

  1. An Analytical Model for Two-Order Asperity Degradation of Rock Joints Under Constant Normal Stiffness Conditions

    NASA Astrophysics Data System (ADS)

    Li, Yingchun; Wu, Wei; Li, Bo

    2018-05-01

    Jointed rock masses during underground excavation are commonly located under the constant normal stiffness (CNS) condition. This paper presents an analytical formulation to predict the shear behaviour of rough rock joints under the CNS condition. The dilatancy and deterioration of two-order asperities are quantified by considering the variation of normal stress. We separately consider the dilation angles of waviness and unevenness, which decrease to zero as the normal stress approaches the transitional stress. The sinusoidal function naturally yields the decay of dilation angle as a function of relative normal stress. We assume that the magnitude of transitional stress is proportionate to the square root of asperity geometric area. The comparison between the analytical prediction and experimental data shows the reliability of the analytical model. All the parameters involved in the analytical model possess explicit physical meanings and are measurable from laboratory tests. The proposed model is potentially practicable for assessing the stability of underground structures at various field scales.

  2. 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.

  3. Perchlorate reduction by autotrophic bacteria in the presence of zero-valent iron.

    PubMed

    Yu, Xueyuan; Amrhein, Christopher; Deshusses, Marc A; Matsumoto, Mark R

    2006-02-15

    A series of batch experiments were performed to study the combination of zero-valent iron (ZVI) with perchlorate-reducing microorganisms (PRMs) to remove perchlorate from groundwater. In this method, H2 produced during the process of iron corrosion by water is used by PRMs as an electron donor to reduce perchlorate to chloride. Perchlorate degradation rates followed Monod kinetics, with a normalized maximum utilization rate (rmax) of 9200 microg g(-1) (dry wt) h(-1) and a half-velocity constant (Ks) of 8900 microg L(-1). The overall rate of perchlorate reduction was affected by the biomass density within the system. An increase in the OD600 from 0.025 to 0.08 led to a corresponding 4-fold increase of perchlorate reduction rate. PRM adaptation to the local environment and initiation of perchlorate reduction was rapid under neutral pH conditions. At the initial OD600 of 0.015, perchlorate reduction followed pseudo-first-order reaction rates with constants of 0.059 and 0.033 h(-1) at initial pH 7 and 8, respectively. Once perchlorate reduction was established, the bioreductive process was insensitive to the increases of pH from near neutral to 9.0. In the presence of nitrate, perchlorate reduction rate was reduced, but not inhibited completely.

  4. Zero-order release of aspirin, theophylline and atenolol in water from novel methylcellulose glutarate matrix tablets.

    PubMed

    Khairuzzaman, A; Ahmed, S U; Savva, M; Patel, N K

    2006-08-02

    A novel hydrocolloidal polymer, methylcellulose glutarate (MC-GA), was prepared by esterifying methylcellulose with glutaric anhydride. The formation of ester was confirmed by FTIR and NMR spectroscopy, DSC and elemental analysis. The physicochemical properties such as, rate of swelling in water, viscosity and hygroscopicity of MC-GA were determined and compared with those of methycellulose A (MC). Aspirin, theophylline and atenolol tablets were compacted on a Carver press using the wet granulation method. Each tablet contained: 200 mg active, 80 mg anhydrous lactose, 8 mg povidone, 4 mg magnesium stearate, 4 mg talc, 50mg MC or MC-GA (drug-to-polymer ratio, 4:1). Contrary to the first-order release profile of all the drugs from the MC matrix tablets, a zero-order release was obtained from the MC-GA matrix tablets in water.

  5. 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

  6. The rate constant of a quantum-diffusion-controlled bimolecular reaction

    NASA Astrophysics Data System (ADS)

    Bondarev, B. V.

    1986-04-01

    A quantum-mechanical equation is derived in the tight-bond approximation which describes the motion and chemical interaction of a pair of species A and B when their displacement in the matrix is caused by tunnelling. Within the framework of the discrete model of random walks, definitions are given of the probability and rate constant of a reaction A + B → P (products) proceeding in a condensed medium. A method is suggested for calculating the rate constant of a quantum-diffusion-controlled bimolecular reaction. By this method, an expression is obtained for the rate constant in the stationary spherically symmetrical case. An equation for the density matrix is also proposed which describes the motion and chemical interaction of a pair of species when the quantum and classical diffusion are competitive.

  7. Temperature and pressure dependence of the absolute rate constant for the reactions of NH2 radicals with acetylene and ethylene

    NASA Technical Reports Server (NTRS)

    Bosco, S. R.; Nava, D. F.; Brobst, W. D.; Stief, L. J.

    1984-01-01

    The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.

  8. Design for the optical retardation in broadband zero-order half-wave plates.

    PubMed

    Liu, Jin; Cai, Yi; Chen, Hongyi; Zeng, Xuanke; Zou, Da; Xu, Shixiang

    2011-04-25

    This paper presents a novel design for broadband zero-order half-wave plates to eliminate the first-order or up to second-order wavelength-dependent birefringent phase retardation (BPR) with 2 or 3 different birefringent materials. The residual BPRs of the plates increase monotonously with the wavelength deviation from a selected wavelength, so the plates are applicable to the broadband light pulses which gather most of the light energy around their central wavelengths. The model chooses the materials by the birefringent dispersion coefficient and evaluates the performances of the plates by the weighted average of the absolute value of residual BPR in order to emphasize the contributions of the incident spectral components whose possess higher energies.

  9. Validation of zero-order feedback strategies for medium range air-to-air interception in a horizontal plane

    NASA Technical Reports Server (NTRS)

    Shinar, J.

    1982-01-01

    A zero order feedback solution of a variable speed interception game between two aircraft in the horizontal plane, obtained by using the method of forced singular perturbation (FSP), is compared with the exact open loop solution. The comparison indicates that for initial distances of separation larger than eight turning radii of the evader, the accuracy of the feedback approximation is better than one percent. The result validates the zero order FSP approximation for medium range air combat analysis.

  10. Influences of brain tissue poroelastic constants on intracranial pressure (ICP) during constant-rate infusion.

    PubMed

    Li, Xiaogai; von Holst, Hans; Kleiven, Svein

    2013-01-01

    A 3D finite element (FE) model has been developed to study the mean intracranial pressure (ICP) response during constant-rate infusion using linear poroelasticity. Due to the uncertainties in the poroelastic constants for brain tissue, the influence of each of the main parameters on the transient ICP infusion curve was studied. As a prerequisite for transient analysis, steady-state simulations were performed first. The simulated steady-state pressure distribution in the brain tissue for a normal cerebrospinal fluid (CSF) circulation system showed good correlation with experiments from the literature. Furthermore, steady-state ICP closely followed the infusion experiments at different infusion rates. The verified steady-state models then served as a baseline for the subsequent transient models. For transient analysis, the simulated ICP shows a similar tendency to that found in the experiments, however, different values of the poroelastic constants have a significant effect on the infusion curve. The influence of the main poroelastic parameters including the Biot coefficient α, Skempton coefficient B, drained Young's modulus E, Poisson's ratio ν, permeability κ, CSF absorption conductance C(b) and external venous pressure p(b) was studied to investigate the influence on the pressure response. It was found that the value of the specific storage term S(ε) is the dominant factor that influences the infusion curve, and the drained Young's modulus E was identified as the dominant parameter second to S(ε). Based on the simulated infusion curves from the FE model, artificial neural network (ANN) was used to find an optimised parameter set that best fit the experimental curve. The infusion curves from both the FE simulation and using ANN confirmed the limitation of linear poroelasticity in modelling the transient constant-rate infusion.

  11. Newman-Penrose constants of the Kerr-Newman metric

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

    Gong Xuefei; Shang Yu; Bai Shan

    The Newman-Unti formalism of the Kerr-Newman metric near future null infinity is developed, with which the Newman-Penrose constants for both the gravitational and electromagnetic fields of the Kerr-Newman metric are computed and shown to be zero. The multipole structure near future null infinity in the sense of Janis-Newman of the Kerr-Newman metric is then further studied. It is found that up to the 2{sup 4}-pole, modulo a constant dependent upon the order of the pole, these multipole moments agree with those of Geroch-Hansen multipole moments defined at spatial infinity.

  12. 18 CFR 806.12 - Constant-rate aquifer testing.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... withdraw or increase a withdrawal of groundwater shall perform a constant-rate aquifer test in accordance... groundwater availability analysis to determine the availability of water during a 1-in-10-year recurrence...

  13. 18 CFR 806.12 - Constant-rate aquifer testing.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... withdraw or increase a withdrawal of groundwater shall perform a constant-rate aquifer test in accordance... groundwater availability analysis to determine the availability of water during a 1-in-10-year recurrence...

  14. 18 CFR 806.12 - Constant-rate aquifer testing.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... withdraw or increase a withdrawal of groundwater shall perform a constant-rate aquifer test in accordance... groundwater availability analysis to determine the availability of water during a 1-in-10-year recurrence...

  15. 18 CFR 806.12 - Constant-rate aquifer testing.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... withdraw or increase a withdrawal of groundwater shall perform a constant-rate aquifer test in accordance... groundwater availability analysis to determine the availability of water during a 1-in-10-year recurrence...

  16. Rate constant for the reaction of atomic chlorine with methane

    NASA Technical Reports Server (NTRS)

    Lin, C. L.; Leu, M. T.; Demore, W. B.

    1978-01-01

    The rate constant and temperature dependence of the Cl + CH4 reaction have been investigated by the techniques of competitive chlorination of CH4/C2H6 mixtures and by discharge-flow/mass spectroscopy. The objectives were to determine an accurate value for the rate constant for use in stratospheric modeling, and to clarify discrepancies in results previously obtained by different techniques. The results deduced from the competitive chlorination study are in good agreement with the absolute values measured by the mass spectrometric method, and at temperatures above 300 K are in good agreement with measurements by other techniques based on resonance fluorescence detection of atomic chlorine. However, in the 220-300 K region, the competitive experiments indicate lower rate constants than those obtained by resonance fluorescence methods, and do not reproduce the curved Arrhenius plots seen in some of those studies.

  17. Biodegradation testing of chemicals with high Henry's constants - Separating mass and effective concentration reveals higher rate constants.

    PubMed

    Birch, Heidi; Andersen, Henrik R; Comber, Mike; Mayer, Philipp

    2017-05-01

    During simulation-type biodegradation tests, volatile chemicals will continuously partition between water phase and headspace. This study addressed how (1) this partitioning affects test results and (2) can be accounted for by combining equilibrium partition and dynamic biodegradation models. An aqueous mixture of 9 (semi)volatile chemicals was first generated using passive dosing and then diluted with environmental surface water producing concentrations in the ng/L to μg/L range. After incubation for 2 h to 4 weeks, automated Headspace Solid Phase Microextraction (HS-SPME) was applied directly on the test systems to measure substrate depletion by biodegradation relatively to abiotic controls. HS-SPME was also applied to determine air to water partitioning ratios. Biodegradation rate constants relating to the chemical in the water phase, k water , were generally a factor 1 to 11 times higher than biodegradation rate constants relating to the total mass of chemical in the test system, k system , with one exceptional factor of 72 times for a long chain alkane. True water phase degradation rate constants were found (i) more appropriate for risk assessment than test system rate constants, (ii) to facilitate extrapolation to other air-water systems and (iii) to be better defined input parameters for aquatic exposure and fate models. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Rate constant for OH with selected large alkanes : shock-tube measurements and an improved group scheme.

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

    Sivaramakrishnan, R.; Michael, J. V.; Chemical Sciences and Engineering Division

    High-temperature rate constant experiments on OH with the five large (C{sub 5}-C{sub 8}) saturated hydrocarbons n-heptane, 2,2,3,3-tetramethylbutane (2,2,3,3-TMB), n-pentane, n-hexane, and 2,3-dimethylbutane (2,3-DMB) were performed with the reflected-shock-tube technique using multipass absorption spectrometric detection of OH radicals at 308 nm. Single-point determinations at {approx}1200 K on n-heptane, 2,2,3,3-TMB, n-hexane, and 2,3-DMB were previously reported by Cohen and co-workers; however, the present work substantially extends the database to both lower and higher temperature. The present experiments span a wide temperature range, 789-1308 K, and represent the first direct measurements of rate constants at T > 800 K for n-pentane. The presentmore » work utilized 48 optical passes corresponding to a total path length of {approx}4.2 m. As a result of this increased path length, the high OH concentration detection sensitivity permitted pseudo-first-order analyses for unambiguously measuring rate constants.« less

  19. ESTIMATION OF PHOSPHATE ESTER HYDROLYSIS RATE CONSTANTS - ALKALINE HYDROLYSIS

    EPA Science Inventory

    SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to allow the calculation of alkaline hydrolysis rate constants of phosphate esters in water. The rate is calculated from the energy difference between the initial and transition state...

  20. Zero-multipole summation method for efficiently estimating electrostatic interactions in molecular system.

    PubMed

    Fukuda, Ikuo

    2013-11-07

    The zero-multipole summation method has been developed to efficiently evaluate the electrostatic Coulombic interactions of a point charge system. This summation prevents the electrically non-neutral multipole states that may artificially be generated by a simple cutoff truncation, which often causes large amounts of energetic noise and significant artifacts. The resulting energy function is represented by a constant term plus a simple pairwise summation, using a damped or undamped Coulombic pair potential function along with a polynomial of the distance between each particle pair. Thus, the implementation is straightforward and enables facile applications to high-performance computations. Any higher-order multipole moment can be taken into account in the neutrality principle, and it only affects the degree and coefficients of the polynomial and the constant term. The lowest and second moments correspond respectively to the Wolf zero-charge scheme and the zero-dipole summation scheme, which was previously proposed. Relationships with other non-Ewald methods are discussed, to validate the current method in their contexts. Good numerical efficiencies were easily obtained in the evaluation of Madelung constants of sodium chloride and cesium chloride crystals.

  1. Physiological and Transcriptional Responses of Different Industrial Microbes at Near-Zero Specific Growth Rates.

    PubMed

    Ercan, Onur; Bisschops, Markus M M; Overkamp, Wout; Jørgensen, Thomas R; Ram, Arthur F; Smid, Eddy J; Pronk, Jack T; Kuipers, Oscar P; Daran-Lapujade, Pascale; Kleerebezem, Michiel

    2015-09-01

    The current knowledge of the physiology and gene expression of industrially relevant microorganisms is largely based on laboratory studies under conditions of rapid growth and high metabolic activity. However, in natural ecosystems and industrial processes, microbes frequently encounter severe calorie restriction. As a consequence, microbial growth rates in such settings can be extremely slow and even approach zero. Furthermore, uncoupling microbial growth from product formation, while cellular integrity and activity are maintained, offers perspectives that are economically highly interesting. Retentostat cultures have been employed to investigate microbial physiology at (near-)zero growth rates. This minireview compares information from recent physiological and gene expression studies on retentostat cultures of the industrially relevant microorganisms Lactobacillus plantarum, Lactococcus lactis, Bacillus subtilis, Saccharomyces cerevisiae, and Aspergillus niger. Shared responses of these organisms to (near-)zero growth rates include increased stress tolerance and a downregulation of genes involved in protein synthesis. Other adaptations, such as changes in morphology and (secondary) metabolite production, were species specific. This comparison underlines the industrial and scientific significance of further research on microbial (near-)zero growth physiology. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

  2. The gaseous explosive reaction at constant pressure : the reaction order and reaction rate

    NASA Technical Reports Server (NTRS)

    Stevens, F W

    1931-01-01

    The data given in this report covers the explosive limits of hydrocarbon fuels. Incidental to the purpose of the investigation here reported, the explosive limits will be found to be expressed for the condition of constant pressure, in the fundamental terms of concentrations (partial pressures) of fuel and oxygen.

  3. Estimating zero-g flow rates in open channels having capillary pumping vanes

    NASA Astrophysics Data System (ADS)

    Srinivasan, Radhakrishnan

    2003-02-01

    In vane-type surface tension propellant management devices (PMD) commonly used in satellite fuel tanks, the propellant is transported along guiding vanes from a reservoir at the inlet of the device to a sump at the outlet from where it is pumped to the satellite engine. The pressure gradient driving this free-surface flow under zero-gravity (zero-g) conditions is generated by surface tension and is related to the differential curvatures of the propellant-gas interface at the inlet and outlet of the PMD. A new semi-analytical procedure is prescribed for accurately calculating the extremely small fuel flow rates under reasonably idealized conditions. Convergence of the algorithm is demonstrated by detailed numerical calculations. Owing to the substantial cost and the technical hurdles involved in accurately estimating these minuscule flow rates by either direct numerical simulation or by experimental methods which simulate zero-g conditions in the lab, it is expected that the proposed method will be an indispensable tool in the design and operation of satellite fuel tanks.

  4. 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.

  5. 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.

  6. Zero-order release of poorly water-soluble drug from polymeric films made via aqueous slurry casting.

    PubMed

    Zhang, Lu; Alfano, Joy; Race, Doran; Davé, Rajesh N

    2018-05-30

    In spite of significant recent interest in polymeric films containing poorly water-soluble drugs, dissolution mechanism of thicker films has not been investigated. Consequently, release mechanisms of poorly water-soluble drugs from thicker hydroxypropyl methylcellulose (HPMC) films are investigated, including assessing thickness above which they exhibit zero-order drug release. Micronized, surface modified particles of griseofulvin, a model drug of BSC class II, were incorporated into aqueous slurry-cast films of different thicknesses (100, 500, 1000, 1500 and 2000 μm). Films 1000 μm and thicker were formed by either stacking two or more layers of ~500 μm, or forming a monolithic thick film. Compared to monolithic thick films, stacked films required simpler manufacturing process (easier casting, short drying time) and resulted in better critical quality attributes (appearance, uniformity of thickness and drug per unit area). Both the film forming approaches exhibited similar release profiles and followed the semi-empirical power law. As thickness increased from 100 μm to 2000 μm, the release mechanism changed from Fickian diffusion to zero-order release for films ≥1000 μm. The diffusional power law exponent, n, achieved value of 1, confirming zero-order release, whereas the percentage drug release varied linearly with sample surface area, and sample thickness due to fixed sample diameter. Thus, multi-layer hydrophilic polymer aqueous slurry-cast thick films containing poorly water-soluble drug particles provide a convenient dosage form capable of zero-order drug release with release time modulated through number of layers. Copyright © 2018 Elsevier B.V. All rights reserved.

  7. Absolute rate constants of alkoxyl radical reactions in aqueous solution. [Tert-butyl hydroperoxide

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

    Erben-Russ, M.; Michel, C.; Bors, W.

    1987-04-23

    The pulse radiolysis technique was used to generate the alkoxyl radical derived from tert-butyl hydroperoxide (/sup t/BuOOH) in aqueous solution. The reactions of this radical with 2,2'-azinobis(3-ethyl-6-benzothiazolinesulfonate) (ABTS) and promethazine were monitored by kinetic spectroscopy. The unimolecular decay rate constant of the tert-butoxyl radical (/sup t/BuO) was determined to be 1.4 x 10/sup 6/ s/sup -1/. On the basis of this value, the rate constants for /sup t/BuO attack on quercetin, crocin, crocetin, ascorbate, isoascorbate, trolox c, glutathione, thymidine, adenosine, guanosine, and unsaturated fatty acids were determined. In addition, the reaction of /sup t/BuO with the polyunsaturated fatty acids (PUFA)more » was observed by directly monitoring the formation of the fatty acid pentadienyl radicals. Interestingly, the attack of /sup t/BuO on PUFA was found to be faster by about one order of magnitude as compared to the same reaction in a nonpolar solvent.« less

  8. Exploring Fiscal Policy at Zero Interest Rates in Intermediate Macroeconomics

    ERIC Educational Resources Information Center

    Ramamurthy, Srikanth; Sedgley, Norman

    2013-01-01

    Since the financial meltdown of 2007, advanced macroeconomic theory has delved more deeply into the question of the appropriate fiscal policy when the nominal interest rate is close to or at zero percent. Such analysis is typically conducted with the aid of New Keynesian Dynamic Stochastic General Equilibrium models. The policy implications are,…

  9. ESTIMATION OF CARBOXYLIC ACID ESTER HYDROLYSIS RATE CONSTANTS

    EPA Science Inventory

    SPARC chemical reactivity models were extended to calculate hydrolysis rate constants for carboxylic acid esters from molecular structure. The energy differences between the initial state and the transition state for a molecule of interest are factored into internal and external...

  10. Recovering a full dimensional quantum rate constant from a reduced dimensionality calculation: Application to the OH+CO{r_arrow}H+CO{sub 2} reaction

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

    Dzegilenko, F.N.; Bowman, J.M.

    1996-08-01

    Two reduced dimensionality theories are used to calculate the thermal rate constant for the OH+CO{r_arrow}H+CO{sub 2} reaction. The standard theory employs energy-shift approximations to extract the full six degree-of-freedom quantum rate constant for this reaction from the previous two degree-of-freedom (2-DOF) quantum calculations of Hernandez and Clary [M.I. Hernandez and D.C. Clary, J. Chem. Phys. {bold 101}, 2779 (1994)]. Three extra bending modes and one extra {open_quote}{open_quote}spectator{close_quote}{close_quote} CO stretch mode are treated adiabatically in the harmonic fashion. The parameters of the exit channel transition state are used to evaluate the frequencies of those additional modes. A new reduced dimensionality theorymore » is also applied to this reaction. This theory explicitly addresses the finding from the 2-DOF calculations that the reaction proceeds mainly via complex formation. A J-shifting approximation has been used to take into account the initial states with non-zero values of total angular momentum in both reduced dimensionality theories. Cumulative reaction probabilities and thermal rate constants are calculated and compared with the previous quasiclassical and reduced dimensionality quantum calculations and with experiment. The rate constant from the new reduced dimensionality theory is between a factor of 5 and 100 times smaller than the statistical transition state theory result, and is in much better agreement with experiment. {copyright} {ital 1996 American Institute of Physics.}« less

  11. The contrasting roles of Planck's constant in classical and quantum theories

    NASA Astrophysics Data System (ADS)

    Boyer, Timothy H.

    2018-04-01

    We trace the historical appearance of Planck's constant in physics, and we note that initially the constant did not appear in connection with quanta. Furthermore, we emphasize that Planck's constant can appear in both classical and quantum theories. In both theories, Planck's constant sets the scale of atomic phenomena. However, the roles played in the foundations of the theories are sharply different. In quantum theory, Planck's constant is crucial to the structure of the theory. On the other hand, in classical electrodynamics, Planck's constant is optional, since it appears only as the scale factor for the (homogeneous) source-free contribution to the general solution of Maxwell's equations. Since classical electrodynamics can be solved while taking the homogenous source-free contribution in the solution as zero or non-zero, there are naturally two different theories of classical electrodynamics, one in which Planck's constant is taken as zero and one where it is taken as non-zero. The textbooks of classical electromagnetism present only the version in which Planck's constant is taken to vanish.

  12. Rate constants and temperature dependences for the reactions of hydroxyl radical with several halogenated methanes, ethanes, and propanes by relative rate measurements

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

    Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.

  13. Constant-Round Concurrent Zero Knowledge From Falsifiable Assumptions

    DTIC Science & Technology

    2013-01-01

    assumptions (e.g., [DS98, Dam00, CGGM00, Gol02, PTV12, GJO+12]), or in alternative models (e.g., super -polynomial-time simulation [Pas03b, PV10]). In the...T (·)-time computations, where T (·) is some “nice” (slightly) super -polynomial function (e.g., T (n) = nlog log logn). We refer to such proof...put a cap on both using a (slightly) super -polynomial function, and thus to guarantee soundness of the concurrent zero-knowledge protocol, we need

  14. Schwarzian derivative treatment of the quantum second-order supersymmetry anomaly, and coupling-constant metamorphosis

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

    Plyushchay, Mikhail S., E-mail: mikhail.plyushchay@usach.cl

    A canonical quantization scheme applied to a classical supersymmetric system with quadratic in momentum supercharges gives rise to a quantum anomaly problem described by a specific term to be quadratic in Planck constant. We reveal a close relationship between the anomaly and the Schwarzian derivative, and specify a quantization prescription which generates the anomaly-free supersymmetric quantum system with second order supercharges. We also discuss the phenomenon of a coupling-constant metamorphosis that associates quantum systems with the first-order supersymmetry to the systems with the second-order supercharges.

  15. A study on industrial accident rate forecasting and program development of estimated zero accident time in Korea.

    PubMed

    Kim, Tae-gu; Kang, Young-sig; Lee, Hyung-won

    2011-01-01

    To begin a zero accident campaign for industry, the first thing is to estimate the industrial accident rate and the zero accident time systematically. This paper considers the social and technical change of the business environment after beginning the zero accident campaign through quantitative time series analysis methods. These methods include sum of squared errors (SSE), regression analysis method (RAM), exponential smoothing method (ESM), double exponential smoothing method (DESM), auto-regressive integrated moving average (ARIMA) model, and the proposed analytic function method (AFM). The program is developed to estimate the accident rate, zero accident time and achievement probability of an efficient industrial environment. In this paper, MFC (Microsoft Foundation Class) software of Visual Studio 2008 was used to develop a zero accident program. The results of this paper will provide major information for industrial accident prevention and be an important part of stimulating the zero accident campaign within all industrial environments.

  16. Generation of a non-zero discord bipartite state with classical second-order interference.

    PubMed

    Choi, Yujun; Hong, Kang-Hee; Lim, Hyang-Tag; Yune, Jiwon; Kwon, Osung; Han, Sang-Wook; Oh, Kyunghwan; Kim, Yoon-Ho; Kim, Yong-Su; Moon, Sung

    2017-02-06

    We report an investigation on quantum discord in classical second-order interference. In particular, we theoretically show that a bipartite state with D = 0.311 of discord can be generated via classical second-order interference. We also experimentally verify the theory by obtaining D = 0.197 ± 0.060 of non-zero discord state. Together with the fact that the nonclassicalities originated from physical constraints and information theoretic perspectives are not equivalent, this result provides an insight to understand the nature of quantum discord.

  17. Unusual solvent effects on the fluorescence quenching rate constants of a thioxanthone derivative by n-butylamine and isoprene

    NASA Astrophysics Data System (ADS)

    Burget, D.; Jacques, P.

    1998-07-01

    The fluorescence quenching rate constants of a thioxanthone derivative by two electron donors ( n-butylamine and isoprene) were studied in eighteen solvents of different polarity. Both the empirical polarity parameter ET(30) and the more elaborate solvatochromic comparative method (SCM) π*, α, β (used without any precautions) failed to explain the relevant data. However, when in the frame of the SCM the sequential procedure is applied, unexpected solvent effects were revealed for hydroxylic solvents. These effects can be well accounted for by introducing a parameter χ for the whole set of solvents studied, equal to one or zero, depending on whether OH groups are involved or not in the quenching mechanism. A clue to the introduction of the parameter χ is presented.

  18. Near-zero thermal expansion in magnetically ordered state in dysprosium at high pressures and low temperatures

    NASA Astrophysics Data System (ADS)

    Hope, Kevin M.; Samudrala, Gopi K.; Vohra, Yogesh K.

    2017-01-01

    The atomic volume of rare earth metal dysprosium (Dy) has been measured up to high pressures of 35 GPa and low temperatures between 200 and 7 K in a diamond anvil cell using angle dispersive X-ray diffraction at a synchrotron source. The hexagonal close-packed (hcp), alpha-Samarium (α-Sm), and double hexagonal close-packed (dhcp) phases are observed to be stable in Dy under high-pressure and low-temperature conditions achieved in our experiments. Dy is known to undergo magnetic ordering below 176 K at ambient pressure with magnetic ordering Néel temperature (TN) that changes rapidly with increasing pressure. Our experimental measurement shows that Dy has near-zero thermal expansion in the magnetically ordered state and normal thermal expansion in the paramagnetic state for all the three known high pressure phases (hcp, α-Sm, and dhcp) to 35 GPa. This near-zero thermal expansion behavior in Dy is observed below the magnetic ordering temperature TN at all pressures up to 35 GPa.

  19. 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

  20. Theoretical Evaluation of the Transient Response of Constant Head and Constant Flow-Rate Permeability Tests

    USGS Publications Warehouse

    Zhang, M.; Takahashi, M.; Morin, R.H.; Esaki, T.

    1998-01-01

    A theoretical analysis is presented that compares the response characteristics of the constant head and the constant flowrate (flow pump) laboratory techniques for quantifying the hydraulic properties of geologic materials having permeabilities less than 10-10 m/s. Rigorous analytical solutions that describe the transient distributions of hydraulic gradient within a specimen are developed, and equations are derived for each method. Expressions simulating the inflow and outflow rates across the specimen boundaries during a constant-head permeability test are also presented. These solutions illustrate the advantages and disadvantages of each method, including insights into measurement accuracy and the validity of using Darcy's law under certain conditions. The resulting observations offer practical considerations in the selection of an appropriate laboratory test method for the reliable measurement of permeability in low-permeability geologic materials.

  1. a Zero-Order Picture of the Infrared Spectrum for the Methoxy Radical: Assignment of States

    NASA Astrophysics Data System (ADS)

    Johnson, Britta; Sibert, Edwin

    2016-06-01

    The ground tilde{X}^2E vibrations of the methoxy radical have intrigued both experimentalists and theorists alike due to the presence of a conical intersection at the C3v molecular geometry. This conical intersection causes methoxy's vibrational spectrum to be strongly influenced by Jahn-Teller vibronic coupling which leads to large amplitude vibrations and extensive mixing of the two lowest electronic states. This coupling combined with spin-orbit and Fermi couplings greatly complicates the assignments of states. Using the potential force field and calculated spectra of Nagesh and Sibert1,2, we assign quantum numbers to the infrared spectrum. When the zero-order states are the diabatic normal mode states, there is sufficient mode mixing that the normal mode quantum numbers are poor labels for the final states. We define a series of zero-order Hamiltonians which include additional coupling elements beyond the normal mode picture but still allow for the assignment of Jahn-Teller quantum numbers. In methoxy, the two lowest frequency e} modes, the bend (q_5) and the rock (q_6), are the modes with the strongest Jahn-Teller coupling. In general, a zero-order Hamiltonian which includes first-order Jahn-Teller coupling in q_6 is sufficient for most states of interest. Working in a representation which includes first-order Jahn-Teller coupling in q_6, we identify states in which additional coupling elements must be included; these couplings include first-order Jahn-Teller coupling in q_5, higher order Jahn-Teller coupling in q_5 and q_6, and, in the dueterated case, Jahn-Teller coupling which is modulated by the corresponding a modes. [^1] Nagesh, J.; Sibert, E. L. J. Phys. Chem. A 2012, 116, 3846-3855. Lee, Y.F.; Chou, W.T.; Johnson, B.A.; Tabor, D.P. ; Sibert, E.L.; Lee, Y.P. J. Mol. Spectrosc. 2015, 310, 57-67. Barckholtz, T. A.; Miller, T. A. Int. Revs. in Phys. Chem. 1998, 17, 435-524.

  2. Temporal framing and the hidden-zero effect: rate-dependent outcomes on delay discounting.

    PubMed

    Naudé, Gideon P; Kaplan, Brent A; Reed, Derek D; Henley, Amy J; DiGennaro Reed, Florence D

    2018-05-01

    Recent research suggests that presenting time intervals as units (e.g., days) or as specific dates, can modulate the degree to which humans discount delayed outcomes. Another framing effect involves explicitly stating that choosing a smaller-sooner reward is mutually exclusive to receiving a larger-later reward, thus presenting choices as an extended sequence. In Experiment 1, participants (N = 201) recruited from Amazon Mechanical Turk completed the Monetary Choice Questionnaire in a 2 (delay framing) by 2 (zero framing) design. Regression suggested a main effect of delay, but not zero, framing after accounting for other demographic variables and manipulations. We observed a rate-dependent effect for the date-framing group, such that those with initially steep discounting exhibited greater sensitivity to the manipulation than those with initially shallow discounting. Subsequent analyses suggest these effects cannot be explained by regression to the mean. Experiment 2 addressed the possibility that the null effect of zero framing was due to within-subject exposure to the hidden- and explicit-zero conditions. A new Amazon Mechanical Turk sample completed the Monetary Choice Questionnaire in either hidden- or explicit-zero formats. Analyses revealed a main effect of reward magnitude, but not zero framing, suggesting potential limitations to the generality of the hidden-zero effect. © 2018 Society for the Experimental Analysis of Behavior.

  3. Kinetics of Fe2+-Mg order-disorder in orthopyroxene: experimental studies and applications to cooling rates of rocks

    NASA Astrophysics Data System (ADS)

    Stimpfl, M.; Ganguly, J.; Molin, G.

    2005-10-01

    We determined the forward rate constant (K+) for the Fe2+-Mg order-disorder between the M2 and M1 sites of orthopyroxene (OPx), which is described by the homogeneous reaction Fe2+ (M2) + Mg(M1) ↔ Mg(M2) + Fe2+ (M1), by both ordering and disordering experiments at isothermal condition and also by continuous cooling experiments. The rate constant was determined as a function of temperature in the range of 550-750°C, oxygen fugacity between quartz-fayalite-iron and Ni-NiO buffers, and at compositions of 16 and 50 mol% ferrosilite component. The K+ value derived from disordering experiment was found to be larger than that derived from ordering experiment at 550°C, while at T>580°C, these two values are essentially the same. The fO2 dependence of the rate constant can be described by the relation K+ α (fO2) n with n=5.5-6.5, which is compatible with the theoretically expected relation. The Arrhenius relation at the WI buffer condition is given by ln (C_{text{o}} {text{K}}^+) = - {41511 - 12600{text{X}}_{{text{Fe}}} }/{{T({text{K}})}} + 28.26 + 5.27{text{X}}_{{text{Fe}}}, min^{-1} where C o represents the total number of M2 + M1 sites occupied by Fe2+ and Mg per unit volume of the crystal. The above relation can be used to calculate the cooling rates of natural OPx crystals around the closure temperature ( T c) of Fe-Mg ordering, which are usually below 300°C for slowly cooled rocks. We determined the Fe-Mg ordering states of several OPx crystals (˜ Fs50) from the Central Gneissic Complex (Khtada Lake), British Columbia, which yields T c ˜290°C. Numerical simulation of the change of Fe2+-Mg ordering in OPx as a function of temperature using the above expression of rate constant and a non-linear cooling model yields quenched values of ordering states that are in agreement with the observed values for cooling rates of 11-17°C/Myr below 300°C. The inferred cooling rate is in agreement with the available geochronological constraints.

  4. Bound state potential energy surface construction: ab initio zero-point energies and vibrationally averaged rotational constants.

    PubMed

    Bettens, Ryan P A

    2003-01-15

    Collins' method of interpolating a potential energy surface (PES) from quantum chemical calculations for reactive systems (Jordan, M. J. T.; Thompson, K. C.; Collins, M. A. J. Chem. Phys. 1995, 102, 5647. Thompson, K. C.; Jordan, M. J. T.; Collins, M. A. J. Chem. Phys. 1998, 108, 8302. Bettens, R. P. A.; Collins, M. A. J. Chem. Phys. 1999, 111, 816) has been applied to a bound state problem. The interpolation method has been combined for the first time with quantum diffusion Monte Carlo calculations to obtain an accurate ground state zero-point energy, the vibrationally average rotational constants, and the vibrationally averaged internal coordinates. In particular, the system studied was fluoromethane using a composite method approximating the QCISD(T)/6-311++G(2df,2p) level of theory. The approach adopted in this work (a) is fully automated, (b) is fully ab initio, (c) includes all nine nuclear degrees of freedom, (d) requires no assumption of the functional form of the PES, (e) possesses the full symmetry of the system, (f) does not involve fitting any parameters of any kind, and (g) is generally applicable to any system amenable to quantum chemical calculations and Collins' interpolation method. The calculated zero-point energy agrees to within 0.2% of its current best estimate. A0 and B0 are within 0.9 and 0.3%, respectively, of experiment.

  5. 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.

  6. 18 CFR 806.12 - Constant-rate aquifer testing.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... groundwater availability analysis to determine the availability of water during a 1-in-10-year recurrence... 18 Conservation of Power and Water Resources 2 2010-04-01 2010-04-01 false Constant-rate aquifer testing. 806.12 Section 806.12 Conservation of Power and Water Resources SUSQUEHANNA RIVER BASIN...

  7. Kinetics of zero-valent iron reductive transformation of the anthraquinone dye Reactive Blue 4.

    PubMed

    Epolito, William J; Yang, Hanbae; Bottomley, Lawrence A; Pavlostathis, Spyros G

    2008-12-30

    The effect of operational conditions and initial dye concentration on the reductive transformation (decolorization) of the textile dye Reactive Blue 4 (RB4) using zero-valent iron (ZVI) filings was evaluated in batch assays. The decolorization rate increased with decreasing pH and increasing temperature, mixing intensity, and addition of salt (100gL(-1) NaCl) and base (3gL(-1) Na2CO3 and 1gL(-1) NaOH), conditions typical of textile reactive dyebaths. ZVI RB4 decolorization kinetics at a single initial dye concentration were evaluated using a pseudo first-order model. Under dyebath conditions and at an initial RB4 concentration of 1000mgL(-1), the pseudo first-order rate constant (kobs) was 0.029+/-0.006h(-1), corresponding to a half-life of 24.2h and a ZVI surface area-normalized rate constant (kSA) of 2.9x10(-4)Lm(-2)h(-1). However, as the initial dye concentration increased, the kobs decreased, suggesting saturation of ZVI surface reactive sites. Non-linear regression of initial decolorization rate values as a function of initial dye concentration, based on a reactive sites saturation model, resulted in a maximum decolorization rate (Vm) of 720+/-88mgL(-1)h(-1) and a half-saturation constant (K) of 1299+/-273mgL(-1). Decolorization of RB4 via a reductive transformation, which was essentially irreversible (2-5% re-oxidation), is believed to be the dominant decolorization mechanism. However, some degree of RB4 irreversible sorption cannot be completely discounted. The results of this study show that ZVI treatment is a promising technology for the decolorization of commercial, anthraquinone-bearing, spent reactive dyebaths.

  8. ESTIMATION OF PHOSPHATE ESTER HYDROLYSIS RATE CONSTANTS. I. ALKALINE HYDROLYSIS

    EPA Science Inventory

    SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to allow the calculation of alkaline hydrolysis rate constants of phosphate esters in water. The rate is calculated from the energy difference between the initial and transition state...

  9. 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.

  10. 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

  11. Lower Current Large Deviations for Zero-Range Processes on a Ring

    NASA Astrophysics Data System (ADS)

    Chleboun, Paul; Grosskinsky, Stefan; Pizzoferrato, Andrea

    2017-04-01

    We study lower large deviations for the current of totally asymmetric zero-range processes on a ring with concave current-density relation. We use an approach by Jensen and Varadhan which has previously been applied to exclusion processes, to realize current fluctuations by travelling wave density profiles corresponding to non-entropic weak solutions of the hyperbolic scaling limit of the process. We further establish a dynamic transition, where large deviations of the current below a certain value are no longer typically attained by non-entropic weak solutions, but by condensed profiles, where a non-zero fraction of all the particles accumulates on a single fixed lattice site. This leads to a general characterization of the rate function, which is illustrated by providing detailed results for four generic examples of jump rates, including constant rates, decreasing rates, unbounded sublinear rates and asymptotically linear rates. Our results on the dynamic transition are supported by numerical simulations using a cloning algorithm.

  12. End of Life Disposal for Three Libration Point Missions through Manipulation of the Jacobi Constant and Zero Velocity Curves

    NASA Technical Reports Server (NTRS)

    Peterson, Jeremy D.; Brown, Jonathan M.

    2015-01-01

    The aim of this investigation is to determine the feasibility of mission disposal by inserting the spacecraft into a heliocentric orbit along the unstable manifold and then manipulating the Jacobi constant to prevent the spacecraft from returning to the Earth-Moon system. This investigation focuses around L1 orbits representative of ACE, WIND, and SOHO. It will model the impulsive delta-V necessary to close the zero velocity curves after escape through the L1 gateway in the circular restricted three body model and also include full ephemeris force models and higher fidelity finite maneuver models for the three spacecraft.

  13. Estimating reaction rate coefficients within a travel-time modeling framework.

    PubMed

    Gong, R; Lu, C; Wu, W-M; Cheng, H; Gu, B; Watson, D; Jardine, P M; Brooks, S C; Criddle, C S; Kitanidis, P K; Luo, J

    2011-01-01

    A generalized, efficient, and practical approach based on the travel-time modeling framework is developed to estimate in situ reaction rate coefficients for groundwater remediation in heterogeneous aquifers. The required information for this approach can be obtained by conducting tracer tests with injection of a mixture of conservative and reactive tracers and measurements of both breakthrough curves (BTCs). The conservative BTC is used to infer the travel-time distribution from the injection point to the observation point. For advection-dominant reactive transport with well-mixed reactive species and a constant travel-time distribution, the reactive BTC is obtained by integrating the solutions to advective-reactive transport over the entire travel-time distribution, and then is used in optimization to determine the in situ reaction rate coefficients. By directly working on the conservative and reactive BTCs, this approach avoids costly aquifer characterization and improves the estimation for transport in heterogeneous aquifers which may not be sufficiently described by traditional mechanistic transport models with constant transport parameters. Simplified schemes are proposed for reactive transport with zero-, first-, nth-order, and Michaelis-Menten reactions. The proposed approach is validated by a reactive transport case in a two-dimensional synthetic heterogeneous aquifer and a field-scale bioremediation experiment conducted at Oak Ridge, Tennessee. The field application indicates that ethanol degradation for U(VI)-bioremediation is better approximated by zero-order reaction kinetics than first-order reaction kinetics. Copyright © 2010 The Author(s). Journal compilation © 2010 National Ground Water Association.

  14. Estimating Reaction Rate Coefficients Within a Travel-Time Modeling Framework

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

    Gong, R; Lu, C; Luo, Jian

    A generalized, efficient, and practical approach based on the travel-time modeling framework is developed to estimate in situ reaction rate coefficients for groundwater remediation in heterogeneous aquifers. The required information for this approach can be obtained by conducting tracer tests with injection of a mixture of conservative and reactive tracers and measurements of both breakthrough curves (BTCs). The conservative BTC is used to infer the travel-time distribution from the injection point to the observation point. For advection-dominant reactive transport with well-mixed reactive species and a constant travel-time distribution, the reactive BTC is obtained by integrating the solutions to advective-reactive transportmore » over the entire travel-time distribution, and then is used in optimization to determine the in situ reaction rate coefficients. By directly working on the conservative and reactive BTCs, this approach avoids costly aquifer characterization and improves the estimation for transport in heterogeneous aquifers which may not be sufficiently described by traditional mechanistic transport models with constant transport parameters. Simplified schemes are proposed for reactive transport with zero-, first-, nth-order, and Michaelis-Menten reactions. The proposed approach is validated by a reactive transport case in a two-dimensional synthetic heterogeneous aquifer and a field-scale bioremediation experiment conducted at Oak Ridge, Tennessee. The field application indicates that ethanol degradation for U(VI)-bioremediation is better approximated by zero-order reaction kinetics than first-order reaction kinetics.« less

  15. EFFECTS OF PH ON DECHLORINATION OF TRICHLOROETHYLENE BY ZERO-VALENT IRON

    EPA Science Inventory

    The surface normalized reaction rate constants (ksa) of trichloroethylene (TCE) and zero-valent iron (ZVI) was quantified in batch reactors at pH values between 1.7 and 10. The ksa of TCE linearly decreased from 0.044 to 0.009 L/hr-m2 between pH 3.8 and 8.0, whereas the ksa at pH...

  16. Near-zero thermal expansion in magnetically ordered state in dysprosium at high pressures and low temperatures

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

    Hope, Kevin M.; Samudrala, Gopi K.; Vohra, Yogesh K.

    The atomic volume of rare earth metal Dysprosium (Dy) has been measured up to high pressures of 35 GPa and low temperatures between 200 K and 7 K in a diamond anvil cell using angle dispersive x-ray diffraction at a synchrotron source. The hexagonal close-packed (hcp), alpha-Samarium (α-Sm), and double hexagonal close packed (dhcp) phases are observed to be stable in Dy under high-pressure and low-temperature conditions achieved in our experiments. Dy is known to undergo magnetic ordering below 176 K at ambient pressure with magnetic ordering Néel temperature (T N) that changes rapidly with increasing pressure. Our experimental measurementmore » shows that Dy has near-zero thermal expansion in the magnetically ordered state and normal thermal expansion in the paramagnetic state for all the three known high pressure phases (hcp, α-Sm, and dhcp) to 35 GPa. This near-zero thermal expansion behavior in Dy is observed below the magnetic ordering temperature T N at all pressures up to 35 GPa.« less

  17. Near-zero thermal expansion in magnetically ordered state in dysprosium at high pressures and low temperatures

    DOE PAGES

    Hope, Kevin M.; Samudrala, Gopi K.; Vohra, Yogesh K.

    2017-01-01

    The atomic volume of rare earth metal Dysprosium (Dy) has been measured up to high pressures of 35 GPa and low temperatures between 200 K and 7 K in a diamond anvil cell using angle dispersive x-ray diffraction at a synchrotron source. The hexagonal close-packed (hcp), alpha-Samarium (α-Sm), and double hexagonal close packed (dhcp) phases are observed to be stable in Dy under high-pressure and low-temperature conditions achieved in our experiments. Dy is known to undergo magnetic ordering below 176 K at ambient pressure with magnetic ordering Néel temperature (T N) that changes rapidly with increasing pressure. Our experimental measurementmore » shows that Dy has near-zero thermal expansion in the magnetically ordered state and normal thermal expansion in the paramagnetic state for all the three known high pressure phases (hcp, α-Sm, and dhcp) to 35 GPa. This near-zero thermal expansion behavior in Dy is observed below the magnetic ordering temperature T N at all pressures up to 35 GPa.« less

  18. Pseudo-extravasation rate constant of dynamic susceptibility contrast-MRI determined from pharmacokinetic first principles.

    PubMed

    Li, Xin; Varallyay, Csanad G; Gahramanov, Seymur; Fu, Rongwei; Rooney, William D; Neuwelt, Edward A

    2017-11-01

    Dynamic susceptibility contrast-magnetic resonance imaging (DSC-MRI) is widely used to obtain informative perfusion imaging biomarkers, such as the relative cerebral blood volume (rCBV). The related post-processing software packages for DSC-MRI are available from major MRI instrument manufacturers and third-party vendors. One unique aspect of DSC-MRI with low-molecular-weight gadolinium (Gd)-based contrast reagent (CR) is that CR molecules leak into the interstitium space and therefore confound the DSC signal detected. Several approaches to correct this leakage effect have been proposed throughout the years. Amongst the most popular is the Boxerman-Schmainda-Weisskoff (BSW) K 2 leakage correction approach, in which the K 2 pseudo-first-order rate constant quantifies the leakage. In this work, we propose a new method for the BSW leakage correction approach. Based on the pharmacokinetic interpretation of the data, the commonly adopted R 2 * expression accounting for contributions from both intravascular and extravasating CR components is transformed using a method mathematically similar to Gjedde-Patlak linearization. Then, the leakage rate constant (K L ) can be determined as the slope of the linear portion of a plot of the transformed data. Using the DSC data of high-molecular-weight (~750 kDa), iron-based, intravascular Ferumoxytol (FeO), the pharmacokinetic interpretation of the new paradigm is empirically validated. The primary objective of this work is to empirically demonstrate that a linear portion often exists in the graph of the transformed data. This linear portion provides a clear definition of the Gd CR pseudo-leakage rate constant, which equals the slope derived from the linear segment. A secondary objective is to demonstrate that transformed points from the initial transient period during the CR wash-in often deviate from the linear trend of the linearized graph. The inclusion of these points will have a negative impact on the accuracy of the leakage

  19. Zero-profile Anchored Spacer Reduces Rate of Dysphagia Compared With ACDF With Anterior Plating.

    PubMed

    Hofstetter, Christoph P; Kesavabhotla, Kartik; Boockvar, John A

    2015-06-01

    Retrospective cohort study. To study clinical and radiologic outcomes after anterior cervical discectomy and fusion (ACDF) using a zero-profile anchored spacer compared with a standard interposition graft with anterior plating. Anterior plating increases fusion rates in ACDF but is associated with higher rates of postoperative dysphagia. Reduction of plate thickness or zero-profile fixation of the interposition graft have been suggested to decrease the incidence of postoperative dysphagia. Retrospective cohort study of 70 consecutive patients of whom the first 35 patients underwent ACDF with anterior plating and the remaining patients received an LDR device. Patient demographics, operative details, neurological impairment, complications, and radiographic imaging were reviewed. Dysphagia occurring in the immediate postoperative period and lasting for >3 months was recorded. Both the zero-profile anchored spacer and a standard interposition graft with anterior plating resulted in improvement of neurological outcome at a mean follow-up time of 13.9 months. Fusion rates were found to be similar between ACDF with anterior plating (96.0%) and LDR (95.2%). Evaluation of postoperative radiographs revealed significantly more swelling of the prevertebral space (20.4±0.9 mm) after implantation of an anterior locking plate compared with a zero-profile device (15.6±0.7 mm, P<0.001). This difference remained significant at 6-month follow-up (P=0.035). Seven patients (20%) with ACDF and plating complained about swallowing difficulties beyond 3 months compared with only 1 patient with the LDR device (P=0.027). The severity of dysphagia was mild in all but 2 patients. Both patients with moderate and severe swallowing difficulties had undergone ACDF with anterior plating. Zero-profile anchored spacers lead to similar clinical and radiographic outcomes compared with ACDF with plating and may carry a lower risk of postoperative dysphagia.

  20. 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.

  1. Determination of the strong coupling constant from jet rates in deep inelastic scattering

    NASA Astrophysics Data System (ADS)

    Ahmed, T.; Aid, S.; Andreev, V.; Andrieu, B.; Appuhn, R.-D.; Arpagaus, M.; Babaev, A.; Baehr, J.; Bán, J.; Baranov, P.; Barrelet, E.; Bartel, W.; Barth, M.; Bassler, U.; Beck, H. P.; Behrend, H.-J.; Belousov, A.; Berger, Ch.; Bergstein, H.; Bernardi, G.; Bernet, R.; Bertrand-Coremans, G.; Besançon, M.; Beyer, R.; Biddulph, P.; Bizot, J. C.; Blobel, V.; Borras, K.; Botterweck, F.; Boudry, V.; Braemer, A.; Brasse, F.; Braunschweig, W.; Brisson, V.; Bruncko, D.; Brune, C.; Buchholz, R.; Büngener, L.; Bürger, J.; Büsser, F. W.; Buniatian, A.; Burke, S.; Buschhorn, G.; Campbell, A. J.; Carli, T.; Charles, F.; Clarke, D.; Clegg, A. B.; Clerbaux, B.; Colombo, M.; Contreras, J. G.; Cormack, C.; Coughlan, J. A.; Courau, A.; Coutures, Ch.; Cozzika, G.; Criegee, L.; Cussans, D. G.; Cvach, J.; Dagoret, S.; Dainton, J. B.; Danilov, M.; Dau, W. D.; Daum, K.; David, M.; Deffur, E.; Delcourt, B.; Del Buono, L.; De Roeck, A.; De Wolf, E. A.; Di Nezza, P.; Dollfus, C.; Dowell, J. D.; Dreis, H. B.; Droutskoi, A.; Duboc, J.; Düllmann, D.; Dünger, O.; Duhm, H.; Ebert, J.; Ebert, T. R.; Eckerlin, G.; Efremenko, V.; Egli, S.; Ehrlichmann, H.; Eichenberger, S.; Eichler, R.; Eisele, F.; Eisenhandler, E.; Ellison, R. J.; Elsen, E.; Erdmann, M.; Erdmann, W.; Evrard, E.; Favart, L.; Fedotov, A.; Feeken, D.; Felst, R.; Feltesse, J.; Ferencei, J.; Ferrarotto, F.; Flamm, K.; Fleischer, M.; Flieser, M.; Flügge, G.; Fomenko, A.; Fominykh, B.; Forbush, M.; Formánek, J.; Foster, J. M.; Franke, G.; Fretwurst, E.; Gabathuler, E.; Gabathuler, K.; Gamerdinger, K.; Garvey, J.; Gayler, J.; Gebauer, M.; Gellrich, A.; Genzel, H.; Gerhards, R.; Goerlach, U.; Goerlich, L.; Gogitidze, N.; Goldberg, M.; Goldner, D.; Gonzalez-Pineiro, B.; Gorelov, I.; Goritchev, P.; Grab, C.; Grässler, H.; Grässler, R.; Greenshaw, T.; Grindhammer, G.; Gruber, A.; Gruber, C.; Haack, J.; Haidt, D.; Hajduk, L.; Hamon, O.; Hampel, M.; Hanlon, E. M.; Hapke, M.; Haynes, W. J.; Heatherington, J.; Heinzelmann, G.; Henderson, R. C. W.; Henschel, H.; Herma, R.; Herynek, I.; Hess, M. F.; Hildesheim, W.; Hill, P.; Hill, K. H.; Hilton, C. D.; Hladký, J.; Hoeger, K. C.; Höppner, M.; Horisberger, R.; Huet, Ph.; Hufnagel, H.; Ibbotson, M.; Itterbeck, H.; Jabiol, M.-A.; Jacholkowska, A.; Jacobsson, C.; Jaffre, M.; Janoth, J.; Jansen, T.; Jönsson, L.; Johannsen, K.; Johnson, D. P.; Johnson, L.; Jung, H.; Kalmus, P. I. P.; Kant, D.; Kaschowitz, R.; Kasselmann, P.; Kathage, U.; Kaufmann, H. H.; Kazarian, S.; Kenyon, I. R.; Kermiche, S.; Keuler, C.; Kiesling, C.; Klein, M.; Kleinwort, C.; Knies, G.; Ko, W.; Köhler, T.; Köhne, J. H.; Kolanoski, H.; Kole, F.; Kolya, S. D.; Korbel, V.; Korn, M.; Kostka, P.; Kotelnikov, S. K.; Krämerkämper, T.; Krasny, M. W.; Krehbiel, H.; Krücker, D.; Krüger, U.; Krüner-Marquis, U.; Kubenka, J. P.; Küster, H.; Kuhlen, M.; Kurča, T.; Kurzhöfer, J.; Kuznik, B.; Lacour, D.; Lamarche, F.; Lander, R.; Landon, M. P. J.; Lange, W.; Lanius, P.; Laporte, J.-F.; Lebedev, A.; Leverenz, C.; Levonian, S.; Ley, Ch.; Lindner, A.; Lindström, G.; Linsel, F.; Lipinski, J.; List, B.; Loch, P.; Lohmander, H.; Lopez, G. C.; Lubimov, V.; Lüke, D.; Magnussen, N.; Malinovski, E.; Mani, S.; Maraček, R.; Marage, P.; Marks, J.; Marshall, R.; Martens, J.; Martin, R.; Martyn, H.-U.; Martyniak, J.; Masson, S.; Mavroidis, T.; Maxfield, S. J.; McMahon, S. J.; Mehta, A.; Meier, K.; Mercer, D.; Merz, T.; Meyer, C. A.; Meyer, H.; Meyer, J.; Mikocki, S.; Milstead, D.; Moreau, F.; Morris, J. V.; Müller, G.; Müller, K.; Murín, P.; Nagovizin, V.; Nahnhauer, R.; Naroska, B.; Naumann, Th.; Newman, P. R.; Newton, D.; Neyret, D.; Nguyen, H. K.; Niebergall, F.; Niebuhr, C.; Nisius, R.; Nowak, G.; Noyes, G. W.; Nyberg-Werther, M.; Oakden, M.; Oberlack, H.; Obrock, U.; Olsson, J. E.; Panaro, E.; Panitch, A.; Pascaud, C.; Patel, G. D.; Peppel, E.; Perez, E.; Phillips, J. P.; Pichler, Ch.; Pitzl, D.; Pope, G.; Prell, S.; Prosi, R.; Rädel, G.; Raupach, F.; Reimer, P.; Reinshagen, S.; Ribarics, P.; Rick, H.; Riech, V.; Riedlberger, J.; Riess, S.; Rietz, M.; Robertson, S. M.; Robmann, P.; Roloff, H. E.; Roosen, R.; Rosenbauer, K.; Rostovtsev, A.; Rouse, F.; Royon, C.; Rüter, K.; Rusakov, S.; Rybicki, K.; Rylko, R.; Sahlmann, N.; Sanchez, E.; Sankey, D. P. C.; Savitsky, M.; Schacht, P.; Schiek, S.; Schleper, P.; von Schlippe, W.; Schmidt, C.; Schmidt, D.; Schmidt, G.; Schöning, A.; Schröder, V.; Schuhmann, E.; Schwab, B.; Schwind, A.; Seehausen, U.; Sefkow, F.; Seidel, M.; Sell, R.; Semenov, A.; Shekelyan, V.; Sheviakov, I.; Shooshtari, H.; Shtarkov, L. N.; Siegmon, G.; Siewert, U.; Sirois, Y.; Skillicorn, I. O.; Smirnov, P.; Smith, J. R.; Soloviev, Y.; Spitzer, H.; Starosta, R.; Steenbock, M.; Steffen, P.; Steinberg, R.; Stella, B.; Stephens, K.; Stier, J.; Stiewe, J.; Stösslein, U.; Strachota, J.; Straumann, U.; Struczinski, W.; Sutton, J. P.; Tapprogge, S.; Taylor, R. E.; Tchernyshov, V.; Thiebaux, C.; Thompson, G.; Truöl, P.; Turnau, J.; Tutas, J.; Uelkes, P.; Usik, A.; Valkár, S.; Valkárová, A.; Vallée, C.; Van Esch, P.; Van Mechelen, P.; Vartapetian, A.; Vazdik, Y.; Vecko, M.; Verrecchia, P.; Villet, G.; Wacker, K.; Wagener, A.; Wagener, M.; Walker, I. W.; Walther, A.; Weber, G.; Weber, M.; Wegener, D.; Wegner, A.; Wellisch, H. P.; West, L. R.; Willard, S.; Winde, M.; Winter, G.-G.; Wright, A. E.; Wünsch, E.; Wulff, N.; Yiou, T. P.; Žáček, J.; Zarbock, D.; Zhang, Z.; Zhokin, A.; Zimmer, M.; Zimmermann, W.; Zomer, F.; Zuber, K.; H1 Collaboration

    1995-02-01

    Jet rates in deep inelastic electron proton scattering are studied with the H1 detector at HERA for momentum transfers squared between 10 and 4000 GeV 2. It is shown that they can be quantitatively described by perturbative QCD in next to leading order making use of the parton densities of the proton and with the strong coupling constant αs as a free parameter. The measured value, αs( MZ2) = 0.123 ± 0.018, is in agreement both with determinations from e+e- annihilation at LEP using the same observable and with the world average.

  2. Virtual Instrument for Determining Rate Constant of Second-Order Reaction by pX Based on LabVIEW 8.0

    PubMed Central

    Meng, Hu; Li, Jiang-Yuan; Tang, Yong-Huai

    2009-01-01

    The virtual instrument system based on LabVIEW 8.0 for ion analyzer which can measure and analyze ion concentrations in solution is developed and comprises homemade conditioning circuit, data acquiring board, and computer. It can calibrate slope, temperature, and positioning automatically. When applied to determine the reaction rate constant by pX, it achieved live acquiring, real-time displaying, automatical processing of testing data, generating the report of results; and other functions. This method simplifies the experimental operation greatly, avoids complicated procedures of manual processing data and personal error, and improves veracity and repeatability of the experiment results. PMID:19730752

  3. Virtual Instrument for Determining Rate Constant of Second-Order Reaction by pX Based on LabVIEW 8.0.

    PubMed

    Meng, Hu; Li, Jiang-Yuan; Tang, Yong-Huai

    2009-01-01

    The virtual instrument system based on LabVIEW 8.0 for ion analyzer which can measure and analyze ion concentrations in solution is developed and comprises homemade conditioning circuit, data acquiring board, and computer. It can calibrate slope, temperature, and positioning automatically. When applied to determine the reaction rate constant by pX, it achieved live acquiring, real-time displaying, automatical processing of testing data, generating the report of results; and other functions. This method simplifies the experimental operation greatly, avoids complicated procedures of manual processing data and personal error, and improves veracity and repeatability of the experiment results.

  4. Qutrit witness from the Grothendieck constant of order four

    NASA Astrophysics Data System (ADS)

    Diviánszky, Péter; Bene, Erika; Vértesi, Tamás

    2017-07-01

    In this paper, we prove that KG(3 ) constant of order d . To this end, we use a branch-and-bound algorithm commonly used in the solution of NP-hard problems. It has recently been proven that KG(3 ) ≤1.4644 . Here we prove that KG(4 ) ≥1.4841 , which has implications for device-independent witnessing dimensions greater than two. Furthermore, the algorithm with some modifications may find applications in various black-box quantum information tasks with large number of inputs and outputs.

  5. Creating a zero-order resonator using an optical surface transformation

    PubMed Central

    Sun, Fei; Ge, Xiaochen; He, Sailing

    2016-01-01

    A novel zero-order resonator has been designed by an optical surface transformation (OST) method. The resonator proposed here has many novel features. Firstly, the mode volume can be very small (e.g. in the subwavelength scale). Secondly, the resonator is open (no reflecting walls are utilized) and resonant effects can be found in a continuous spectrum (i.e. a continuum of eigenmodes). Thirdly, we only need one homogenous medium to realize the proposed resonator. The shape of the resonator can be a ring structure of arbitrary shape. In addition to the natural applications (e.g. optical storage) of an optical resonator, we also suggest some other applications of our novel optical open resonator (e.g. power combination, squeezing electromagnetic energy in the free space). PMID:26888359

  6. Adaptive Window Zero-Crossing-Based Instantaneous Frequency Estimation

    NASA Astrophysics Data System (ADS)

    Sekhar, S. Chandra; Sreenivas, TV

    2004-12-01

    We address the problem of estimating instantaneous frequency (IF) of a real-valued constant amplitude time-varying sinusoid. Estimation of polynomial IF is formulated using the zero-crossings of the signal. We propose an algorithm to estimate nonpolynomial IF by local approximation using a low-order polynomial, over a short segment of the signal. This involves the choice of window length to minimize the mean square error (MSE). The optimal window length found by directly minimizing the MSE is a function of the higher-order derivatives of the IF which are not available a priori. However, an optimum solution is formulated using an adaptive window technique based on the concept of intersection of confidence intervals. The adaptive algorithm enables minimum MSE-IF (MMSE-IF) estimation without requiring a priori information about the IF. Simulation results show that the adaptive window zero-crossing-based IF estimation method is superior to fixed window methods and is also better than adaptive spectrogram and adaptive Wigner-Ville distribution (WVD)-based IF estimators for different signal-to-noise ratio (SNR).

  7. Determination of the rate constant for the NH2(X(2)B1) + NH2(X(2)B1) reaction at low pressure and 293 K.

    PubMed

    Bahng, Mi-Kyung; Macdonald, R Glen

    2008-12-25

    The rate constant for the reaction NH(2)(X(2)B(1)) + NH(2)(X(2)B(1)) --> products was measured in CF(4), N(2) and Ar carrier gases at 293 +/- 2 K over a pressure range from 2 to 10 Torr. The NH(2) radical was produced by the 193 nm photolysis of NH(3) dilute in the carrier gas. Both the loss of NH(3) and its subsequent recovery and the production of NH(2) and subsequent reaction were monitored simultaneously following the photolysis laser pulse. Both species were detected using quantitative time-resolved high-resolution absorption spectroscopy. The NH(3) molecule was monitored in the NIR using a rotation transition of the nu(1) + nu(3) first combination band near 1500 nm, and the NH(2) radical was monitored using the (1)2(21) <-- (1)3(31) rotational transition of the (0,7,0)A(2)A(1) <-- (0,0,0) X(2)B(1) band near 675 nm. The low-pressure rate constant showed a linear dependence on pressure. The slope of the pressure dependence was dominated by a recombination rate constant for NH(2) + NH(2) given by (8.0 +/- 0.5) x 10(-29), (5.7 +/- 0.7) x 10(-29), and (3.9 +/- 0.4) x 10(-29) cm(6) molecule(-2) s(-1) in CF(4), N(2), and Ar bath gases, respectively, where the uncertainties are +/-2sigma in the scatter of the measurements. The average of the three independent measurements of the sum of the disproportionation rate constants (the zero pressure rate constant) was (3.4 +/- 6) x 10(-13) cm(3) molecule(-1) s(-1), where the uncertainty is +/-2sigma in the scatter of the measurements.

  8. New approach for identifying the zero-order fringe in variable wavelength interferometry

    NASA Astrophysics Data System (ADS)

    Galas, Jacek; Litwin, Dariusz; Daszkiewicz, Marek

    2016-12-01

    The family of VAWI techniques (for transmitted and reflected light) is especially efficient for characterizing objects, when in the interference system the optical path difference exceeds a few wavelengths. The classical approach that consists in measuring the deflection of interference fringes fails because of strong edge effects. Broken continuity of interference fringes prevents from correct identification of the zero order fringe, which leads to significant errors. The family of these methods has been proposed originally by Professor Pluta in the 1980s but that time image processing facilities and computers were hardly available. Automated devices unfold a completely new approach to the classical measurement procedures. The Institute team has taken that new opportunity and transformed the technique into fully automated measurement devices offering commercial readiness of industry-grade quality. The method itself has been modified and new solutions and algorithms simultaneously have extended the field of application. This has concerned both construction aspects of the systems and software development in context of creating computerized instruments. The VAWI collection of instruments constitutes now the core of the Institute commercial offer. It is now practically applicable in industrial environment for measuring textile and optical fibers, strips of thin films, testing of wave plates and nonlinear affects in different materials. This paper describes new algorithms for identifying the zero order fringe, which increases the performance of the system as a whole and presents some examples of measurements of optical elements.

  9. Self-ordered, controlled structure nanoporous membranes using constant current anodization.

    PubMed

    Lee, Kwan; Tang, Yun; Ouyang, Min

    2008-12-01

    We report a constant current (CC) based anodization technique to fabricate and control structure of mechanically stable anodic aluminum oxide (AAO) membranes with a long-range ordered hexagonal nanopore pattern. For the first time we show that interpore distance (Dint) of a self-ordered nanopore feature can be continuously tuned over a broad range with CC anodization and is uniquely defined by the conductivity of sulfuric acid as electrolyte. We further demonstrate that this technique can offer new degrees of freedom for engineering planar nanopore structures by fine tailoring the CC based anodization process. Our results not only facilitate further understanding of self-ordering mechanism of alumina membranes but also provide a fast, simple (without requirement of prepatterning or preoxide layer), and flexible methodology for controlling complex nanoporous structures, thus offering promising practical applications in nanotechnology.

  10. EFFECTIVE ACIDITY CONSTANT BEHAVIOR NEAR ZERO CHARGE CONDITIONS

    EPA Science Inventory

    Surface site (>SOH group) acidity reactions require expressions of the form: Ka = [>SOHn-1(z-1)]aH+EXP(-DG/RT)/[>SOHnz] (where all variables have their usual meaning). One can rearrange this expression to generate an effective acidity constant historically defined as: Qa = Ka...

  11. Optical phase distribution evaluation by using zero order Generalized Morse Wavelet

    NASA Astrophysics Data System (ADS)

    Kocahan, Özlem; Elmas, Merve Naz; Durmuş, ćaǧla; Coşkun, Emre; Tiryaki, Erhan; Özder, Serhat

    2017-02-01

    When determining the phase from the projected fringes by using continuous wavelet transform (CWT), selection of wavelet is an important step. A new wavelet for phase retrieval from the fringe pattern with the spatial carrier frequency in the x direction is presented. As a mother wavelet, zero order generalized Morse wavelet (GMW) is chosen because of the flexible spatial and frequency localization property, and it is exactly analytic. In this study, GMW method is explained and numerical simulations are carried out to show the validity of this technique for finding the phase distributions. Results for the Morlet and Paul wavelets are compared with the results of GMW analysis.

  12. Rate constants of agonist binding to muscarinic receptors in rat brain medulla. Evaluation by competition kinetics

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

    Schreiber, G.; Henis, Y.I.; Sokolovsky, M.

    The method of competition kinetics, which measures the binding kinetics of an unlabeled ligand through its effect on the binding kinetics of a labeled ligand, was employed to investigate the kinetics of muscarinic agonist binding to rat brain medulla pons homogenates. The agonists studied were acetylcholine, carbamylcholine, and oxotremorine, with N-methyl-4-(TH)piperidyl benzilate employed as the radiolabeled ligand. Our results suggested that the binding of muscarinic agonists to the high affinity sites is characterized by dissociation rate constants higher by 2 orders of magnitude than those of antagonists, with rather similar association rate constants. Our findings also suggest that isomerization ofmore » the muscarinic receptors following ligand binding is significant in the case of antagonists, but not of agonists. Moreover, it is demonstrated that in the medulla pons preparation, agonist-induced interconversion between high and low affinity bindings sites does not occur to an appreciable extent.« less

  13. Semiclassical Calculation of Reaction Rate Constants for Homolytical Dissociations

    NASA Technical Reports Server (NTRS)

    Cardelino, Beatriz H.

    2002-01-01

    There is growing interest in extending organometallic chemical vapor deposition (OMCVD) to III-V materials that exhibit large thermal decomposition at their optimum growth temperature, such as indium nitride. The group III nitrides are candidate materials for light-emitting diodes and semiconductor lasers operating into the blue and ultraviolet regions. To overcome decomposition of the deposited compound, the reaction must be conducted at high pressures, which causes problems of uniformity. Microgravity may provide the venue for maintaining conditions of laminar flow under high pressure. Since the selection of optimized parameters becomes crucial when performing experiments in microgravity, efforts are presently geared to the development of computational OMCVD models that will couple the reactor fluid dynamics with its chemical kinetics. In the present study, we developed a method to calculate reaction rate constants for the homolytic dissociation of III-V compounds for modeling OMCVD. The method is validated by comparing calculations with experimental reaction rate constants.

  14. Effective rate constants for nanostructured heterogeneous catalysts

    NASA Astrophysics Data System (ADS)

    Hendy, Shaun; Gaston, Nicola; Zhang, Philip; Lund, Nat

    2012-02-01

    There is currently a high level of interest in the use of nanostructured materials for catalysis. For instance, gold, which is largely inert in the bulk, can exhibit strong catalytic activity when in nanoparticle form. With precious metal catalysts such as Pt and Pd in high demand, the use of these materials in nanoparticle form can also substantially reduce costs by exposure of more surface area for the same volume of material. When reactants are plentiful, the effective activity of a nanoparticulate catalyst will increase roughly with its surface area. However, under diffusion-limited conditions, the reactant must diffuse to active sites on the catalyst, so a high surface area and a high density of active sites may bring diminishing returns if reactant is consumed faster than it arrives. Here we apply a mathematical homogenisation approach to derive simple expressions for the effective reactivity of a nanostructured catalyst under diffusion limited conditions that relate the intrinsic rate constants of the surfaces presented by the catalyst to an effective rate constant. When highly active catalytic sites, such as step edges or other defects are present, we show that distinct limiting cases emerge depending on the degree of overlap of the reactant depletion zone about each site. In gases, the size of this depletion zone is approximately the mean free path, so the effective reactivity will depend on the structure of the catalyst on that scale. We discuss implications for the optimal design of nanoparticle catalysts.

  15. Kinetic rate constant prediction supports the conformational selection mechanism of protein binding.

    PubMed

    Moal, Iain H; Bates, Paul A

    2012-01-01

    The prediction of protein-protein kinetic rate constants provides a fundamental test of our understanding of molecular recognition, and will play an important role in the modeling of complex biological systems. In this paper, a feature selection and regression algorithm is applied to mine a large set of molecular descriptors and construct simple models for association and dissociation rate constants using empirical data. Using separate test data for validation, the predicted rate constants can be combined to calculate binding affinity with accuracy matching that of state of the art empirical free energy functions. The models show that the rate of association is linearly related to the proportion of unbound proteins in the bound conformational ensemble relative to the unbound conformational ensemble, indicating that the binding partners must adopt a geometry near to that of the bound prior to binding. Mirroring the conformational selection and population shift mechanism of protein binding, the models provide a strong separate line of evidence for the preponderance of this mechanism in protein-protein binding, complementing structural and theoretical studies.

  16. HO + CO reaction rates and H/D kinetic isotope effects: master equation models with ab initio SCTST rate constants.

    PubMed

    Weston, Ralph E; Nguyen, Thanh Lam; Stanton, John F; Barker, John R

    2013-02-07

    Ab initio microcanonical rate constants were computed using Semi-Classical Transition State Theory (SCTST) and used in two master equation formulations (1D, depending on active energy with centrifugal corrections, and 2D, depending on total energy and angular momentum) to compute temperature-dependent rate constants for the title reactions using a potential energy surface obtained by sophisticated ab initio calculations. The 2D master equation was used at the P = 0 and P = ∞ limits, while the 1D master equation with centrifugal corrections and an empirical energy transfer parameter could be used over the entire pressure range. Rate constants were computed for 75 K ≤ T ≤ 2500 K and 0 ≤ [He] ≤ 10(23) cm(-3). For all temperatures and pressures important for combustion and for the terrestrial atmosphere, the agreement with the experimental rate constants is very good, but at very high pressures and T ≤ 200 K, the theoretical rate constants are significantly smaller than the experimental values. This effect is possibly due to the presence in the experiments of dimers and prereactive complexes, which were not included in the model calculations. The computed H/D kinetic isotope effects are in acceptable agreement with experimental data, which show considerable scatter. Overall, the agreement between experimental and theoretical H/D kinetic isotope effects is much better than in previous work, and an assumption of non-RRKM behavior does not appear to be needed to reproduce experimental observations.

  17. Phototransformation rate constants of PAHs associated with soot particles.

    PubMed

    Kim, Daekyun; Young, Thomas M; Anastasio, Cort

    2013-01-15

    Photodegradation is a key process governing the residence time and fate of polycyclic aromatic hydrocarbons (PAHs) in particles, both in the atmosphere and after deposition. We have measured photodegradation rate constants of PAHs in bulk deposits of soot particles illuminated with simulated sunlight. The photodegradation rate constants at the surface (k(p)(0)), the effective diffusion coefficients (D(eff)), and the light penetration depths (z(0.5)) for PAHs on soot layers of variable thickness were determined by fitting experimental data with a model of coupled photolysis and diffusion. The overall disappearance rates of irradiated low molecular weight PAHs (with 2-3 rings) on soot particles were influenced by fast photodegradation and fast diffusion kinetics, while those of high molecular weight PAHs (with 4 or more rings) were apparently controlled by either the combination of slow photodegradation and slow diffusion kinetics or by very slow diffusion kinetics alone. The value of z(0.5) is more sensitive to the soot layer thickness than the k(p)(0) value. As the thickness of the soot layer increases, the z(0.5) values increase, but the k(p)(0) values are almost constant. The effective diffusion coefficients calculated from dark experiments are generally higher than those from the model fitting method for illumination experiments. Due to the correlation between k(p)(0) and z(0.5) in thinner layers, D(eff) should be estimated by an independent method for better accuracy. Despite some limitations of the model used in this study, the fitted parameters were useful for describing empirical results of photodegradation of soot-associated PAHs. Copyright © 2012 Elsevier B.V. All rights reserved.

  18. Phototransformation Rate Constants of PAHs Associated with Soot Particles

    PubMed Central

    Kim, Daekyun; Young, Thomas M.; Anastasio, Cort

    2013-01-01

    Photodegradation is a key process governing the residence time and fate of polycyclic aromatic hydrocarbons (PAHs) in particles, both in the atmosphere and after deposition. We have measured photodegradation rate constants of PAHs in bulk deposits of soot particles illuminated with simulated sunlight. The photodegradation rate constants at the surface (k0p), the effective diffusion coefficients (Deff), and the light penetration depths (z0.5) for PAHs on soot layers of variable thickness were determined by fitting experimental data with a model of coupled photolysis and diffusion. The overall disappearance rates of irradiated low molecular weight PAHs (with 2-3 rings) on soot particles were influenced by fast photodegradation and fast diffusion kinetics, while those of high molecular weight PAHs (with 4 or more rings) were apparently controlled by either the combination of slow photodegradation and slow diffusion kinetics or by very slow diffusion kinetics alone. The value of z0.5 is more sensitive to the soot layer thickness than the k0p value. As the thickness of the soot layer increases, the z0.5 values increase, but the k0p values are almost constant. The effective diffusion coefficients calculated from dark experiments are generally higher than those from the model fitting method for illumination experiments. Due to the correlation between k0p and z0.5 in thinner layers, Deff should be estimated by an independent method for better accuracy. Despite some limitations of the model used in this study, the fitted parameters were useful for describing empirical results of photodegradation of soot-associated PAHs. PMID:23247292

  19. Theoretical rate constants of super-exchange hole transfer and thermally induced hopping in DNA.

    PubMed

    Shimazaki, Tomomi; Asai, Yoshihiro; Yamashita, Koichi

    2005-01-27

    Recently, the electronic properties of DNA have been extensively studied, because its conductivity is important not only to the study of fundamental biological problems, but also in the development of molecular-sized electronics and biosensors. We have studied theoretically the reorganization energies, the activation energies, the electronic coupling matrix elements, and the rate constants of hole transfer in B-form double-helix DNA in water. To accommodate the effects of DNA nuclear motions, a subset of reaction coordinates for hole transfer was extracted from classical molecular dynamics (MD) trajectories of DNA in water and then used for ab initio quantum chemical calculations of electron coupling constants based on the generalized Mulliken-Hush model. A molecular mechanics (MM) method was used to determine the nuclear Franck-Condon factor. The rate constants for two types of mechanisms of hole transfer-the thermally induced hopping (TIH) and the super-exchange mechanisms-were determined based on Marcus theory. We found that the calculated matrix elements are strongly dependent on the conformations of the nucleobase pairs of hole-transferable DNA and extend over a wide range of values for the "rise" base-step parameter but cluster around a particular value for the "twist" parameter. The calculated activation energies are in good agreement with experimental results. Whereas the rate constant for the TIH mechanism is not dependent on the number of A-T nucleobase pairs that act as a bridge, the rate constant for the super-exchange process rapidly decreases when the length of the bridge increases. These characteristic trends in the calculated rate constants effectively reproduce those in the experimental data of Giese et al. [Nature 2001, 412, 318]. The calculated rate constants were also compared with the experimental results of Lewis et al. [Nature 2000, 406, 51].

  20. 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

  1. Determination of equilibrium and rate constants for complex formation by fluorescence correlation spectroscopy supplemented by dynamic light scattering and Taylor dispersion analysis.

    PubMed

    Zhang, Xuzhu; Poniewierski, Andrzej; Jelińska, Aldona; Zagożdżon, Anna; Wisniewska, Agnieszka; Hou, Sen; Hołyst, Robert

    2016-10-04

    The equilibrium and rate constants of molecular complex formation are of great interest both in the field of chemistry and biology. Here, we use fluorescence correlation spectroscopy (FCS), supplemented by dynamic light scattering (DLS) and Taylor dispersion analysis (TDA), to study the complex formation in model systems of dye-micelle interactions. In our case, dyes rhodamine 110 and ATTO-488 interact with three differently charged surfactant micelles: octaethylene glycol monododecyl ether C 12 E 8 (neutral), cetyltrimethylammonium chloride CTAC (positive) and sodium dodecyl sulfate SDS (negative). To determine the rate constants for the dye-micelle complex formation we fit the experimental data obtained by FCS with a new form of the autocorrelation function, derived in the accompanying paper. Our results show that the association rate constants for the model systems are roughly two orders of magnitude smaller than those in the case of the diffusion-controlled limit. Because the complex stability is determined by the dissociation rate constant, a two-step reaction mechanism, including the diffusion-controlled and reaction-controlled rates, is used to explain the dye-micelle interaction. In the limit of fast reaction, we apply FCS to determine the equilibrium constant from the effective diffusion coefficient of the fluorescent components. Depending on the value of the equilibrium constant, we distinguish three types of interaction in the studied systems: weak, intermediate and strong. The values of the equilibrium constant obtained from the FCS and TDA experiments are very close to each other, which supports the theoretical model used to interpret the FCS data.

  2. 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).

  3. Charring rate of wood exposed to a constant heat flux

    Treesearch

    R. H. White; H. C. Tran

    1996-01-01

    A critical factor in the fire endurance of a wood member is its rate of charring. Most available charring rate data have been obtained using the time-temperature curves of the standard fire resistance tests (ASTM E 119 and ISO 834) to define the fire exposure. The increased use of heat release calorimeters using exposures of constant heat flux levels has broadened the...

  4. Study on improving the turbidity measurement of the absolute coagulation rate constant.

    PubMed

    Sun, Zhiwei; Liu, Jie; Xu, Shenghua

    2006-05-23

    The existing theories dealing with the evaluation of the absolute coagulation rate constant by turbidity measurement were experimentally tested for different particle-sized (radius = a) suspensions at incident wavelengths (lambda) ranging from near-infrared to ultraviolet light. When the size parameter alpha = 2pi a/lambda > 3, the rate constant data from previous theories for fixed-sized particles show significant inconsistencies at different light wavelengths. We attribute this problem to the imperfection of these theories in describing the light scattering from doublets through their evaluation of the extinction cross section. The evaluations of the rate constants by all previous theories become untenable as the size parameter increases and therefore hampers the applicable range of the turbidity measurement. By using the T-matrix method, we present a robust solution for evaluating the extinction cross section of doublets formed in the aggregation. Our experiments show that this new approach is effective in extending the applicability range of the turbidity methodology and increasing measurement accuracy.

  5. 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

  6. 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

  7. Ligand-assisted degradation of carbon tetrachloride by microscale zero-valent iron.

    PubMed

    Zhang, Xianlan; Deng, Baolin; Guo, Jing; Wang, Yang; Lan, Yeqing

    2011-04-01

    Degradation of carbon tetrachloride (CT) by microscale zero-valent iron (ZVI) was investigated in batch systems with or without organic ligands (ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, malic acid and oxalic acid) at pHs from 3.5 to 7.5. The results demonstrated that at 25°C, the dechlorination of CT by microscale ZVI is slow in the absence of organic ligands, with a pseudo-first-order rate constant of 0.0217 h(-1) at pH 3.5 and being further dropped to 0.0052 h(-1) at pH 7.5. However, addition of organic ligands significantly enhanced the rates and the extents of CT removal, as indicated by the rate constant increases of 39, 31, 32, 28 and 18 times in the presence of EDTA, citric acid, tartaric acid, malic acid and oxalic acid, respectively, at pH 3.5 and 25°C. The effect of EDTA was most significant; the dechlorination of CT at an initial concentration of 20 mg l(-1) increased from 16.3% (no ligands) to 89.1% (with EDTA) at the end of 8h reaction. The enhanced CT degradation in the presence of organic ligands was primarily attributed to the elimination of a surface passivation layer of Fe(III) (hydr)oxides on the microscale ZVI through chelating of organic ligands with Fe(III), which maintained the exposure of active sites on ZVI surface to CT. Copyright © 2010 Elsevier Ltd. All rights reserved.

  8. Spin-lattice relaxation-rate anomaly at structural phase transitions

    NASA Astrophysics Data System (ADS)

    Levanyuk, A. P.; Minyukov, S. A.; Etrillard, J.; Toudic, B.

    1997-12-01

    The theory of spin-lattice relaxation (SLR)-rate anomaly at structural phase transitions proposed about 30 years ago is reconsidered taking into account that knowledge about the relevant lattice response functions has changed considerably. We use both the results of previous authors and perform original calculations of the response functions when it is necessary. We consider displacive systems and use the perturbation theory to treat the lattice anharmonicities in a broad temperature region whenever possible. Some comments about the order-disorder systems are made as well. The possibility of linear coupling of the order parameter and the resonance frequency is always assumed. It is found that in the symmetrical phase the anomaly is due to the one-phonon processes, the anomalous part being proportional to either (T-Tc)-1 or (T-Tc)-1/2 depending on some condition on the soft-mode dispersion. In both cases the value of the SLR rate at the boundary of applicabity of the theory (close to the phase transition) is estimated to be 102-103 times more than the typical value of the SLR rate in an ideal crystal. An essential specific feature of the nonsymmetrical phase is appearance of third-order anharmonicities that are well known to lead to a low-frequency dispersion of the order-parameter damping constant. We have found that this constant exhibits, in addition, a strong wave-vector dispersion, so that the damping constant determing the SLR rate is quite different from that at zero wave vector. In the case of two-component order parameter the damping constant for the component with nonzero equilibrium value is different from that for the other component, the difference is of the same order of magnitude as the damping constants themselves. In the case of the incommensurate phase a part of the mentioned third-order anharmonicity is responsible for longitudinal-transversal interaction that is well known to influence the static longitudinal response function. We calculate as

  9. 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.

  10. High Order Accuracy Methods for Supersonic Reactive Flows

    DTIC Science & Technology

    2008-06-25

    k = 0, · · · , N and N is the polynomial order used. The positive constant M is chosen such that σ(N) becomes machine zero. Typically M ∼ 32. Table...function used in this study is the Exponential filter given by σ(η) = exp(−αηp), (38) where α = − ln() and is the machine zero. The spectral...respectively. All numerical experiments were run 49 on a 667 MHz Compaq Alpha machine with 1GB memory and with an Alpha internal floating point processor. 9.1

  11. A first-passage scheme for determination of overall rate constants for non-diffusion-limited suspensions

    NASA Astrophysics Data System (ADS)

    Lu, Shih-Yuan; Yen, Yi-Ming

    2002-02-01

    A first-passage scheme is devised to determine the overall rate constant of suspensions under the non-diffusion-limited condition. The original first-passage scheme developed for diffusion-limited processes is modified to account for the finite incorporation rate at the inclusion surface by using a concept of the nonzero survival probability of the diffusing entity at entity-inclusion encounters. This nonzero survival probability is obtained from solving a relevant boundary value problem. The new first-passage scheme is validated by an excellent agreement between overall rate constant results from the present development and from an accurate boundary collocation calculation for the three common spherical arrays [J. Chem. Phys. 109, 4985 (1998)], namely simple cubic, body-centered cubic, and face-centered cubic arrays, for a wide range of P and f. Here, P is a dimensionless quantity characterizing the relative rate of diffusion versus surface incorporation, and f is the volume fraction of the inclusion. The scheme is further applied to random spherical suspensions and to investigate the effect of inclusion coagulation on overall rate constants. It is found that randomness in inclusion arrangement tends to lower the overall rate constant for f up to the near close-packing value of the regular arrays because of the inclusion screening effect. This screening effect turns stronger for regular arrays when f is near and above the close-packing value of the regular arrays, and consequently the overall rate constant of the random array exceeds that of the regular array. Inclusion coagulation too induces the inclusion screening effect, and leads to lower overall rate constants.

  12. 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.

  13. 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.

  14. Rate constant for the reaction SO + BrO yields SO2 + Br

    NASA Technical Reports Server (NTRS)

    Brunning, J.; Stief, L.

    1986-01-01

    The rate of the radical-radical reaction SO + BrO yields SO2 + Br has been determined at 298 K in a discharge flow system near 1 torr pressure with detection of SO and BrO via collision-free sampling mass spectrometry. The rate constant was determined using two different methods: measuring the decay of SO radicals in the presence of an excess of BrO and measuring the decay of BrO radicals in excess SO. The results from the two methods are in reasonable agreement and the simple mean of the two values gives the recommended rate constant at 298 K, k = (5.7 + or - 2.0) x 10 to the -11th cu cm/s. This represents the first determination of this rate constant and it is consistent with a previously derived lower limit based on SO2 formation. Comparison is made with other radical-radical reactions involving SO or BrO. The reaction SO + BrO yields SO2 + Br is of interest for models of the upper atmosphere of the earth and provides a potential coupling between atmospheric sulfur and bromine chemistry.

  15. Boson mapping techniques applied to constant gauge fields in QCD

    NASA Technical Reports Server (NTRS)

    Hess, Peter Otto; Lopez, J. C.

    1995-01-01

    Pairs of coordinates and derivatives of the constant gluon modes are mapped to new gluon-pair fields and their derivatives. Applying this mapping to the Hamiltonian of constant gluon fields results for large coupling constants into an effective Hamiltonian which separates into one describing a scalar field and another one for a field with spin two. The ground state is dominated by pairs of gluons coupled to color and spin zero with slight admixtures of color zero and spin two pairs. As color group we used SU(2).

  16. Zero Thermal Noise in Resistors at Zero Temperature

    NASA Astrophysics Data System (ADS)

    Kish, Laszlo B.; Niklasson, Gunnar A.; Granqvist, Claes-Göran

    2016-06-01

    The bandwidth of transistors in logic devices approaches the quantum limit, where Johnson noise and associated error rates are supposed to be strongly enhanced. However, the related theory — asserting a temperature-independent quantum zero-point (ZP) contribution to Johnson noise, which dominates the quantum regime — is controversial and resolution of the controversy is essential to determine the real error rate and fundamental energy dissipation limits of logic gates in the quantum limit. The Callen-Welton formula (fluctuation-dissipation theorem) of voltage and current noise for a resistance is the sum of Nyquist’s classical Johnson noise equation and a quantum ZP term with a power density spectrum proportional to frequency and independent of temperature. The classical Johnson-Nyquist formula vanishes at the approach of zero temperature, but the quantum ZP term still predicts non-zero noise voltage and current. Here, we show that this noise cannot be reconciled with the Fermi-Dirac distribution, which defines the thermodynamics of electrons according to quantum-statistical physics. Consequently, Johnson noise must be nil at zero temperature, and non-zero noise found for certain experimental arrangements may be a measurement artifact, such as the one mentioned in Kleen’s uncertainty relation argument.

  17. Immobilization of chromate in hyperalkaline waste streams by green rusts and zero-valent iron.

    PubMed

    Rogers, Christine M; Burke, Ian T; Ahmed, Imad A M; Shaw, Samuel

    2014-01-01

    Zero-valent iron (ZVI) and green rusts can be used as reductants to convert chromium from soluble, highly toxic Cr(VI) to insoluble Cr(III). This study compared the reduction rates of Cr(VI) by ZVI and two carbonate green rust phases in alkaline/hyperalkaline solutions. Batch experiments were carried out with synthetic chromate solutions at pH 7.7-12.3 and a chromite ore processing residue (COPR) leachate (pH approximately 12.2). Green rust removes chromate from high pH solutions (pH 10-12.5) very rapidly (<400 s). Chromate reduction rates for both green rust phases were consistently higher than for ZVI throughout the pH range studied; the surface area normalized rate constants were two orders of magnitude higher in the COPR leachate solution at pH 12.2. The performances of both green rusts were unaffected by changes in pH. In contrast, ZVI exhibited a marked decline in reduction rate with increasing pH to become almost ineffective above pH12.

  18. Enhanced decolorization of methyl orange using zero-valent copper nanoparticles under assistance of hydrodynamic cavitation.

    PubMed

    Li, Pan; Song, Yuan; Wang, Shuai; Tao, Zheng; Yu, Shuili; Liu, Yanan

    2015-01-01

    The rate of reduction reactions of zero-valent metal nanoparticles is restricted by their agglomeration. Hydrodynamic cavitation was used to overcome the disadvantage in this study. Experiments for decolorization of methyl orange azo dye by zero-valent copper nanoparticles were carried out in aqueous solution with and without hydrodynamic cavitation. The results showed that hydrodynamic cavitation greatly accelerated the decolorization rate of methyl orange. The size of nanoparticles was decreased after hydrodynamic cavitation treatment. The effects of important operating parameters such as discharge pressure, initial solution pH, and copper nanoparticle concentration on the degradation rates were studied. It was observed that there was an optimum discharge pressure to get best decolorization performance. Lower solution pH were favorable for the decolorization. The pseudo-first-order kinetic constant for the degradation of methyl orange increased linearly with the copper dose. UV-vis spectroscopic and Fourier transform infrared (FT-IR) analyses confirmed that many degradation intermediates were formed. The results indicated hydroxyl radicals played a key role in the decolorization process. Therefore, the enhancement of decolorization by hydrodynamic cavitation could due to the deagglomeration of nanoparticles as well as the oxidation by the in situ generated hydroxyl radicals. These findings greatly increase the potential of the Cu(0)/hydrodynamic cavitation technique for use in the field of treatment of wastewater containing hazardous materials. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Noninvasive blood-flow meter using a curved cannula with zero compensation for an axial flow blood pump.

    PubMed

    Kosaka, Ryo; Fukuda, Kyohei; Nishida, Masahiro; Maruyama, Osamu; Yamane, Takashi

    2013-01-01

    In order to monitor the condition of a patient using a left ventricular assist system (LVAS), blood flow should be measured. However, the reliable determination of blood-flow rate has not been established. The purpose of the present study is to develop a noninvasive blood-flow meter using a curved cannula with zero compensation for an axial flow blood pump. The flow meter uses the centrifugal force generated by the flow rate in the curved cannula. Two strain gauges served as sensors. The first gauges were attached to the curved area to measure static pressure and centrifugal force, and the second gauges were attached to straight area to measure static pressure. The flow rate was determined by the differences in output from the two gauges. The zero compensation was constructed based on the consideration that the flow rate could be estimated during the initial driving condition and the ventricular suction condition without using the flow meter. A mock circulation loop was constructed in order to evaluate the measurement performance of the developed flow meter with zero compensation. As a result, the zero compensation worked effectively for the initial calibration and the zero-drift of the measured flow rate. We confirmed that the developed flow meter using a curved cannula with zero compensation was able to accurately measure the flow rate continuously and noninvasively.

  20. QSPR prediction of the hydroxyl radical rate constant of water contaminants.

    PubMed

    Borhani, Tohid Nejad Ghaffar; Saniedanesh, Mohammadhossein; Bagheri, Mehdi; Lim, Jeng Shiun

    2016-07-01

    In advanced oxidation processes (AOPs), the aqueous hydroxyl radical (HO) acts as a strong oxidant to react with organic contaminants. The hydroxyl radical rate constant (kHO) is important for evaluating and modelling of the AOPs. In this study, quantitative structure-property relationship (QSPR) method is applied to model the hydroxyl radical rate constant for a diverse dataset of 457 water contaminants from 27 various chemical classes. The constricted binary particle swarm optimization and multiple-linear regression (BPSO-MLR) are used to obtain the best model with eight theoretical descriptors. An optimized feed forward neural network (FFNN) is developed to investigate the complex performance of the selected molecular parameters with kHO. Although the FFNN prediction results are more accurate than those obtained using BPSO-MLR, the application of the latter is much more convenient. Various internal and external validation techniques indicate that the obtained models could predict the logarithmic hydroxyl radical rate constants of a large number of water contaminants with less than 4% absolute relative error. Finally, the above-mentioned proposed models are compared to those reported earlier and the structural factors contributing to the AOP degradation efficiency are discussed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Zero absolute vorticity: insight from experiments in rotating laminar plane Couette flow.

    PubMed

    Suryadi, Alexandre; Segalini, Antonio; Alfredsson, P Henrik

    2014-03-01

    For pressure-driven turbulent channel flows undergoing spanwise system rotation, it has been observed that the absolute vorticity, i.e., the sum of the averaged spanwise flow vorticity and system rotation, tends to zero in the central region of the channel. This observation has so far eluded a convincing theoretical explanation, despite experimental and numerical evidence reported in the literature. Here we show experimentally that three-dimensional laminar structures in plane Couette flow, which appear under anticyclonic system rotation, give the same effect, namely, that the absolute vorticity tends to zero if the rotation rate is high enough. It is shown that this is equivalent to a local Richardson number of approximately zero, which would indicate a stable condition. We also offer an explanation based on Kelvin's circulation theorem to demonstrate that the absolute vorticity should remain constant and approximately equal to zero in the central region of the channel when going from the nonrotating fully turbulent state to any state with sufficiently high rotation.

  2. 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

  3. Rate constant for the fraction of atomic chlorine with formaldehyde from 200 to 500K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Nava, D. F.; Payne, W. A.; Stief, L. J.

    1978-01-01

    A flash photolysis - resonance fluorescence technique was used to measure rate constant. The results were independent of substantial variations in H2CO, total pressure (Ar), and flash intensity (i.e., initial Cl). The rate constant was shown to be invariant with temperature, the best representation for this temperature range being K = (7.48 + or - 0.50) x 10 to the minus 11 power cu cm molecule-1 s-1 where the error is one standard deviation. The rate constant is theoretically discussed and the potential importance of the reaction in stratospheric chemistry is considered.

  4. Zero-Order Chemical Kinetics as a Context to Investigate Student Understanding of Catalysts and Half-Life

    ERIC Educational Resources Information Center

    Bain, Kinsey; Rodriguez, Jon-Marc G.; Towns, Marcy H.

    2018-01-01

    Zero-order systems provide an interesting opportunity for students to think about the underlying mechanism behind the physical phenomena being modeled. The work reported here is part of a larger study that seeks to characterize how students integrate chemistry and mathematics in the context of chemical kinetics. Thirty-six general chemistry…

  5. 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.

  6. 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.

  7. A simple method relating specific rate constants k(E,J) and Thermally averaged rate constants k(infinity)(T) of unimolecular bond fission and the reverse barrierless association reactions.

    PubMed

    Troe, J; Ushakov, V G

    2006-06-01

    This work describes a simple method linking specific rate constants k(E,J) of bond fission reactions AB --> A + B with thermally averaged capture rate constants k(cap)(T) of the reverse barrierless combination reactions A + B --> AB (or the corresponding high-pressure dissociation or recombination rate constants k(infinity)(T)). Practical applications are given for ionic and neutral reaction systems. The method, in the first stage, requires a phase-space theoretical treatment with the most realistic minimum energy path potential available, either from reduced dimensionality ab initio or from model calculations of the potential, providing the centrifugal barriers E(0)(J). The effects of the anisotropy of the potential afterward are expressed in terms of specific and thermal rigidity factors f(rigid)(E,J) and f(rigid)(T), respectively. Simple relationships provide a link between f(rigid)(E,J) and f(rigid)(T) where J is an average value of J related to J(max)(E), i.e., the maximum J value compatible with E > or = E0(J), and f(rigid)(E,J) applies to the transitional modes. Methods for constructing f(rigid)(E,J) from f(rigid)(E,J) are also described. The derived relationships are adaptable and can be used on that level of information which is available either from more detailed theoretical calculations or from limited experimental information on specific or thermally averaged rate constants. The examples used for illustration are the systems C6H6+ <==> C6H5+ + H, C8H10+ --> C7H7+ + CH3, n-C9H12+ <==> C7H7+ + C2H5, n-C10H14+ <==> C7H7+ + C3H7, HO2 <==> H + O2, HO2 <==> HO + O, and H2O2 <==> 2HO.

  8. Transition to zero cosmological constant and phantom dark energy as solutions involving change of orientation of spacetime manifold

    NASA Astrophysics Data System (ADS)

    Guendelman, E. I.; Kaganovich, A. B.

    2008-12-01

    The main conclusion of long-standing discussions concerning the role of solutions with degenerate metric (g ≡ det(gμν) = 0 and even with gμν = 0) was that in the first-order formalism they are physically acceptable and must be included in the path integral. In particular, they may describe topology changes and reduction of the 'metrical dimension' of spacetime. The latter implies disappearance of the volume element \\sqrt{-g}d^4x of a 4D spacetime in a neighborhood of the point with g = 0. We pay attention to the fact that besides \\sqrt{-g} , the 4D spacetime differentiable manifold also possesses a 'manifold volume measure' (MVM) described by a 4-form which is sign indefinite and generically independent of the metric. The first-order formalism proceeds with an originally independent connection and metric structures of the spacetime manifold. In this paper we bring up the question of whether the first-order formalism should be supplemented with degrees of freedom of the spacetime differentiable manifold itself, e.g. by means of the MVM. It turns out that adding the MVM degrees of freedom to the action principle in the first-order formalism one can realize very interesting dynamics. Such a two measures field theory (TMT) enables radically new approaches to the resolution of the cosmological constant problem. We show that fine tuning free solutions describing a transition to the Λ = 0 state involve oscillations of gμν and MVM around zero. The latter can be treated as a dynamics involving changes of orientation of the spacetime manifold. As we have shown earlier, in realistic scale invariant models (SIM), solutions formulated in the Einstein frame satisfy all existing tests of general relativity (GR). Here we reveal surprisingly that in SIM, all ground-state solutions with Λ ≠ 0 appear to be degenerate either in g00 or in MVM. Sign indefiniteness of MVM in a natural way yields a dynamical realization of a phantom cosmology (w < -1). It is very important

  9. A second-order shock-expansion method applicable to bodies of revolution near zero lift

    NASA Technical Reports Server (NTRS)

    1957-01-01

    A second-order shock-expansion method applicable to bodies of revolution is developed by the use of the predictions of the generalized shock-expansion method in combination with characteristics theory. Equations defining the zero-lift pressure distributions and the normal-force and pitching-moment derivatives are derived. Comparisons with experimental results show that the method is applicable at values of the similarity parameter, the ratio of free-stream Mach number to nose fineness ratio, from about 0.4 to 2.

  10. Rate Constants and Activation Energies for Gas-Phase Reactions of Three Cyclic Volatile Methyl Siloxanes with the Hydroxyl Radical.

    PubMed

    Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie; Macleod, Matthew

    2015-07-01

    Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second-order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ), and dodecamethylcyclohexasiloxane (D 6 ) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140-mL gas-phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D 4 and D 5 with the OH radical are 1.9 × 10 -12 (95% confidence interval (CI): (1.7-2.2) × 10 -12 ) and 2.6 × 10 -12 (CI: (2.3-2.9) × 10 -12 ) cm 3 molecule -1 s -1 , respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D 6 is 2.8 × 10 -12 (CI: (2.5-3.2) × 10 -12 ) cm 3 molecule -1 s -1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D 5 were 33% higher than for D 4 (CI: 30-37%), whereas the rates for D 6 were only 8% higher than for D 5 (CI: 5-10%). The activation energies of the reactions of D 4 , D 5 , and D 6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol.

  11. Statistical Models for the Analysis of Zero-Inflated Pain Intensity Numeric Rating Scale Data.

    PubMed

    Goulet, Joseph L; Buta, Eugenia; Bathulapalli, Harini; Gueorguieva, Ralitza; Brandt, Cynthia A

    2017-03-01

    Pain intensity is often measured in clinical and research settings using the 0 to 10 numeric rating scale (NRS). NRS scores are recorded as discrete values, and in some samples they may display a high proportion of zeroes and a right-skewed distribution. Despite this, statistical methods for normally distributed data are frequently used in the analysis of NRS data. We present results from an observational cross-sectional study examining the association of NRS scores with patient characteristics using data collected from a large cohort of 18,935 veterans in Department of Veterans Affairs care diagnosed with a potentially painful musculoskeletal disorder. The mean (variance) NRS pain was 3.0 (7.5), and 34% of patients reported no pain (NRS = 0). We compared the following statistical models for analyzing NRS scores: linear regression, generalized linear models (Poisson and negative binomial), zero-inflated and hurdle models for data with an excess of zeroes, and a cumulative logit model for ordinal data. We examined model fit, interpretability of results, and whether conclusions about the predictor effects changed across models. In this study, models that accommodate zero inflation provided a better fit than the other models. These models should be considered for the analysis of NRS data with a large proportion of zeroes. We examined and analyzed pain data from a large cohort of veterans with musculoskeletal disorders. We found that many reported no current pain on the NRS on the diagnosis date. We present several alternative statistical methods for the analysis of pain intensity data with a large proportion of zeroes. Published by Elsevier Inc.

  12. Pichia pastoris Exhibits High Viability and a Low Maintenance Energy Requirement at Near-Zero Specific Growth Rates

    PubMed Central

    Rebnegger, Corinna; Vos, Tim; Graf, Alexandra B.; Valli, Minoska; Pronk, Jack T.

    2016-01-01

    ABSTRACT The yeast Pichia pastoris is a widely used host for recombinant protein production. Understanding its physiology at extremely low growth rates is a first step in the direction of decoupling product formation from cellular growth and therefore of biotechnological relevance. Retentostat cultivation is an excellent tool for studying microbes at extremely low specific growth rates but has so far not been implemented for P. pastoris. Retentostat feeding regimes were based on the maintenance energy requirement (mS) and maximum biomass yield on glucose (YX/Smax) estimated from steady-state glucose-limited chemostat cultures. Aerobic retentostat cultivation enabled reproducible, smooth transitions from a specific growth rate (μ) of 0.025 h−1 to near-zero specific growth rates (μ < 0.001 h−1). At these near-zero specific growth rates, viability remained at least 97%. The value of mS at near-zero growth rates was 3.1 ± 0.1 mg glucose per g biomass and h, which was 3-fold lower than the mS estimated from faster-growing chemostat cultures. This difference indicated that P. pastoris reduces its maintenance energy requirement at extremely low μ, a phenomenon not previously observed in eukaryotes. Intracellular levels of glycogen and trehalose increased, while μ progressively declined during retentostat cultivation. Transcriptional reprogramming toward zero growth included the upregulation of many transcription factors as well as stress-related genes and the downregulation of cell cycle genes. This study underlines the relevance of comparative analysis of maintenance energy metabolism, which has an important impact on large-scale industrial processes. IMPORTANCE The yeast Pichia pastoris naturally lives on trees and can utilize different carbon sources, among them glucose, glycerol, and methanol. In biotechnology, it is widely used for the production of recombinant proteins. For both the understanding of life in its natural habitat and optimized production

  13. 38 CFR 4.31 - Zero percent evaluations.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 38 Pensions, Bonuses, and Veterans' Relief 1 2010-07-01 2010-07-01 false Zero percent evaluations... FOR RATING DISABILITIES General Policy in Rating § 4.31 Zero percent evaluations. In every instance where the schedule does not provide a zero percent evaluation for a diagnostic code, a zero percent...

  14. 38 CFR 4.31 - Zero percent evaluations.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 38 Pensions, Bonuses, and Veterans' Relief 1 2014-07-01 2014-07-01 false Zero percent evaluations... FOR RATING DISABILITIES General Policy in Rating § 4.31 Zero percent evaluations. In every instance where the schedule does not provide a zero percent evaluation for a diagnostic code, a zero percent...

  15. 38 CFR 4.31 - Zero percent evaluations.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 38 Pensions, Bonuses, and Veterans' Relief 1 2012-07-01 2012-07-01 false Zero percent evaluations... FOR RATING DISABILITIES General Policy in Rating § 4.31 Zero percent evaluations. In every instance where the schedule does not provide a zero percent evaluation for a diagnostic code, a zero percent...

  16. 38 CFR 4.31 - Zero percent evaluations.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 38 Pensions, Bonuses, and Veterans' Relief 1 2013-07-01 2013-07-01 false Zero percent evaluations... FOR RATING DISABILITIES General Policy in Rating § 4.31 Zero percent evaluations. In every instance where the schedule does not provide a zero percent evaluation for a diagnostic code, a zero percent...

  17. 38 CFR 4.31 - Zero percent evaluations.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 38 Pensions, Bonuses, and Veterans' Relief 1 2011-07-01 2011-07-01 false Zero percent evaluations... FOR RATING DISABILITIES General Policy in Rating § 4.31 Zero percent evaluations. In every instance where the schedule does not provide a zero percent evaluation for a diagnostic code, a zero percent...

  18. Magnetic resonance studies of atomic hydrogen at zero field and low temperature: Recombination and binding on liquid helium

    NASA Astrophysics Data System (ADS)

    Jochemsen, R.; Morrow, M.; Berlinsky, A. J.; Hardy, W. N.

    1982-07-01

    Magnetic resonance studies at zero field are reported for atomic hydrogen gas confined in a closed glass bulb with helium-coated walls for T < 1 K in a dilution refrigerator. Low-energy r.f. discharge pulses have been used to produce H atoms at temperatures as low as T = 0.06 K. The atom density nH (10 9 < nH < 10 13) measured by the strength of the free induction decay signal, follows a second-order rate equation {dn H}/{dt} = -Kn H2. At the lowest temperatures recombination is dominated by the process H + H+ wall → H 2 + wall. From the temperature dependence of the rate constant K we have determined the binding energy of H on liquid 4He and 3He, and also the cross section for recombination on the surface.

  19. Path integral Monte Carlo determination of the fourth-order virial coefficient for unitary two-component Fermi gas with zero-range interactions

    NASA Astrophysics Data System (ADS)

    Yan, Yangqian; Blume, D.

    2016-05-01

    The unitary equal-mass Fermi gas with zero-range interactions constitutes a paradigmatic model system that is relevant to atomic, condensed matter, nuclear, particle, and astro physics. This work determines the fourth-order virial coefficient b4 of such a strongly-interacting Fermi gas using a customized ab inito path integral Monte Carlo (PIMC) algorithm. In contrast to earlier theoretical results, which disagreed on the sign and magnitude of b4, our b4 agrees with the experimentally determined value, thereby resolving an ongoing literature debate. Utilizing a trap regulator, our PIMC approach determines the fourth-order virial coefficient by directly sampling the partition function. An on-the-fly anti-symmetrization avoids the Thomas collapse and, combined with the use of the exact two-body zero-range propagator, establishes an efficient general means to treat small Fermi systems with zero-range interactions. We gratefully acknowledge support by the NSF.

  20. Propagation rate constants for the peroxidation of sterols on the biosynthetic pathway to cholesterol.

    PubMed

    Lamberson, Connor R; Muchalski, Hubert; McDuffee, Kari B; Tallman, Keri A; Xu, Libin; Porter, Ned A

    2017-10-01

    The free radical chain autoxidation of cholesterol and the oxidation products formed, i.e. oxysterols, have been the focus of intensive study for decades. The peroxidation of sterol precursors to cholesterol such as 7-dehydrocholesterol (7-DHC) and desmosterol as well as their oxysterols has received less attention. The peroxidation of these sterol precursors can become important under circumstances in which genetic conditions or exposures to small molecules leads to an increase of these biosynthetic intermediates in tissues and fluids. 7-DHC, for example, has a propagation rate constant for peroxidation some 200 times that of cholesterol and this sterol is found at elevated levels in a devastating human genetic condition, Smith-Lemli-Opitz syndrome (SLOS). The propagation rate constants for peroxidation of sterol intermediates on the biosynthetic pathway to cholesterol were determined by a competition kinetic method, i.e. a peroxyl radical clock. In this work, propagation rate constants for lathosterol, zymostenol, desmosterol, 7-dehydrodesmosterol and other sterols in the Bloch and Kandutsch-Russell pathways are assigned and these rate constants are related to sterol structural features. Furthermore, potential oxysterols products are proposed for sterols whose oxysterol products have not been determined. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. The use of ordered mixtures for improving the dissolution rate of low solubility compounds.

    PubMed

    Nyström, C; Westerberg, M

    1986-03-01

    The dissolution rate of micronized griseofulvin has been investigated, both for the agglomerated raw material and the material formulated as an ordered mixture, by means of the USP XX paddle method. During the experiments, which were performed at sink condition and constant temperature, the effects of adding a surfactant and of agitation were tested. The ordered mixture with sodium chloride gave a fast dissolution rate, practically independent of the test parameters. Micronized griseofulvin alone gave dissolution profiles that were improved by adding polysorbate 80 and by increased agitation, but the dissolution rates obtained were much lower than those for the ordered mixture. It was concluded that the rate limiting step in the dissolution of griseofulvin as the raw material is the penetration of the dissolution medium into the agglomerates. With an ordered mixture, these agglomerates were deaggregated during the mixing process, producing a system in which the entire external surface area of the primary particles was exposed to the dissolution medium. This conclusion was supported by calculation of the contact surface areas taking part in the dissolution process for the systems tested. The procedure developed in this study could be applied to preformulation work where a cohesive, low solubility drug of hydrophobic nature is to be formulated.

  2. Likelihood inference of non-constant diversification rates with incomplete taxon sampling.

    PubMed

    Höhna, Sebastian

    2014-01-01

    Large-scale phylogenies provide a valuable source to study background diversification rates and investigate if the rates have changed over time. Unfortunately most large-scale, dated phylogenies are sparsely sampled (fewer than 5% of the described species) and taxon sampling is not uniform. Instead, taxa are frequently sampled to obtain at least one representative per subgroup (e.g. family) and thus to maximize diversity (diversified sampling). So far, such complications have been ignored, potentially biasing the conclusions that have been reached. In this study I derive the likelihood of a birth-death process with non-constant (time-dependent) diversification rates and diversified taxon sampling. Using simulations I test if the true parameters and the sampling method can be recovered when the trees are small or medium sized (fewer than 200 taxa). The results show that the diversification rates can be inferred and the estimates are unbiased for large trees but are biased for small trees (fewer than 50 taxa). Furthermore, model selection by means of Akaike's Information Criterion favors the true model if the true rates differ sufficiently from alternative models (e.g. the birth-death model is recovered if the extinction rate is large and compared to a pure-birth model). Finally, I applied six different diversification rate models--ranging from a constant-rate pure birth process to a decreasing speciation rate birth-death process but excluding any rate shift models--on three large-scale empirical phylogenies (ants, mammals and snakes with respectively 149, 164 and 41 sampled species). All three phylogenies were constructed by diversified taxon sampling, as stated by the authors. However only the snake phylogeny supported diversified taxon sampling. Moreover, a parametric bootstrap test revealed that none of the tested models provided a good fit to the observed data. The model assumptions, such as homogeneous rates across species or no rate shifts, appear to be

  3. Hydrolysis rate constants and activation parameters for phosphate- and phosphonate-bridged phthalonitrile monomers under acid, neutral and alkali conditions.

    PubMed

    Belsky, Kirill S; Sulimov, Artem V; Bulgakov, Boris A; Babkin, Alexandr V; Kepman, Alexey V

    2017-08-01

    Hydrolysis data for Bis(3-(3,4-dicyanophenoxy)phenyl) phenyl phosphate and Bis(3-(3,4-dicyanophenoxy)phenyl) phenylphosphonate under pH 4, 7 and 10 are presented. Conversion/time plots collected by HPLC analysis, typical chromatograms and NMR spectra of the reactions products are given. Pseudo-first order rate constants are determined for both substrates at 25, 50 and 80 °C. Activation parameters were calculated from Arrhenius equation.

  4. Path-Integral Monte Carlo Determination of the Fourth-Order Virial Coefficient for a Unitary Two-Component Fermi Gas with Zero-Range Interactions

    NASA Astrophysics Data System (ADS)

    Yan, Yangqian; Blume, D.

    2016-06-01

    The unitary equal-mass Fermi gas with zero-range interactions constitutes a paradigmatic model system that is relevant to atomic, condensed matter, nuclear, particle, and astrophysics. This work determines the fourth-order virial coefficient b4 of such a strongly interacting Fermi gas using a customized ab initio path-integral Monte Carlo (PIMC) algorithm. In contrast to earlier theoretical results, which disagreed on the sign and magnitude of b4 , our b4 agrees within error bars with the experimentally determined value, thereby resolving an ongoing literature debate. Utilizing a trap regulator, our PIMC approach determines the fourth-order virial coefficient by directly sampling the partition function. An on-the-fly antisymmetrization avoids the Thomas collapse and, combined with the use of the exact two-body zero-range propagator, establishes an efficient general means to treat small Fermi systems with zero-range interactions.

  5. Frost heave susceptibility of saturated soil under constant rate of freezing

    NASA Astrophysics Data System (ADS)

    Ryokai, K.; Iguro, M.; Yoneyama, K.

    Introduced are the results of experiments carried out to quantitatively obtain the frost heave pressure and displacement of soil subjected to artificial freezing or freezing around in-ground liquefied natural gas storage tanks. This experiment is conducted to evaluate the frost heave susceptibility of saturated soil under overconsolidation. In other words, this experiment was carried out to obtain the relation of the over-burden pressure and freezing rate to the frost heave ratio by observing the frost heave displacement and freezing time of specimens by freezing the specimens at a constant freezing rate under a constant overburden pressure, while letting water freely flow in and out of the system. Introduced are the procedures for frost heave test required to quantitatively obtain the frost heave displacement and pressure of soil. Furthermore, the relation between the frost heave susceptibility and physical properties of soil obtained by this test is reported.

  6. Measurement of Hubble constant: non-Gaussian errors in HST Key Project data

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

    Singh, Meghendra; Gupta, Shashikant; Pandey, Ashwini

    2016-08-01

    Assuming the Central Limit Theorem, experimental uncertainties in any data set are expected to follow the Gaussian distribution with zero mean. We propose an elegant method based on Kolmogorov-Smirnov statistic to test the above; and apply it on the measurement of Hubble constant which determines the expansion rate of the Universe. The measurements were made using Hubble Space Telescope. Our analysis shows that the uncertainties in the above measurement are non-Gaussian.

  7. Development of near zero-order release PLGA-based microspheres of a novel antipsychotic.

    PubMed

    Zhao, Jinlong; Wang, Lexi; Fan, Chunyu; Yu, Kongtong; Liu, Ximing; Zhao, Xiaolei; Wang, Dan; Liu, Wenhua; Su, Zhengxing; Sun, Fengying; Li, Youxin

    2017-01-10

    The novel antipsychotic isoperidone, a prodrug of paliperidone, was designed to improve liposolubility for the development of poly(D,L-lactide-co-glycolide) (PLGA)-based microspheres to achieve near zero-order release behaviour in vivo. Microspheres with a smooth surface were obtained using the oil-in-water emulsion solvent evaporation method and yielded a high encapsulation efficiency of 92%. Pharmacokinetic studies in beagle dogs showed a one-week plateau phase followed by a two-week quasi-zero-order release with no burst release. The in vitro release method with a good in vitro-in vivo correlation was also established. Pharmacodynamic evaluation was performed using the MK-801-induced schizophrenic behavioural mouse model, and the sustained suppressive effect lasted two weeks. The pharmacokinetic-pharmacodynamic (PK-PD) relationship of isoperidone microspheres was compared to that of oral administration of free drug. The results revealed a strong correlation between the plasma drug level and the antipsychotic effect. A stable drug plasma concentration was detected in mice both intraday and interday from 8 to 22 d after a single injection of isoperidone microspheres, and a sustained suppressive effect on the schizophrenic model was also observed. In comparison, the mouse group receiving oral daily administration exhibited more dose-dependent effects, and the pharmacological effect diminished rapidly in conjunction with a reduction of the plasma drug levels 8h after the last administration of isoperidone on day 3. The above results confirm the superiority of long-acting release over oral administration and indicate a valuable alternative for the clinical treatment of schizophrenia. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Ultrahigh-sensitive multimode interference-based fiber optic liquid-level sensor realized using illuminating zero-order Bessel-Gauss beam

    NASA Astrophysics Data System (ADS)

    Saha, Ardhendu; Datta, Arijit; Kaman, Surjit

    2018-03-01

    A proposal toward the enhancement in the sensitivity of a multimode interference-based fiber optic liquid-level sensor is explored analytically using a zero-order Bessel-Gauss (BG) beam as the input source. The sensor head consists of a suitable length of no-core fiber (NCF) sandwiched between two specialty high-order mode fibers. The coupling efficiency of various order modes inside the sensor structure is assessed using guided-mode propagation analysis and the performance of the proposed sensor has been benchmarked against the conventional sensor using a Gaussian beam. Furthermore, the study has been corroborated using a finite-difference beam propagation method in Lumerical's Mode Solutions software to investigate the propagation of the zero-order BG beam inside the sensor structure. Based on the simulation outcomes, the proposed scheme yields a maximum absolute sensitivity of up to 3.551 dB / mm and a sensing resolution of 2.816 × 10 - 3 mm through the choice of an appropriate length of NCF at an operating wavelength of 1.55 μm. Owing to this superior sensing performance, the reported sensing technology expedites an avenue to devise a high-performance fiber optic-level sensor that finds profound implication in different physical, biological, and chemical sensing purposes.

  9. Rate Constants and Activation Energies for Gas‐Phase Reactions of Three Cyclic Volatile Methyl Siloxanes with the Hydroxyl Radical

    PubMed Central

    Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie

    2015-01-01

    ABSTRACT Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second‐order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140‐mL gas‐phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D4 and D5 with the OH radical are 1.9 × 10−12 (95% confidence interval (CI): (1.7–2.2) × 10−12) and 2.6 × 10−12 (CI: (2.3–2.9) × 10−12) cm3 molecule−1 s−1, respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D6 is 2.8 × 10−12 (CI: (2.5–3.2) × 10−12) cm3 molecule−1 s−1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D5 were 33% higher than for D4 (CI: 30–37%), whereas the rates for D6 were only 8% higher than for D5 (CI: 5–10%). The activation energies of the reactions of D4, D5, and D6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol. PMID:27708500

  10. 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

  11. A novel condition for stable nonlinear sampled-data models using higher-order discretized approximations with zero dynamics.

    PubMed

    Zeng, Cheng; Liang, Shan; Xiang, Shuwen

    2017-05-01

    Continuous-time systems are usually modelled by the form of ordinary differential equations arising from physical laws. However, the use of these models in practice and utilizing, analyzing or transmitting these data from such systems must first invariably be discretized. More importantly, for digital control of a continuous-time nonlinear system, a good sampled-data model is required. This paper investigates the new consistency condition which is weaker than the previous similar results presented. Moreover, given the stability of the high-order approximate model with stable zero dynamics, the novel condition presented stabilizes the exact sampled-data model of the nonlinear system for sufficiently small sampling periods. An insightful interpretation of the obtained results can be made in terms of the stable sampling zero dynamics, and the new consistency condition is surprisingly associated with the relative degree of the nonlinear continuous-time system. Our controller design, based on the higher-order approximate discretized model, extends the existing methods which mainly deal with the Euler approximation. Copyright © 2017 ISA. Published by Elsevier Ltd. All rights reserved.

  12. Autostereoscopic three-dimensional display by combining a single spatial light modulator and a zero-order nulled grating

    NASA Astrophysics Data System (ADS)

    Su, Yanfeng; Cai, Zhijian; Liu, Quan; Lu, Yifan; Guo, Peiliang; Shi, Lingyan; Wu, Jianhong

    2018-04-01

    In this paper, an autostereoscopic three-dimensional (3D) display system based on synthetic hologram reconstruction is proposed and implemented. The system uses a single phase-only spatial light modulator to load the synthetic hologram of the left and right stereo images, and the parallax angle between two reconstructed stereo images is enlarged by a grating to meet the split angle requirement of normal stereoscopic vision. To realize the crosstalk-free autostereoscopic 3D display with high light utilization efficiency, the groove parameters of the grating are specifically designed by the rigorous coupled-wave theory for suppressing the zero-order diffraction, and then the zero-order nulled grating is fabricated by the holographic lithography and the ion beam etching. Furthermore, the diffraction efficiency of the fabricated grating is measured under the illumination of a laser beam with a wavelength of 532 nm. Finally, the experimental verification system for the proposed autostereoscopic 3D display is presented. The experimental results prove that the proposed system is able to generate stereoscopic 3D images with good performances.

  13. Constant-load versus heart rate-targeted exercise - Responses of systolic intervals

    NASA Technical Reports Server (NTRS)

    Lance, V. Q.; Spodick, D. H.

    1975-01-01

    Various systolic intervals were measured prior to and during heart rate-targeted bicycle ergometer exercise. There were striking similarities within each matched exercise set for Q-Im, isovolumetric contraction time, preejection period (PEP), and PEP/left ventricular ejection time (LVET). LVET was significantly shorter for rate-targeted exercise. It is concluded that either constant-load or rate-targeted bicycle ergometry may be used with the choice of method determined by the purpose of the protocol, and that systolic intervals (except LVET) should not be much altered owing to the method chosen.

  14. Meta-Analysis of Zero or Near-Zero Fluoroscopy Use During Ablation of Cardiac Arrhythmias.

    PubMed

    Yang, Li; Sun, Ge; Chen, Xiaomei; Chen, Guangzhi; Yang, Shanshan; Guo, Ping; Wang, Yan; Wang, Dao Wen

    2016-11-15

    Data regarding the efficacy and safety of zero or near-zero fluoroscopic ablation of cardiac arrhythmias are limited. A literature search was conducted using PubMed and Embase for relevant studies through January 2016. Ten studies involving 2,261 patients were identified. Compared with conventional radiofrequency ablation method, zero or near-zero fluoroscopy ablation significantly showed reduced fluoroscopic time (standard mean difference [SMD] -1.62, 95% CI -2.20 to -1.05; p <0.00001), ablation time (SMD -0.16, 95% CI -0.29 to -0.04; p = 0.01), and radiation dose (SMD -1.94, 95% CI -3.37 to -0.51; p = 0.008). In contrast, procedure duration was not significantly different from that of conventional radiofrequency ablation (SMD -0.03, 95% CI -0.16 to 0.09; p = 0.58). There were no significant differences between both groups in immediate success rate (odds ratio [OR] 0.99, 95% CI 0.49 to 2.01; p = 0.99), long-term success rate (OR 1.13, 95% CI 0.42 to 3.02; p = 0.81), complication rates (OR 0.98, 95% CI 0.49 to 1.96; p = 0.95), and recurrence rates (OR 1.29, 95% CI 0.74 to 2.24; p = 0.37). In conclusion, radiation was significantly reduced in the zero or near-zero fluoroscopy ablation groups without compromising efficacy and safety. Copyright © 2016 Elsevier Inc. All rights reserved.

  15. 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.

  16. Creatine kinase rate constant in the human heart measured with 3D‐localization at 7 tesla

    PubMed Central

    Robson, Matthew D.; Neubauer, Stefan; Rodgers, Christopher T.

    2016-01-01

    Purpose We present a new Bloch‐Siegert four Angle Saturation Transfer (BOAST) method for measuring the creatine kinase (CK) first‐order effective rate constant kf in human myocardium at 7 tesla (T). BOAST combines a variant of the four‐angle saturation transfer (FAST) method using amplitude‐modulated radiofrequency pulses, phosphorus Bloch‐Siegert B1+‐mapping to determine the per‐voxel flip angles, and nonlinear fitting to Bloch simulations for postprocessing. Methods Optimal flip angles and repetition time parameters were determined from Monte Carlo simulations. BOAST was validated in the calf muscle of two volunteers at 3T and 7T. The myocardial CK forward rate constant was then measured in 10 volunteers at 7T in 82 min (after 1H localization). Results BOAST kfCK values were 0.281 ± 0.002 s−1 in the calf and 0.35 ± 0.05 s−1 in myocardium. These are consistent with literature values from lower fields. Using a literature values for adenosine triphosphate concentration, we computed CK flux values of 4.55 ± 1.52 mmol kg−1 s−1. The sensitive volume for BOAST depends on the B1 inhomogeneity of the transmit coil. Conclusion BOAST enables measurement of the CK rate constant in the human heart at 7T, with spatial localization in three dimensions to 5.6 mL voxels, using a 10‐cm loop coil. Magn Reson Med 78:20–32, 2017. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. PMID:27579566

  17. Energy in first order 2 +1 gravity

    NASA Astrophysics Data System (ADS)

    Corichi, Alejandro; Rubalcava-García, Iraís

    2015-08-01

    We consider Λ =0 three-dimensional gravity with asymptotically flat boundary conditions. This system was studied by Ashtekar and Varadarajan within the second-order formalism—with metric variables—who showed that the Regge-Teitelboim formalism yields a consistent Hamiltonian description where, surprisingly, the energy is bounded from below and from above. The energy of the spacetime is, however, determined up to an arbitrary constant. The natural choice was to fix that freedom such that Minkowski spacetime has zero energy. More recently, Marolf and Patiño started from the Einstein-Hilbert action supplemented with the Gibbons-Hawking term and showed that, in the (2 +1 ) decomposition of the theory, the energy is shifted from the Ashtekar-Varadarajan analysis in such a way that Minkowski spacetime possesses a negative energy. In this contribution we consider the first-order formalism, where the fundamental variables are a s o (2 ,1 ) connection waIJ and a triad eaI . We consider two actions. A natural extension to 3 dimensions of the consistent action in 4 D Palatini gravity is shown to be finite and differentiable. For this action, the (2 +1 ) decomposition (that we perform using two methods) yields a Hamiltonian boundary term that corresponds to energy. It assigns zero energy to Minkowski spacetime. We then put forward a totally gauge invariant action and show that it is also well defined and differentiable. Interestingly, it turns out to be related, on shell, to the 3D Palatini action by an additive constant in such a way that its associated energy is given by the Marolf-Patiño expression. Thus, we conclude that, from the perspective of the first-order formalism, Minkowski spacetime can consistently have either zero, or a negative energy equal to -1 /4 G , depending on the choice of consistent action employed as starting point.

  18. RELATIVE RATE CONSTANTS OF CONTAMINANT CANDIDATE LIST PESTICIDES WITH HYDROXYL RADICALS

    EPA Science Inventory

    The objective of this study was to establish the rate constants for the reactions of selected pesticides listed on the US EPA Contaminant Candidate List, with UV and hydroxyl radicals (·OH). Batch experiments were conducted in phosphate buffered solution at pH 7. All pestici...

  19. Bimolecular Rate Constants for FAD-Dependent Glucose Dehydrogenase from Aspergillus terreus and Organic Electron Acceptors.

    PubMed

    Tsuruoka, Nozomu; Sadakane, Takuya; Hayashi, Rika; Tsujimura, Seiya

    2017-03-10

    The flavin adenine dinucleotide-dependent glucose dehydrogenase (FAD-GDH) from Aspergillus species require suitable redox mediators to transfer electrons from the enzyme to the electrode surface for the application of bioelectrical devices. Although several mediators for FAD-GDH are already in use, they are still far from optimum in view of potential, kinetics, sustainability, and cost-effectiveness. Herein, we investigated the efficiency of various phenothiazines and quinones in the electrochemical oxidation of FAD-GDH from Aspergillus terreus . At pH 7.0, the logarithm of the bimolecular oxidation rate constants appeared to depend on the redox potentials of all the mediators tested. Notably, the rate constant of each molecule for FAD-GDH was approximately 2.5 orders of magnitude higher than that for glucose oxidase from Aspergillus sp. The results suggest that the electron transfer kinetics is mainly determined by the formal potential of the mediator, the driving force of electron transfer, and the electron transfer distance between the redox active site of the mediator and the FAD, affected by the steric or chemical interactions. Higher k ₂ values were found for ortho-quinones than for para-quinones in the reactions with FAD-GDH and glucose oxidase, which was likely due to less steric hindrance in the active site in the case of the ortho-quinones.

  20. Multi-target QSPR modeling for simultaneous prediction of multiple gas-phase kinetic rate constants of diverse chemicals

    NASA Astrophysics Data System (ADS)

    Basant, Nikita; Gupta, Shikha

    2018-03-01

    The reactions of molecular ozone (O3), hydroxyl (•OH) and nitrate (NO3) radicals are among the major pathways of removal of volatile organic compounds (VOCs) in the atmospheric environment. The gas-phase kinetic rate constants (kO3, kOH, kNO3) are thus, important in assessing the ultimate fate and exposure risk of atmospheric VOCs. Experimental data for rate constants are not available for many emerging VOCs and the computational methods reported so far address a single target modeling only. In this study, we have developed a multi-target (mt) QSPR model for simultaneous prediction of multiple kinetic rate constants (kO3, kOH, kNO3) of diverse organic chemicals considering an experimental data set of VOCs for which values of all the three rate constants are available. The mt-QSPR model identified and used five descriptors related to the molecular size, degree of saturation and electron density in a molecule, which were mechanistically interpretable. These descriptors successfully predicted three rate constants simultaneously. The model yielded high correlations (R2 = 0.874-0.924) between the experimental and simultaneously predicted endpoint rate constant (kO3, kOH, kNO3) values in test arrays for all the three systems. The model also passed all the stringent statistical validation tests for external predictivity. The proposed multi-target QSPR model can be successfully used for predicting reactivity of new VOCs simultaneously for their exposure risk assessment.

  1. NASA Net Zero Energy Buildings Roadmap

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

    Pless, S.; Scheib, J.; Torcellini, P.

    In preparation for the time-phased net zero energy requirement for new federal buildings starting in 2020, set forth in Executive Order 13514, NASA requested that the National Renewable Energy Laboratory (NREL) to develop a roadmap for NASA's compliance. NASA detailed a Statement of Work that requested information on strategic, organizational, and tactical aspects of net zero energy buildings. In response, this document presents a high-level approach to net zero energy planning, design, construction, and operations, based on NREL's first-hand experience procuring net zero energy construction, and based on NREL and other industry research on net zero energy feasibility. The strategicmore » approach to net zero energy starts with an interpretation of the executive order language relating to net zero energy. Specifically, this roadmap defines a net zero energy acquisition process as one that sets an aggressive energy use intensity goal for the building in project planning, meets the reduced demand goal through energy efficiency strategies and technologies, then adds renewable energy in a prioritized manner, using building-associated, emission- free sources first, to offset the annual energy use required at the building; the net zero energy process extends through the life of the building, requiring a balance of energy use and production in each calendar year.« less

  2. Effects of carbonate species on the kinetics of dechlorination of 1,1,1-trichloroethane by zero-valent iron.

    PubMed

    Agrawal, Abinash; Ferguson, William J; Gardner, Bruce O; Christ, John A; Bandstra, Joel Z; Tratnyek, Paul G

    2002-10-15

    The effect of precipitates on the reactivity of iron metal (Fe0) with 1,1,1-trichloroethane (TCA) was studied in batch systems designed to model groundwaters that contain dissolved carbonate species (i.e., C(IV)). At representative concentrations for high-C(IV) groundwaters (approximately 10(-2) M), the pH in batch reactors containing Fe0 was effectively buffered until most of the aqueous C(IV) precipitated. The precipitate was mainly FeCO3 (siderite) but may also have included some carbonate green rust. Exposure of the Fe0 to dissolved C(IV) accelerated reduction of TCA, and the products formed under these conditions consisted mainly of ethane and ethene, with minor amounts of several butenes. The kinetics of TCA reduction were first-order when C(IV)-enhanced corrosion predominated but showed mixed-order kinetics (zero- and first-order) in experiments performed with passivated Fe0 (i.e., before the onset of pitting corrosion and after repassivation by precipitation of FeCO3). All these data were described by fitting a Michaelis-Menten-type kinetic model and approximating the first-order rate constant as the ratio of the maximum reaction rate (Vm) and the concentration of TCA at half of the maximum rate (K(1/2)). The decrease in Vm/K(1/2) with increasing C(IV) exposure time was fit to a heuristic model assuming proportionality between changes in TCA reduction rate and changes in surface coverage with FeCO3.

  3. Real-time association rate constant measurement using combination tapered fiber-optic biosensor (CTFOB) dip-probes

    NASA Astrophysics Data System (ADS)

    Simmonds, Boris; Wang, Chun-Wei; Kapoor, Rakesh

    2010-02-01

    This document reports a novel method of measuring association rate constant (ka) for antibody-antigen interaction using evanescent wave-based combination tapered fiber-optic biosensor (CTFOB) dip-probes. The method was demonstrated by measuring association rate constant for bovine serum albumin (BSA) and anti-BSA antibody interaction. "Direct method" was used for detection; goat anti-BSA "capture" antibodies were immobilized on the probe surfaces while the antigen (BSA) was directly labeled with Alexa 488 dye. The probes were subsequently submerged in 3nM Labeled BSA in egg albumin (1 mg/ml). The fluorescence signal recorded was proportional to BSA anti-BSA conjugates and continuous signal was acquired suing a fiber optic spectrometer (Ocean Optics, Inc.). A 476 nm diode laser was use as an excitation source. Association constant was estimated from a plot of signal as a function of time. Measured association rate constant ka for the binding of BSA with anti-BSA at room temperature is (8.33 +/- 0.01) x 104 M-1s-1.

  4. A new analytical method for estimating lumped parameter constants of linear viscoelastic models from strain rate tests

    NASA Astrophysics Data System (ADS)

    Mattei, G.; Ahluwalia, A.

    2018-04-01

    We introduce a new function, the apparent elastic modulus strain-rate spectrum, E_{app} ( \\dot{ɛ} ), for the derivation of lumped parameter constants for Generalized Maxwell (GM) linear viscoelastic models from stress-strain data obtained at various compressive strain rates ( \\dot{ɛ}). The E_{app} ( \\dot{ɛ} ) function was derived using the tangent modulus function obtained from the GM model stress-strain response to a constant \\dot{ɛ} input. Material viscoelastic parameters can be rapidly derived by fitting experimental E_{app} data obtained at different strain rates to the E_{app} ( \\dot{ɛ} ) function. This single-curve fitting returns similar viscoelastic constants as the original epsilon dot method based on a multi-curve global fitting procedure with shared parameters. Its low computational cost permits quick and robust identification of viscoelastic constants even when a large number of strain rates or replicates per strain rate are considered. This method is particularly suited for the analysis of bulk compression and nano-indentation data of soft (bio)materials.

  5. Comparison of rate constants for (PO3-) transfer by the Mg(II), Cd(II), and Li(I) forms of phosphoglucomutase.

    PubMed

    Ray, W J; Post, C B; Puvathingal, J M

    1989-01-24

    Net rate constants that define the steady-state rate through a sequence of steps and the corresponding effective energy barriers for two (PO3-)-transfer steps in the phosphoglucomutase reaction were compared as a function of metal ion, M, where M = Mg2+ and Cd2+. These steps involve the reaction of either the 1-phosphate or the 6-phosphate of glucose 1,6-bisphosphate (Glc-P2) bound to the dephosphoenzyme (ED) to produce the phosphoenzyme (EP) and the free monophosphates, glucose 1-phosphate (Glc-1-P) or glucose 6-phosphate (Glc-6-P): EP.M + Glc-1-P----ED.M.Glc-P2----EP.M.Glc-6-P6. Before this comparison was made, net rate constants for the Cd2+ enzyme, obtained at high enzyme concentration via 31P NMR saturation-transfer studies [Post, C. B., Ray, W. J., Jr., & Gorenstein, D. G. (1989) Biochemistry (preceding paper in this issue)], were appropriately scaled by using the observed constants to calculate both the expected isotope-transfer rate at equilibrium and the steady-state rate under initial velocity conditions and comparing the calculated values with those measured in dilute solution. For the Mg2+ enzyme, narrow limits on possible values of the corresponding net rate constants were imposed on the basis of initial velocity rate constants for the forward and reverse directions plus values for the equilibrium distribution of central complexes, since direct measurement is not feasible. The effective energy barriers for both the Mg2+ and Cd2+ enzymes, calculated from the respective net rate constants, together with previously values for the equilibrium distribution of complexes in both enzymic systems [Ray, W. J., Jr., & Long, J. W. (1976) Biochemistry 15, 4018-4025], show that the 100-fold decrease in the kappa cat for the Cd2+ relative to the Mg2+ enzyme is caused by two factors: the increased stability of the intermediate bisphosphate complex and the decreased ability to cope with the phosphate ester involving the 1-hydroxyl group of the glucose ring. In fact, it

  6. Carbofuran removal in continuous-photocatalytic reactor: Reactor optimization, rate-constant determination and carbofuran degradation pathway analysis.

    PubMed

    Vishnuganth, M A; Remya, Neelancherry; Kumar, Mathava; Selvaraju, N

    2017-05-04

    Carbofuran (CBF) removal in a continuous-flow photocatalytic reactor with granular activated carbon supported titanium dioxide (GAC-TiO 2 ) catalyst was investigated. The effects of feed flow rate, TiO 2 concentration and addition of supplementary oxidants on CBF removal were investigated. The central composite design (CCD) was used to design the experiments and to estimate the effects of feed flow rate and TiO 2 concentration on CBF removal. The outcome of CCD experiments demonstrated that reactor performance was influenced mainly by feed flow rate compared to TiO 2 concentration. A second-order polynomial model developed based on CCD experiments fitted the experimental data with good correlation (R 2 ∼ 0.964). The addition of 1 mL min -1 hydrogen peroxide has shown complete CBF degradation and 76% chemical oxygen demand removal under the following operating conditions of CBF ∼50 mg L -1 , TiO 2 ∼5 mg L -1 and feed flow rate ∼82.5 mL min -1 . Rate constant of the photodegradation process was also calculated by applying the kinetic data in pseudo-first-order kinetics. Four major degradation intermediates of CBF were identified using GC-MS analysis. As a whole, the reactor system and GAC-TiO 2 catalyst used could be constructive in cost-effective CBF removal with no impact to receiving environment through getaway of photocatalyst.

  7. Nonlinear zero-sum differential game analysis by singular perturbation methods

    NASA Technical Reports Server (NTRS)

    Sinar, J.; Farber, N.

    1982-01-01

    A class of nonlinear, zero-sum differential games, exhibiting time-scale separation properties, can be analyzed by singular-perturbation techniques. The merits of such an analysis, leading to an approximate game solution, as well as the 'well-posedness' of the formulation, are discussed. This approach is shown to be attractive for investigating pursuit-evasion problems; the original multidimensional differential game is decomposed to a 'simple pursuit' (free-stream) game and two independent (boundary-layer) optimal-control problems. Using multiple time-scale boundary-layer models results in a pair of uniformly valid zero-order composite feedback strategies. The dependence of suboptimal strategies on relative geometry and own-state measurements is demonstrated by a three dimensional, constant-speed example. For game analysis with realistic vehicle dynamics, the technique of forced singular perturbations and a variable modeling approach is proposed. Accuracy of the analysis is evaluated by comparison with the numerical solution of a time-optimal, variable-speed 'game of two cars' in the horizontal plane.

  8. Lie symmetries of systems of second-order linear ordinary differential equations with constant coefficients.

    PubMed

    Boyko, Vyacheslav M; Popovych, Roman O; Shapoval, Nataliya M

    2013-01-01

    Lie symmetries of systems of second-order linear ordinary differential equations with constant coefficients are exhaustively described over both the complex and real fields. The exact lower and upper bounds for the dimensions of the maximal Lie invariance algebras possessed by such systems are obtained using an effective algebraic approach.

  9. Bounding the Resource Availability of Partially Ordered Events with Constant Resource Impact

    NASA Technical Reports Server (NTRS)

    Frank, Jeremy

    2004-01-01

    We compare existing techniques to bound the resource availability of partially ordered events. We first show that, contrary to intuition, two existing techniques, one due to Laborie and one due to Muscettola, are not strictly comparable in terms of the size of the search trees generated under chronological search with a fixed heuristic. We describe a generalization of these techniques called the Flow Balance Constraint to tightly bound the amount of available resource for a set of partially ordered events with piecewise constant resource impact We prove that the new technique generates smaller proof trees under chronological search with a fixed heuristic, at little increase in computational expense. We then show how to construct tighter resource bounds but at increased computational cost.

  10. Annealed importance sampling with constant cooling rate

    NASA Astrophysics Data System (ADS)

    Giovannelli, Edoardo; Cardini, Gianni; Gellini, Cristina; Pietraperzia, Giangaetano; Chelli, Riccardo

    2015-02-01

    Annealed importance sampling is a simulation method devised by Neal [Stat. Comput. 11, 125 (2001)] to assign weights to configurations generated by simulated annealing trajectories. In particular, the equilibrium average of a generic physical quantity can be computed by a weighted average exploiting weights and estimates of this quantity associated to the final configurations of the annealed trajectories. Here, we review annealed importance sampling from the perspective of nonequilibrium path-ensemble averages [G. E. Crooks, Phys. Rev. E 61, 2361 (2000)]. The equivalence of Neal's and Crooks' treatments highlights the generality of the method, which goes beyond the mere thermal-based protocols. Furthermore, we show that a temperature schedule based on a constant cooling rate outperforms stepwise cooling schedules and that, for a given elapsed computer time, performances of annealed importance sampling are, in general, improved by increasing the number of intermediate temperatures.

  11. 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.

  12. Temperature-Dependent Rate Constants and Substituent Effects for the Reactions of Hydroxyl Radicals With Three Partially Fluorinated Ethers

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

    Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol.

  13. Lie symmetries of systems of second-order linear ordinary differential equations with constant coefficients

    PubMed Central

    Boyko, Vyacheslav M.; Popovych, Roman O.; Shapoval, Nataliya M.

    2013-01-01

    Lie symmetries of systems of second-order linear ordinary differential equations with constant coefficients are exhaustively described over both the complex and real fields. The exact lower and upper bounds for the dimensions of the maximal Lie invariance algebras possessed by such systems are obtained using an effective algebraic approach. PMID:23564972

  14. 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.

  15. Constant fields and constant gradients in open ionic channels.

    PubMed Central

    Chen, D P; Barcilon, V; Eisenberg, R S

    1992-01-01

    Ions enter cells through pores in proteins that are holes in dielectrics. The energy of interaction between ion and charge induced on the dielectric is many kT, and so the dielectric properties of channel and pore are important. We describe ionic movement by (three-dimensional) Nemst-Planck equations (including flux and net charge). Potential is described by Poisson's equation in the pore and Laplace's equation in the channel wall, allowing induced but not permanent charge. Asymptotic expansions are constructed exploiting the long narrow shape of the pore and the relatively high dielectric constant of the pore's contents. The resulting one-dimensional equations can be integrated numerically; they can be analyzed when channels are short or long (compared with the Debye length). Traditional constant field equations are derived if the induced charge is small, e.g., if the channel is short or if the total concentration gradient is zero. A constant gradient of concentration is derived if the channel is long. Plots directly comparable to experiments are given of current vs voltage, reversal potential vs. concentration, and slope conductance vs. concentration. This dielectric theory can easily be tested: its parameters can be determined by traditional constant field measurements. The dielectric theory then predicts current-voltage relations quite different from constant field, usually more linear, when gradients of total concentration are imposed. Numerical analysis shows that the interaction of ion and channel can be described by a mean potential if, but only if, the induced charge is negligible, that is to say, the electric field is spatially constant. Images FIGURE 1 PMID:1376159

  16. Zero-gravity aerosol behavior

    NASA Technical Reports Server (NTRS)

    Edwards, H. W.

    1981-01-01

    The feasibility and scientific benefits of a zero gravity aerosol study in an orbiting laboratory were examined. A macroscopic model was devised to deal with the simultaneous effects of diffusion and coagulation of particles in the confined aerosol. An analytical solution was found by treating the particle coagulation and diffusion constants as ensemble parameters and employing a transformation of variables. The solution was used to carry out simulated zero gravity aerosol decay experiments in a compact cylindrical chamber. The results demonstrate that the limitations of physical space and time imposed by the orbital situation are not prohibitive in terms of observing the history of an aerosol confined under zero gravity conditions. While the absence of convective effects would be a definite benefit for the experiment, the mathematical complexity of the problem is not greatly reduced when the gravitational term drops out of the equation. Since the model does not deal directly with the evolution of the particle size distribution, it may be desirable to develop more detailed models before undertaking an orbital experiment.

  17. Astrophysical factors: Zero energy vs most effective energy

    NASA Astrophysics Data System (ADS)

    Liolios, Theodore E.

    2001-07-01

    Effective astrophysical factors for nonresonant astrophysical nuclear reaction are usually calculated with respect to a zero-energy limit. In the present work that limit is shown to be very disadvantageous compared to the more natural effective-energy limit. The latter is used in order to modify the thermonuclear reaction rate formula in stellar evolution codes so that it takes into account both plasma and laboratory screening effects.

  18. Path-Integral Monte Carlo Determination of the Fourth-Order Virial Coefficient for a Unitary Two-Component Fermi Gas with Zero-Range Interactions.

    PubMed

    Yan, Yangqian; Blume, D

    2016-06-10

    The unitary equal-mass Fermi gas with zero-range interactions constitutes a paradigmatic model system that is relevant to atomic, condensed matter, nuclear, particle, and astrophysics. This work determines the fourth-order virial coefficient b_{4} of such a strongly interacting Fermi gas using a customized ab initio path-integral Monte Carlo (PIMC) algorithm. In contrast to earlier theoretical results, which disagreed on the sign and magnitude of b_{4}, our b_{4} agrees within error bars with the experimentally determined value, thereby resolving an ongoing literature debate. Utilizing a trap regulator, our PIMC approach determines the fourth-order virial coefficient by directly sampling the partition function. An on-the-fly antisymmetrization avoids the Thomas collapse and, combined with the use of the exact two-body zero-range propagator, establishes an efficient general means to treat small Fermi systems with zero-range interactions.

  19. Modeling crystal growth from solution with molecular dynamics simulations: approaches to transition rate constants.

    PubMed

    Reilly, Anthony M; Briesen, Heiko

    2012-01-21

    The feasibility of using the molecular dynamics (MD) simulation technique to study crystal growth from solution quantitatively, as well as to obtain transition rate constants, has been studied. The dynamics of an interface between a solution of Lennard-Jones particles and the (100) face of an fcc lattice comprised of solute particles have been studied using MD simulations, showing that MD is, in principle, capable of following growth behavior over large supersaturation and temperature ranges. Using transition state theory, and a nearest-neighbor approximation growth and dissolution rate constants have been extracted from equilibrium MD simulations at a variety of temperatures. The temperature dependence of the rates agrees well with the expected transition state theory behavior. © 2012 American Institute of Physics

  20. ESTIMATION OF PHOSPHATE ESTER HYDROLYSIS RATE CONSTANTS. II. ACID AND GENERAL BASE CATALYZED HYDROLYSIS

    EPA Science Inventory

    SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to calculate acid and neutral hydrolysis rate constants of phosphate esters in water. The rate is calculated from the energy difference between the initial and transition states of a ...

  1. Comparing Vibrationally Averaged Nuclear Shielding Constants by Quantum Diffusion Monte Carlo and Second-Order Perturbation Theory.

    PubMed

    Ng, Yee-Hong; Bettens, Ryan P A

    2016-03-03

    Using the method of modified Shepard's interpolation to construct potential energy surfaces of the H2O, O3, and HCOOH molecules, we compute vibrationally averaged isotropic nuclear shielding constants ⟨σ⟩ of the three molecules via quantum diffusion Monte Carlo (QDMC). The QDMC results are compared to that of second-order perturbation theory (PT), to see if second-order PT is adequate for obtaining accurate values of nuclear shielding constants of molecules with large amplitude motions. ⟨σ⟩ computed by the two approaches differ for the hydrogens and carbonyl oxygen of HCOOH, suggesting that for certain molecules such as HCOOH where big displacements away from equilibrium happen (internal OH rotation), ⟨σ⟩ of experimental quality may only be obtainable with the use of more sophisticated and accurate methods, such as quantum diffusion Monte Carlo. The approach of modified Shepard's interpolation is also extended to construct shielding constants σ surfaces of the three molecules. By using a σ surface with the equilibrium geometry as a single data point to compute isotropic nuclear shielding constants for each descendant in the QDMC ensemble representing the ground state wave function, we reproduce the results obtained through ab initio computed σ to within statistical noise. Development of such an approach could thereby alleviate the need for any future costly ab initio σ calculations.

  2. Zero-point corrections for isotropic coupling constants for cyclohexadienyl radical, C₆H₇ and C₆H₆Mu: beyond the bond length change approximation.

    PubMed

    Hudson, Bruce S; Chafetz, Suzanne K

    2013-04-25

    Zero-point vibrational level averaging for electron spin resonance (ESR) and muon spin resonance (µSR) hyperfine coupling constants (HFCCs) are computed for H and Mu isotopomers of the cyclohexadienyl radical. A local mode approximation previously developed for computation of the effect of replacement of H by D on ¹³C-NMR chemical shifts is used. DFT methods are used to compute the change in energy and HFCCs when the geometry is changed from the equilibrium values for the stretch and both bend degrees of freedom. This variation is then averaged over the probability distribution for each degree of freedom. The method is tested using data for the methylene group of C₆H₇, cyclohexadienyl radical and its Mu analog. Good agreement is found for the difference between the HFCCs for Mu and H of CHMu and that for H of CHMu and CH₂ of the parent radical methylene group. All three of these HFCCs are the same in the absence of the zero point average, a one-parameter fit of the static HFCC, a(0), can be computed. That value, 45.2 Gauss, is compared to the results of several fixed geometry electronic structure computations. The HFCC values for the ortho, meta and para H atoms are then discussed.

  3. Zero-field magnetic response functions in Landau levels

    PubMed Central

    Gao, Yang; Niu, Qian

    2017-01-01

    We present a fresh perspective on the Landau level quantization rule; that is, by successively including zero-field magnetic response functions at zero temperature, such as zero-field magnetization and susceptibility, the Onsager’s rule can be corrected order by order. Such a perspective is further reinterpreted as a quantization of the semiclassical electron density in solids. Our theory not only reproduces Onsager’s rule at zeroth order and the Berry phase and magnetic moment correction at first order but also explains the nature of higher-order corrections in a universal way. In applications, those higher-order corrections are expected to curve the linear relation between the level index and the inverse of the magnetic field, as already observed in experiments. Our theory then provides a way to extract the correct value of Berry phase as well as the magnetic susceptibility at zero temperature from Landau level fan diagrams in experiments. Moreover, it can be used theoretically to calculate Landau levels up to second-order accuracy for realistic models. PMID:28655849

  4. Laser Measurements of the H Atom + Ozone Rate Constant at Atmospheric Temperatures

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Smith, G. P.; Peng, J.; Reppert, K. J.; Callahan, S. L.

    2015-12-01

    The exothermic H + O3 reaction produces OH(v) Meinel band emissions, used to derive mesospheric H concentrations and chemical heating rates. We have remeasured its rate constant to reduce resulting uncertainties and the measurement extend to lower mesospheric temperatures using modern laser techniques. H atoms are produced by pulsed ultraviolet laser trace photolysis of O3, followed by reaction of O(D) with added H2. A second, delayed, frequency-mixed dye laser measures the reaction decay rate with the remaining ozone by laser induced fluorescence. We monitor either the H atom decay by 2 photon excitation at 205 nm and detection of red fluorescence, or the OH(v=9) product time evolution with excitation of the B-X (0,9) band at 237 nm and emission in blue B-A bands. By cooling the enclosed low pressure flow cell we obtained measurements from 146-305 K. Small kinetic modeling corrections are made for secondary regeneration of H atoms. The results fully confirm the current NASA JPL recommendation for this rate constant, and establish its extrapolation down to the lower temperatures of the mesosphere. This work was supported by the NSF Aeronomy Program and an NSF Physics summer REU student grant.

  5. Free Radical Chemistry of Disinfection Byproducts 2: Rate Constants and Degradation Mechanism of Trichloronitromethane (Chloropicrin)

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

    B. J. Mincher; S. K. Cole; W. J. Cooper

    2007-02-01

    Absolute rate constants for the free-radical-induced degradation of trichloronitromethane (TCNM, chloropicrin) were determined using electron pulse radiolysis and transient absorption spectroscopy. Rate constants for hydroxyl radical, OH, and hydrated electron, eaq-, reactions were (4.97 ± 0.28) × 107 M-1 s-1 and (2.13 ± 0.03) × 1010 M-1 s-1, respectively. It appears that the OH adds to the nitro-group, while the eaq- reacts via dissociative electron attachment to give two carbon centered radicals. The mechanisms of these free radical reactions with TCNM were investigated, using 60Co gamma irradiation at various absorbed doses, measuring the disappearance of TCNM and the appearance ofmore » the product nitrate and chloride ions. The rate constants and mechanistic data were combined in a kinetic computer model that was used to describe the major free radical pathways for the destruction of TCNM in solution. These data are applicable to other advanced oxidation/reduction processes.« less

  6. Unsteady flow past an airfoil pitched at constant rate

    NASA Technical Reports Server (NTRS)

    Lourenco, L.; Vandommelen, L.; Shib, C.; Krothapalli, A.

    1992-01-01

    The unsteady flow past a NACA 0012 airfoil that is undertaking a constant-rate pitching up motion is investigated experimentally by the PIDV technique in a water towing tank. The Reynolds number is 5000, based upon the airfoil's chord and the free-stream velocity. The airfoil is pitching impulsively from 0 to 30 deg. with a dimensionless pitch rate alpha of 0.131. Instantaneous velocity and associated vorticity data have been acquired over the entire flow field. The primary vortex dominates the flow behavior after it separates from the leading edge of the airfoil. Complete stall emerges after this vortex detaches from the airfoil and triggers the shedding of a counter-rotating vortex near the trailing edge. A parallel computational study using the discrete vortex, random walk approximation has also been conducted. In general, the computational results agree very well with the experiment.

  7. Linear free energy relationships between aqueous phase hydroxyl radical reaction rate constants and free energy of activation.

    PubMed

    Minakata, Daisuke; Crittenden, John

    2011-04-15

    The hydroxyl radical (HO(•)) is a strong oxidant that reacts with electron-rich sites on organic compounds and initiates complex radical chain reactions in aqueous phase advanced oxidation processes (AOPs). Computer based kinetic modeling requires a reaction pathway generator and predictions of associated reaction rate constants. Previously, we reported a reaction pathway generator that can enumerate the most important elementary reactions for aliphatic compounds. For the reaction rate constant predictor, we develop linear free energy relationships (LFERs) between aqueous phase literature-reported HO(•) reaction rate constants and theoretically calculated free energies of activation for H-atom abstraction from a C-H bond and HO(•) addition to alkenes. The theoretical method uses ab initio quantum mechanical calculations, Gaussian 1-3, for gas phase reactions and a solvation method, COSMO-RS theory, to estimate the impact of water. Theoretically calculated free energies of activation are found to be within approximately ±3 kcal/mol of experimental values. Considering errors that arise from quantum mechanical calculations and experiments, this should be within the acceptable errors. The established LFERs are used to predict the HO(•) reaction rate constants within a factor of 5 from the experimental values. This approach may be applied to other reaction mechanisms to establish a library of rate constant predictions for kinetic modeling of AOPs.

  8. 10 CFR 217.32 - Elements of a rated order.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 3 2013-01-01 2013-01-01 false Elements of a rated order. 217.32 Section 217.32 Energy DEPARTMENT OF ENERGY OIL ENERGY PRIORITIES AND ALLOCATIONS SYSTEM Placement of Rated Orders § 217.32 Elements of a rated order. Each rated order must include: (a) The appropriate priority rating (e.g. DO-F1 or...

  9. 10 CFR 217.32 - Elements of a rated order.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 3 2012-01-01 2012-01-01 false Elements of a rated order. 217.32 Section 217.32 Energy DEPARTMENT OF ENERGY OIL ENERGY PRIORITIES AND ALLOCATIONS SYSTEM Placement of Rated Orders § 217.32 Elements of a rated order. Each rated order must include: (a) The appropriate priority rating (e.g. DO-F1 or...

  10. 10 CFR 217.32 - Elements of a rated order.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 3 2014-01-01 2014-01-01 false Elements of a rated order. 217.32 Section 217.32 Energy DEPARTMENT OF ENERGY OIL ENERGY PRIORITIES AND ALLOCATIONS SYSTEM Placement of Rated Orders § 217.32 Elements of a rated order. Each rated order must include: (a) The appropriate priority rating (e.g. DO-F1 or...

  11. Zero-order delivery of a highly soluble, low dose drug alfuzosin hydrochloride via gastro-retentive system.

    PubMed

    Liu, Quan; Fassihi, Reza

    2008-02-04

    A composite gastro-retentive matrix for zero-order delivery of highly soluble drug alfuzosin hydrochloride (10mg) has been designed and characterized. Two systems containing polyethylene oxide (PEO), hydroxypropylmethylcellulose (HPMC), sodium bicarbonate, citric acid and polyvinyl pyrrolidone were dry blended and compressed into triple layer and bi-layer composite matrices. Dissolution studies using the USP 27 paddle method at 100 and 50rpm in pH 2.0 and 6.8 were performed using UV spectroscopy at 244nm, with automatic sampling over a 24h period using a marketed product as a reference to calculate the "f(2)" factor. Textural characteristics of each layer, the composite matrix as a whole, and floatation potential were determined under conditions similar to dissolution. Percent matrix swelling and erosion along with digital images were also obtained. Both systems proved to be effective in providing prolonged floatation, zero-order release, and complete disentanglement and erosion based on the analysis of data with "f(2)" of 68 and 71 for PEO and HPMC based systems, respectively. The kinetics of drug release, swelling and erosion, and dynamics of textural changes during dissolution for the designed composite systems offer a novel approach for developing gastro-retentive drug delivery system that has potential to enhance bioavailability and site-specific delivery to the proximal small intestine.

  12. Constant growth rate can be supported by decreasing energy flux and increasing aerobic glycolysis.

    PubMed

    Slavov, Nikolai; Budnik, Bogdan A; Schwab, David; Airoldi, Edoardo M; van Oudenaarden, Alexander

    2014-05-08

    Fermenting glucose in the presence of enough oxygen to support respiration, known as aerobic glycolysis, is believed to maximize growth rate. We observed increasing aerobic glycolysis during exponential growth, suggesting additional physiological roles for aerobic glycolysis. We investigated such roles in yeast batch cultures by quantifying O2 consumption, CO2 production, amino acids, mRNAs, proteins, posttranslational modifications, and stress sensitivity in the course of nine doublings at constant rate. During this course, the cells support a constant biomass-production rate with decreasing rates of respiration and ATP production but also decrease their stress resistance. As the respiration rate decreases, so do the levels of enzymes catalyzing rate-determining reactions of the tricarboxylic-acid cycle (providing NADH for respiration) and of mitochondrial folate-mediated NADPH production (required for oxidative defense). The findings demonstrate that exponential growth can represent not a single metabolic/physiological state but a continuum of changing states and that aerobic glycolysis can reduce the energy demands associated with respiratory metabolism and stress survival. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

  13. On the Composition of Public-Coin Zero-Knowledge Protocols

    DTIC Science & Technology

    2011-05-31

    only languages in BPP have public-coin black-box zero-knowledge protocols that are secure under an unbounded (polynomial) number of parallel...only languages in BPP have public-coin black-box zero-knowledge protocols that are secure under an unbounded (polynomial) number of parallel repetitions...and Krawczyk [GK96b] show that only languages in BPP have constant-round public-coin (stand-alone) black-box ZK protocols with negligible soundness

  14. The Conformal Factor and the Cosmological Constant

    NASA Astrophysics Data System (ADS)

    Giddings, Steven B.

    The issue of the conformal factor in quantum gravity is examined for Lorentzian signature spacetimes. In Euclidean signature, the “wrong” sign of the conformal action makes the path integral undefined, but in Lorentzian signature this sign is tied to the instability of gravity and once this is accounted for the path integral should be well-defined. In this approach it is not obvious that the Baum-Hawking-Coleman mechanism for suppression of the cosmological constant functions. It is conceivable that since the multiuniverse system exhibits an instability for positive cosmological constant, the dynamics should force the system to zero cosmological constant.

  15. Microfabricated microengine with constant rotation rate

    DOEpatents

    Romero, Louis A.; Dickey, Fred M.

    1999-01-01

    A microengine uses two synchronized linear actuators as a power source and converts oscillatory motion from the actuators into constant rotational motion via direct linkage connection to an output gear or wheel. The microengine provides output in the form of a continuously rotating output gear that is capable of delivering drive torque at a constant rotation to a micromechanism. The output gear can have gear teeth on its outer perimeter for directly contacting a micromechanism requiring mechanical power. The gear is retained by a retaining means which allows said gear to rotate freely. The microengine is microfabricated of polysilicon on one wafer using surface micromachining batch fabrication.

  16. Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether

    NASA Technical Reports Server (NTRS)

    DeMore, W.; Bayes, K.

    1998-01-01

    Relative rate experiements were used to measure rate constants and temperature denpendencies of the reactions of OH with propane, n-butane, n-pentane, n-hexane, cyclopropane, cyclobutane, cyclopentane, and dimethyl ether.

  17. Creatine kinase rate constant in the human heart measured with 3D-localization at 7 tesla.

    PubMed

    Clarke, William T; Robson, Matthew D; Neubauer, Stefan; Rodgers, Christopher T

    2017-07-01

    We present a new Bloch-Siegert four Angle Saturation Transfer (BOAST) method for measuring the creatine kinase (CK) first-order effective rate constant k f in human myocardium at 7 tesla (T). BOAST combines a variant of the four-angle saturation transfer (FAST) method using amplitude-modulated radiofrequency pulses, phosphorus Bloch-Siegert B1+-mapping to determine the per-voxel flip angles, and nonlinear fitting to Bloch simulations for postprocessing. Optimal flip angles and repetition time parameters were determined from Monte Carlo simulations. BOAST was validated in the calf muscle of two volunteers at 3T and 7T. The myocardial CK forward rate constant was then measured in 10 volunteers at 7T in 82 min (after 1 H localization). BOAST kfCK values were 0.281 ± 0.002 s -1 in the calf and 0.35 ± 0.05 s -1 in myocardium. These are consistent with literature values from lower fields. Using a literature values for adenosine triphosphate concentration, we computed CK flux values of 4.55 ± 1.52 mmol kg -1 s -1 . The sensitive volume for BOAST depends on the B 1 inhomogeneity of the transmit coil. BOAST enables measurement of the CK rate constant in the human heart at 7T, with spatial localization in three dimensions to 5.6 mL voxels, using a 10-cm loop coil. Magn Reson Med 78:20-32, 2017. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine.

  18. 49 CFR 33.32 - Elements of a rated order.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 1 2014-10-01 2014-10-01 false Elements of a rated order. 33.32 Section 33.32 Transportation Office of the Secretary of Transportation TRANSPORTATION PRIORITIES AND ALLOCATION SYSTEM Placement of Rated Orders § 33.32 Elements of a rated order. Each rated order must include: (a) The...

  19. 49 CFR 33.32 - Elements of a rated order.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 1 2012-10-01 2012-10-01 false Elements of a rated order. 33.32 Section 33.32 Transportation Office of the Secretary of Transportation TRANSPORTATION PRIORITIES AND ALLOCATION SYSTEM Placement of Rated Orders § 33.32 Elements of a rated order. Each rated order must include: (a) The...

  20. 49 CFR 33.32 - Elements of a rated order.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 1 2013-10-01 2013-10-01 false Elements of a rated order. 33.32 Section 33.32 Transportation Office of the Secretary of Transportation TRANSPORTATION PRIORITIES AND ALLOCATION SYSTEM Placement of Rated Orders § 33.32 Elements of a rated order. Each rated order must include: (a) The...

  1. Rate constants for OH with selected large alkanes : shock-tube measurements and an improved group scheme.

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

    Sivaramakrishnan, R.; Michael, J. V.; Chemical Sciences and Engineering Division

    High-temperature rate constant experiments on OH with the five large (C{sub 5}-C{sub 8}) saturated hydrocarbons n-heptane, 2,2,3,3-tetramethylbutane (2,2,3,3-TMB), n-pentane, n-hexane, and 2,3-dimethylbutane (2,3-DMB) were performed with the reflected-shock-tube technique using multipass absorption spectrometric detection of OH radicals at 308 nm. Single-point determinations at {approx}1200 K on n-heptane, 2,2,3,3-TMB, n-hexane, and 2,3-DMB were previously reported by Cohen and co-workers; however, the present work substantially extends the database to both lower and higher temperature. The present experiments span a wide temperature range, 789-1308 K, and represent the first direct measurements of rate constants at T > 800 K for n-pentane. The presentmore » work utilized 48 optical passes corresponding to a total path length of {approx}4.2 m. As a result of this increased path length, the high OH concentration detection sensitivity permitted pseudo-first-order analyses for unambiguously measuring rate constants. The experimental results can be expressed in Arrhenius form in units of cm{sup 3} molecule{sup -1} s{sup -1} as follows: K{sub OH+n-heptane} = (2.48 {+-} 0.17) x 10{sup -10} exp[(-1927 {+-} 69 K)/T] (838-1287 K); k{sub OH+2,2,3,3-TMB} = (8.26 {+-} 0.89) x 10{sup -11} exp[(-1337 {+-} 94 K)/T] (789-1061 K); K{sub OH+n-pentane} = (1.60 {+-} 0.25) x 10{sup -10} exp[(-1903 {+-} 146 K)/T] (823-1308 K); K{sub OH+n-hexane} = (2.79 {+-} 0.39) x 10{sup -10} exp[(-2301 {+-} 134 K)/T] (798-1299 K); and k{sub OH+2,3-DMB} = (1.27 {+-} 0.16) x 10{sup -10} exp[(-1617 {+-} 118 K)/T] (843-1292 K). The available experimental data, along with lower-T determinations, were used to obtain evaluations of the experimental rate constants over the temperature range from {approx}230 to 1300 K for most of the title reactions. These extended-temperature-range evaluations, given as three-parameter fits, are as follows: k{sub OH+n-heptane} = 2.059 x 10{sup -5}T{sup 1.401} exp(33 K

  2. Absolute rate constant for the O plus NO chemiluminescence in the near infrared

    NASA Technical Reports Server (NTRS)

    Golde, M. F.; Roche, A. E.; Kaufman, F.

    1973-01-01

    Infrared chemiluminescence from the process O + NO (+M) NO2 + hv (+M) has been studied between 1.3 and 4.1 micrometer. The wavelength dependence of the continuum between 1.3 and 3.3 micrometer is in fair agreement with previous studies and the measured radiative rate constant at 1.51 micrometer establishes the NO-O glow in this spectral range as a secondary emission standard. Comparison with previous studies of the visible region of the glow implies that the overall radiative rate constant lies in the range (9.4 to 11.2) x 10 to the minus 17 power cu cm sec/1. In the region 3.3 to 4.1 micrometer, the previously observed broad band, peaking at 3.7 micrometer, shows a complex kinetic dependence on O and M.

  3. Maintenance of order in a moving strong condensate

    NASA Astrophysics Data System (ADS)

    Whitehouse, Justin; Costa, André; Blythe, Richard A.; Evans, Martin R.

    2014-11-01

    We investigate the conditions under which a moving condensate may exist in a driven mass transport system. Our paradigm is a minimal mass transport model in which n - 1 particles move simultaneously from a site containing n > 1 particles to the neighbouring site in a preferred direction. In the spirit of a zero-range process the rate u(n) of this move depends only on the occupation of the departure site. We study a hopping rate u(n) = 1 + b/nα numerically and find a moving strong condensate phase for b > bc(α) for all α > 0. This phase is characterised by a condensate that moves through the system and comprises a fraction of the system's mass that tends to unity. The mass lost by the condensate as it moves is constantly replenished from the trailing tail of low occupancy sites that collectively comprise a vanishing fraction of the mass. We formulate an approximate analytical treatment of the model that allows a reasonable estimate of bc(α) to be obtained. We show numerically (for α = 1) that the transition is of mixed order, exhibiting a discontinuity in the order parameter as well as a diverging length scale as b\\searrow bc .

  4. Zero-Point Energy Constraint for Unimolecular Dissociation Reactions. Giving Trajectories Multiple Chances To Dissociate Correctly.

    PubMed

    Paul, Amit K; Hase, William L

    2016-01-28

    A zero-point energy (ZPE) constraint model is proposed for classical trajectory simulations of unimolecular decomposition and applied to CH4* → H + CH3 decomposition. With this model trajectories are not allowed to dissociate unless they have ZPE in the CH3 product. If not, they are returned to the CH4* region of phase space and, if necessary, given additional opportunities to dissociate with ZPE. The lifetime for dissociation of an individual trajectory is the time it takes to dissociate with ZPE in CH3, including multiple possible returns to CH4*. With this ZPE constraint the dissociation of CH4* is exponential in time as expected for intrinsic RRKM dynamics and the resulting rate constant is in good agreement with the harmonic quantum value of RRKM theory. In contrast, a model that discards trajectories without ZPE in the reaction products gives a CH4* → H + CH3 rate constant that agrees with the classical and not quantum RRKM value. The rate constant for the purely classical simulation indicates that anharmonicity may be important and the rate constant from the ZPE constrained classical trajectory simulation may not represent the complete anharmonicity of the RRKM quantum dynamics. The ZPE constraint model proposed here is compared with previous models for restricting ZPE flow in intramolecular dynamics, and connecting product and reactant/product quantum energy levels in chemical dynamics simulations.

  5. Toward an understanding of the turbidity measurement of heterocoagulation rate constants of dispersions containing particles of different sizes.

    PubMed

    Liu, Jie; Xu, Shenghua; Sun, Zhiwei

    2007-11-06

    Our previous studies have shown that the determination of coagulation rate constants by turbidity measurement becomes impossible for a certain operating wavelength (that is, its blind point) because at this wavelength the change in the turbidity of a dispersion completely loses its response to the coagulation process. Therefore, performing the turbidity measurement in the wavelength range near the blind point should be avoided. In this article, we demonstrate that the turbidity measurement of the rate constant for coagulation of a binary dispersion containing particles of two different sizes (heterocoagulation) presents special difficulties because the blind point shifts with not only particle size but also with the component fraction. Some important aspects of the turbidity measurement for the heterocoagulation rate constant are discussed and experimentally tested. It is emphasized that the T-matrix method can be used to correctly evaluate extinction cross sections of doublets formed during the heterocoagulation process, which is the key data determining the rate constant from the turbidity measurement, and choosing the appropriate operating wavelength and component fraction are important to achieving a more accurate rate constant. Finally, a simple scheme in experimentally determining the sensitivity of the turbidity changes with coagulation over a wavelength range is proposed.

  6. Near-field spectral shift of a zero-order Bessel beam scattered from a spherical particle

    NASA Astrophysics Data System (ADS)

    Chen, Feinan; Li, Jia; Belafhal, Abdelmajid; Chafiq, Abdelghani; Sun, Xiaobing

    2018-06-01

    Within the accuracy of the first-order Born approximation, expressions are derived for the near-zone spectrum of a zero-order Bessel beam scattered from a spherical particle whose correlation function satisfies a Gaussian distribution. The dependence of the spectral shift and spectral switch of the scattered field on the effective size of the scattering potential (ESSP) are determined by numerical simulations. It is shown that the spectral shift of the scattered field does not occur along the longitudinal propagation direction. Furthermore, when the medium’s ESSP is comparable with the central wavelength of the beam, the spectrum of the scattered field loses the Gaussian distribution and exhibits a blue shift as the reference point sufficiently far away from central origin. These results may have prospective applications in guiding tiny particles when the near-zone spectrums of scattered beams are captured and analyzed.

  7. Dissolution rate enhancement of gliclazide by ordered mixing.

    PubMed

    Saharan, Vikas A; Choudhury, Pratim K

    2011-09-01

    The poorly water soluble antidiabetic drug gliclazide was selected to study the effect of excipients on dissolution rate enhancement. Ordered mixtures of micronized gliclazide with lactose, mannitol, sorbitol, maltitol and sodium chloride were prepared by manual shaking of glass vials containing the drug and excipient(s). Different water soluble excipients, addition of surfactant and superdisintegrant, drug concentration and carrier particle size influenced the dissolution rate of the drug. Dissolution rate studies of the prepared ordered mixtures revealed an increase in drug dissolution with all water soluble excipients. The order of dissolution rate improvement for gliclazide was mannitol > lactose > maltitol > sorbitol > sodium chloride. Composite granules of the particle size range 355-710 μm were superior in increasing the drug dissolution rate from ordered mixtures. Reducing the carrier particle size decreased the dissolution rate of the drug as well as the increase in drug concentration. Kinetic modeling of drug release data fitted best the Hixson-Crowell model, which indicates that all the ordered mixture formulations followed the cube root law fairly well.

  8. 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.

  9. Synthesis, Characterization, and Sensitivity Analysis of Urea Nitrate (UN)

    DTIC Science & Technology

    2015-04-01

    of the line is the rate of the reaction for the corresponding temperature. The equations for the zero order reaction and half- life equation follow...rate law (k is rate constant; [A] is the concentration of UN) Rate = k[A]n . (1) Eq. 2 shows the half-life (t½) equation for a zero order reaction...MGMT 1 GOVT PRINTG OFC (PDF) A MALHOTRA 2 WEAPONS DEV & (PDF) INTEGRATION DIRCTRT AMRDEC RDMR WDN J NEIDERT G DRAKE

  10. 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.

  11. On the Asymmetric Zero-Range in the Rarefaction Fan

    NASA Astrophysics Data System (ADS)

    Gonçalves, Patrícia

    2014-02-01

    We consider one-dimensional asymmetric zero-range processes starting from a step decreasing profile leading, in the hydrodynamic limit, to the rarefaction fan of the associated hydrodynamic equation. Under that initial condition, and for totally asymmetric jumps, we show that the weighted sum of joint probabilities for second class particles sharing the same site is convergent and we compute its limit. For partially asymmetric jumps, we derive the Law of Large Numbers for a second class particle, under the initial configuration in which all positive sites are empty, all negative sites are occupied with infinitely many first class particles and there is a single second class particle at the origin. Moreover, we prove that among the infinite characteristics emanating from the position of the second class particle it picks randomly one of them. The randomness is given in terms of the weak solution of the hydrodynamic equation, through some sort of renormalization function. By coupling the constant-rate totally asymmetric zero-range with the totally asymmetric simple exclusion, we derive limiting laws for more general initial conditions.

  12. Graviton fluctuations erase the cosmological constant

    NASA Astrophysics Data System (ADS)

    Wetterich, C.

    2017-10-01

    Graviton fluctuations induce strong non-perturbative infrared renormalization effects for the cosmological constant. The functional renormalization flow drives a positive cosmological constant towards zero, solving the cosmological constant problem without the need to tune parameters. We propose a simple computation of the graviton contribution to the flow of the effective potential for scalar fields. Within variable gravity, with effective Planck mass proportional to the scalar field, we find that the potential increases asymptotically at most quadratically with the scalar field. The solutions of the derived cosmological equations lead to an asymptotically vanishing cosmological "constant" in the infinite future, providing for dynamical dark energy in the present cosmological epoch. Beyond a solution of the cosmological constant problem, our simplified computation also entails a sizeable positive graviton-induced anomalous dimension for the quartic Higgs coupling in the ultraviolet regime, substantiating the successful prediction of the Higgs boson mass within the asymptotic safety scenario for quantum gravity.

  13. Accurate acceleration of kinetic Monte Carlo simulations through the modification of rate constants.

    PubMed

    Chatterjee, Abhijit; Voter, Arthur F

    2010-05-21

    We present a novel computational algorithm called the accelerated superbasin kinetic Monte Carlo (AS-KMC) method that enables a more efficient study of rare-event dynamics than the standard KMC method while maintaining control over the error. In AS-KMC, the rate constants for processes that are observed many times are lowered during the course of a simulation. As a result, rare processes are observed more frequently than in KMC and the time progresses faster. We first derive error estimates for AS-KMC when the rate constants are modified. These error estimates are next employed to develop a procedure for lowering process rates with control over the maximum error. Finally, numerical calculations are performed to demonstrate that the AS-KMC method captures the correct dynamics, while providing significant CPU savings over KMC in most cases. We show that the AS-KMC method can be employed with any KMC model, even when no time scale separation is present (although in such cases no computational speed-up is observed), without requiring the knowledge of various time scales present in the system.

  14. Application of first order rate kinetics to explain changes in bloom toxicity—the importance of understanding cell toxin quotas

    NASA Astrophysics Data System (ADS)

    Orr, Philip T.; Willis, Anusuya; Burford, Michele A.

    2018-04-01

    Cyanobacteria are oxygenic photosynthetic Gram-negative bacteria that can form potentially toxic blooms in eutrophic and slow flowing aquatic ecosystems. Bloom toxicity varies spatially and temporally, but understanding the mechanisms that drive these changes remains largely a mystery. Changes in bloom toxicity may result from changes in intracellular toxin pool sizes of cyanotoxins with differing molecular toxicities, and/or from changes in the cell concentrations of toxic and non-toxic cyanobacterial species or strains within bloom populations. We show here how first-order rate kinetics at the cellular level can be used to explain how environmental conditions drive changes in bloom toxicity at the ecological level. First order rate constants can be calculated for changes in cell concentration (μ c: specific cell division rate) or the volumetric biomass concentration (μ g: specific growth rate) between short time intervals throughout the cell cycle. Similar first order rate constants can be calculated for changes in nett volumetric cyanotoxin concentration (μ tox: specific cyanotoxin production rate) over similar time intervals. How μ c (or μ g ) covaries with μ tox over the cell cycle shows conclusively when cyanotoxins are being produced and metabolised, and how the toxicity of cells change in response to environment stressors. When μ tox/μ c>1, cyanotoxin cell quotas increase and individual cells become more toxic because the nett cyanotoxin production rate is higher than the cell division rate. When μ tox/μ c=1, cell cyanotoxin quotas remains fixed because the nett cyanotoxin production rate matches the cell division rate. When μ tox/μ c<1, the cyanotoxin cell quota decreases because either the nett cyanotoxin production rate is lower than the cell division rate, or metabolic breakdown and/or secretion of cyanotoxins is occurring. These fundamental equations describe cyanotoxin metabolism dynamics at the cellular level and provide the necessary

  15. Reaction of H2 with O2 in Excited Electronic States: Reaction Pathways and Rate Constants.

    PubMed

    Pelevkin, Alexey V; Loukhovitski, Boris I; Sharipov, Alexander S

    2017-12-21

    Comprehensive quantum chemical analysis with the use of the multireference state-averaged complete active space self-consistent field approach was carried out to study the reactions of H 2 with O 2 in a 1 Δ g , b 1 Σ g + , c 1 Σ u - , and A' 3 Δ u electronically excited states. The energetically favorable reaction pathways and possible intersystem crossings have been revealed. The energy barriers were refined employing the extended multiconfiguration quasi-degenerate second-order perturbation theory. It has been shown that the interaction of O 2 (a 1 Δ g ) and O 2 (A' 3 Δ u ) with H 2 occurs through the H-abstraction process with relatively low activation barriers that resulted in the formation of the HO 2 molecule in A″ and A' electronic states, respectively. Meanwhile, molecular oxygen in singlet sigma states (b 1 Σ g + and c 1 Σ u - ) was proved to be nonreactive with respect to the molecular hydrogen. Appropriate rate constants for revealed reaction and quenching channels have been estimated using variational transition-state theory including corrections for the tunneling effect, possible nonadiabatic transitions, and anharmonicity of vibrations for transition states and reactants. It was demonstrated that the calculated reaction rate constant for the H 2 + O 2 (a 1 Δ g ) process is in reasonable agreement with known experimental data. The Arrhenius approximations for these processes have been proposed for the temperature range T = 300-3000 K.

  16. Zero-voltage DC/DC converter with asymmetric pulse-width modulation for DC micro-grid system

    NASA Astrophysics Data System (ADS)

    Lin, Bor-Ren

    2018-04-01

    This paper presents a zero-voltage switching DC/DC converter for DC micro-grid system applications. The proposed circuit includes three half-bridge circuit cells connected in primary-series and secondary-parallel in order to lessen the voltage rating of power switches and current rating of rectifier diodes. Thus, low voltage stress of power MOSFETs can be adopted for high-voltage input applications with high switching frequency operation. In order to achieve low switching losses and high circuit efficiency, asymmetric pulse-width modulation is used to turn on power switches at zero voltage. Flying capacitors are used between each circuit cell to automatically balance input split voltages. Therefore, the voltage stress of each power switch is limited at Vin/3. Finally, a prototype is constructed and experiments are provided to demonstrate the circuit performance.

  17. Acoustic emission of rock mass under the constant-rate fluid injection

    NASA Astrophysics Data System (ADS)

    Shadrin Klishin, AV, VI

    2018-03-01

    The authors study acoustic emission in coal bed and difficult-to-cave roof under injection of fluid by pumps at a constant rate. The functional connection between the roof hydrofracture length and the total number of AE pulses is validated, it is also found that the coal bed hydroloosening time, injection rate and time behavior of acoustic emission activity depend on the fluid injection volume required until the fluid breakout in a roadway through growing fractures. In the formulas offered for the practical application, integral parameters that characterize permeability and porosity of rock mass and process parameters of the technology are found during test injection.

  18. High-Order Model and Dynamic Filtering for Frame Rate Up-Conversion.

    PubMed

    Bao, Wenbo; Zhang, Xiaoyun; Chen, Li; Ding, Lianghui; Gao, Zhiyong

    2018-08-01

    This paper proposes a novel frame rate up-conversion method through high-order model and dynamic filtering (HOMDF) for video pixels. Unlike the constant brightness and linear motion assumptions in traditional methods, the intensity and position of the video pixels are both modeled with high-order polynomials in terms of time. Then, the key problem of our method is to estimate the polynomial coefficients that represent the pixel's intensity variation, velocity, and acceleration. We propose to solve it with two energy objectives: one minimizes the auto-regressive prediction error of intensity variation by its past samples, and the other minimizes video frame's reconstruction error along the motion trajectory. To efficiently address the optimization problem for these coefficients, we propose the dynamic filtering solution inspired by video's temporal coherence. The optimal estimation of these coefficients is reformulated into a dynamic fusion of the prior estimate from pixel's temporal predecessor and the maximum likelihood estimate from current new observation. Finally, frame rate up-conversion is implemented using motion-compensated interpolation by pixel-wise intensity variation and motion trajectory. Benefited from the advanced model and dynamic filtering, the interpolated frame has much better visual quality. Extensive experiments on the natural and synthesized videos demonstrate the superiority of HOMDF over the state-of-the-art methods in both subjective and objective comparisons.

  19. Application of an Artificial Neural Network to the Prediction of OH Radical Reaction Rate Constants for Evaluating Global Warming Potential.

    PubMed

    Allison, Thomas C

    2016-03-03

    Rate constants for reactions of chemical compounds with hydroxyl radical are a key quantity used in evaluating the global warming potential of a substance. Experimental determination of these rate constants is essential, but it can also be difficult and time-consuming to produce. High-level quantum chemistry predictions of the rate constant can suffer from the same issues. Therefore, it is valuable to devise estimation schemes that can give reasonable results on a variety of chemical compounds. In this article, the construction and training of an artificial neural network (ANN) for the prediction of rate constants at 298 K for reactions of hydroxyl radical with a diverse set of molecules is described. Input to the ANN consists of counts of the chemical bonds and bends present in the target molecule. The ANN is trained using 792 (•)OH reaction rate constants taken from the NIST Chemical Kinetics Database. The mean unsigned percent error (MUPE) for the training set is 12%, and the MUPE of the testing set is 51%. It is shown that the present methodology yields rate constants of reasonable accuracy for a diverse set of inputs. The results are compared to high-quality literature values and to another estimation scheme. This ANN methodology is expected to be of use in a wide range of applications for which (•)OH reaction rate constants are required. The model uses only information that can be gathered from a 2D representation of the molecule, making the present approach particularly appealing, especially for screening applications.

  20. Transient signal isotope analysis: validation of the method for isotope signal synchronization with the determination of amplifier first-order time constants.

    PubMed

    Gourgiotis, Alkiviadis; Manhès, Gérard; Louvat, Pascale; Moureau, Julien; Gaillardet, Jérôme

    2015-09-30

    During transient signal acquisition by Multi-Collection Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS), an isotope ratio increase or decrease (isotopic drift hereafter) is often observed which is related to the different time responses of the amplifiers involved in multi-collection. This isotopic drift affects the quality of the isotopic data and, in a recent study, a method of internal amplifier signal synchronization for isotope drift correction was proposed. In this work the determination of the amplifier time constants was investigated in order to validate the method of internal amplifier signal synchronization for isotope ratio drift correction. Two different MC-ICPMS instruments, the Neptune and the Neptune Plus, were used, and both the lead transient signals and the signal decay curves of the amplifiers were investigated. Our results show that the first part of the amplifier signal decay curve is characterized by a pure exponential decay. This part of the signal decay was used for the effective calculation of the amplifier first-order time constants. The small differences between these time constants were compared with time lag values obtained from the method of isotope signal synchronization and were found to be in good agreement. This work proposes a way of determining amplifier first-order time constants. We show that isotopic drift is directly related to the amplifier first-order time constants and the method of internal amplifier signal synchronization for isotope ratio drift correction is validated. Copyright © 2015 John Wiley & Sons, Ltd.

  1. Nonparametric change point estimation for survival distributions with a partially constant hazard rate.

    PubMed

    Brazzale, Alessandra R; Küchenhoff, Helmut; Krügel, Stefanie; Schiergens, Tobias S; Trentzsch, Heiko; Hartl, Wolfgang

    2018-04-05

    We present a new method for estimating a change point in the hazard function of a survival distribution assuming a constant hazard rate after the change point and a decreasing hazard rate before the change point. Our method is based on fitting a stump regression to p values for testing hazard rates in small time intervals. We present three real data examples describing survival patterns of severely ill patients, whose excess mortality rates are known to persist far beyond hospital discharge. For designing survival studies in these patients and for the definition of hospital performance metrics (e.g. mortality), it is essential to define adequate and objective end points. The reliable estimation of a change point will help researchers to identify such end points. By precisely knowing this change point, clinicians can distinguish between the acute phase with high hazard (time elapsed after admission and before the change point was reached), and the chronic phase (time elapsed after the change point) in which hazard is fairly constant. We show in an extensive simulation study that maximum likelihood estimation is not robust in this setting, and we evaluate our new estimation strategy including bootstrap confidence intervals and finite sample bias correction.

  2. Wormholes and the cosmological constant problem.

    NASA Astrophysics Data System (ADS)

    Klebanov, I.

    The author reviews the cosmological constant problem and the recently proposed wormhole mechanism for its solution. Summation over wormholes in the Euclidean path integral for gravity turns all the coupling parameters into dynamical variables, sampled from a probability distribution. A formal saddle point analysis results in a distribution with a sharp peak at the cosmological constant equal to zero, which appears to solve the cosmological constant problem. He discusses the instabilities of the gravitational Euclidean path integral and the difficulties with its interpretation. He presents an alternate formalism for baby universes, based on the "third quantization" of the Wheeler-De Witt equation. This approach is analyzed in a minisuperspace model for quantum gravity, where it reduces to simple quantum mechanics. Once again, the coupling parameters become dynamical. Unfortunately, the a priori probability distribution for the cosmological constant and other parameters is typically a smooth function, with no sharp peaks.

  3. Rate constants for reactions of ClO/x/ of atmospheric interest

    NASA Technical Reports Server (NTRS)

    Watson, R. T.

    1977-01-01

    Chemical kinetics measurements on 82 gas phase reactions of chlorine containing species are reviewed. Recommended rate constants are given. The principal species of interest are Cl, Cl2, ClO, Cl2O, ClOO, OClO, CINO, HCl and halo derivatives of methane and ethane. Absorption spectra are given for 21 species. In addition the chemical kinetics methods used to obtain these data are discussed with regard to their applicability and reliability.

  4. Marangoni bubble motion in zero gravity. [Lewis zero gravity drop tower

    NASA Technical Reports Server (NTRS)

    Thompson, R. L.; Dewitt, K. J.

    1979-01-01

    It was shown experimentally that the Marangoni phenomenon is a primary mechanism for the movement of a gas bubble in a nonisothermal liquid in a low gravity environment. A mathematical model consisting of the Navier-Stokes and thermal energy equations, together with the appropriate boundary conditions for both media, is presented. Parameter perturbation theory is used to solve this boundary value problem; the expansion parameter is the Marangoni number. The zeroth, first, and second order approximations for the velocity, temperature and pressure distributions in the liquid and in the bubble, and the deformation and terminal velocity of the bubble are determined. Experimental zero gravity data for a nitrogen bubble in ethylene glycol, ethanol, and silicone oil subjected to a linear temperature gradient were obtained using the NASA Lewis zero gravity drop tower. Comparison of the zeroth order analytical results for the bubble terminal velocity showed good agreement with the experimental measurements. The first and second order solutions for the bubble deformation and bubble terminal velocity are valid for liquids having Prandtl numbers on the order of one, but there is a lack of appropriate data to test the theory fully.

  5. Infrared small target detection based on directional zero-crossing measure

    NASA Astrophysics Data System (ADS)

    Zhang, Xiangyue; Ding, Qinghai; Luo, Haibo; Hui, Bin; Chang, Zheng; Zhang, Junchao

    2017-12-01

    Infrared small target detection under complex background and low signal-to-clutter ratio (SCR) condition is of great significance to the development on precision guidance and infrared surveillance. In order to detect targets precisely and extract targets from intricate clutters effectively, a detection method based on zero-crossing saliency (ZCS) map is proposed. The original map is first decomposed into different first-order directional derivative (FODD) maps by using FODD filters. Then the ZCS map is obtained by fusing all directional zero-crossing points. At last, an adaptive threshold is adopted to segment targets from the ZCS map. Experimental results on a series of images show that our method is effective and robust for detection under complex backgrounds. Moreover, compared with other five state-of-the-art methods, our method achieves better performance in terms of detection rate, SCR gain and background suppression factor.

  6. Fitting the Elementary Rate Constants of the P-gp Transporter Network in the hMDR1-MDCK Confluent Cell Monolayer Using a Particle Swarm Algorithm

    PubMed Central

    Agnani, Deep; Acharya, Poulomi; Martinez, Esteban; Tran, Thuy Thanh; Abraham, Feby; Tobin, Frank; Ellens, Harma; Bentz, Joe

    2011-01-01

    P-glycoprotein, a human multidrug resistance transporter, has been extensively studied due to its importance to human health and disease. In order to understand transport kinetics via P-gp, confluent cell monolayers overexpressing P-gp are widely used. The purpose of this study is to obtain the mass action elementary rate constants for P-gp's transport and to functionally characterize members of P-gp's network, i.e., other transporters that transport P-gp substrates in hMDR1-MDCKII confluent cell monolayers and are essential to the net substrate flux. Transport of a range of concentrations of amprenavir, loperamide, quinidine and digoxin across the confluent monolayer of cells was measured in both directions, apical to basolateral and basolateral to apical. We developed a global optimization algorithm using the Particle Swarm method that can simultaneously fit all datasets to yield accurate and exhaustive fits of these elementary rate constants. The statistical sensitivity of the fitted values was determined by using 24 identical replicate fits, yielding simple averages and standard deviations for all of the kinetic parameters, including the efflux active P-gp surface density. Digoxin required additional basolateral and apical transporters, while loperamide required just a basolateral tranporter. The data were better fit by assuming bidirectional transporters, rather than active importers, suggesting that they are not MRP or active OATP transporters. The P-gp efflux rate constants for quinidine and digoxin were about 3-fold smaller than reported ATP hydrolysis rate constants from P-gp proteoliposomes. This suggests a roughly 3∶1 stoichiometry between ATP hydrolysis and P-gp transport for these two drugs. The fitted values of the elementary rate constants for these P-gp substrates support the hypotheses that the selective pressures on P-gp are to maintain a broad substrate range and to keep xenobiotics out of the cytosol, but not out of the apical membrane. PMID

  7. Effect of dexmedetomidine constant rate infusion on the bispectral index during alfaxalone anaesthesia in dogs.

    PubMed

    Navarrete, Rocio; Quirós-Carmona, Setefilla; Granados, María Del M; Gómez-Villamandos, Rafael J; Domínguez, Juan M; Férnandez-Sarmiento, José A; Muñoz-Rascón, Pilar; Funes, Francisco J; Morgaz, Juan

    2016-07-01

    To assess the effect of two rates of infusion of dexmedetomidine on the bispectral index (BIS) in dogs anaesthetized with alfaxalone constant rate infusion (CRI). Prospective, randomized, 'blinded' experimental study. Six healthy Beagles (three females and three males). Dogs received as premedication saline (group D0), 1 μg kg(-1) (group D1) or 2 μg kg(-1) (group D2) dexmedetomidine, intravenously (IV). Anaesthesia was induced with alfaxalone (6 mg kg(-1) to effect IV) and maintained with alfaxalone at 0.07 mg kg(-1)  minute(-1) and a CRI of saline (D0) or dexmedetomidine 0.5 μg kg(-1)  hour(-1) (D1) or 1 μg kg(-1)  hour(-1) (D2) for 90 minutes. BIS, electromyography (EMG), signal quality index (SQI) and suppression ratio (SR) were measured at 10 minute intervals and the median values were calculated. Nociceptive stimuli were applied every 30 minutes and BIS and cardiorespiratory values were compared before and after stimuli. Cardiorespiratory parameters were recorded throughout the study. BIS and EMG values differed significantly among groups, being lower in D2 (71 ± 8) than in D0 (85 ± 10) and D1 (84 ± 9). SQI was always over 90% and SR was zero throughout all the treatments. There were no significant differences between pre- and post-stimulus values of BIS, EMG and SQI for any treatment, although in D0 and D1, heart rate, respiratory rate and arterial pressures increased significantly after the nociceptive stimulus. Administration of dexmedetomidine (2 μg kg(-1)  + CRI 1 μg kg(-1)  hour(-1) ) decreases the BIS values and avoids the autonomic responses of a nociceptive stimulus during alfaxalone anaesthesia at 0.07 mg kg(-1)  minute(-1) in dogs. However, further studies are needed to verify whether this combination produces an adequate degree of hypnosis under surgical situations. © 2015 Association of Veterinary Anaesthetists and the American College of Veterinary Anesthesia and Analgesia.

  8. Breather solutions of a fourth-order nonlinear Schrödinger equation in the degenerate, soliton, and rogue wave limits

    NASA Astrophysics Data System (ADS)

    Chowdury, Amdad; Krolikowski, Wieslaw; Akhmediev, N.

    2017-10-01

    We present one- and two-breather solutions of the fourth-order nonlinear Schrödinger equation. With several parameters to play with, the solution may take a variety of forms. We consider most of these cases including the general form and limiting cases when the modulation frequencies are 0 or coincide. The zero-frequency limit produces a combination of breather-soliton structures on a constant background. The case of equal modulation frequencies produces a degenerate solution that requires a special technique for deriving. A zero-frequency limit of this degenerate solution produces a rational second-order rogue wave solution with a stretching factor involved. Taking, in addition, the zero limit of the stretching factor transforms the second-order rogue waves into a soliton. Adding a differential shift in the degenerate solution results in structural changes in the wave profile. Moreover, the zero-frequency limit of the degenerate solution with differential shift results in a rogue wave triplet. The zero limit of the stretching factor in this solution, in turn, transforms the triplet into a singlet plus a low-amplitude soliton on the background. A large value of the differential shift parameter converts the triplet into a pure singlet.

  9. Breather solutions of a fourth-order nonlinear Schrödinger equation in the degenerate, soliton, and rogue wave limits.

    PubMed

    Chowdury, Amdad; Krolikowski, Wieslaw; Akhmediev, N

    2017-10-01

    We present one- and two-breather solutions of the fourth-order nonlinear Schrödinger equation. With several parameters to play with, the solution may take a variety of forms. We consider most of these cases including the general form and limiting cases when the modulation frequencies are 0 or coincide. The zero-frequency limit produces a combination of breather-soliton structures on a constant background. The case of equal modulation frequencies produces a degenerate solution that requires a special technique for deriving. A zero-frequency limit of this degenerate solution produces a rational second-order rogue wave solution with a stretching factor involved. Taking, in addition, the zero limit of the stretching factor transforms the second-order rogue waves into a soliton. Adding a differential shift in the degenerate solution results in structural changes in the wave profile. Moreover, the zero-frequency limit of the degenerate solution with differential shift results in a rogue wave triplet. The zero limit of the stretching factor in this solution, in turn, transforms the triplet into a singlet plus a low-amplitude soliton on the background. A large value of the differential shift parameter converts the triplet into a pure singlet.

  10. Determinants of systemic zero-flow arterial pressure.

    PubMed

    Brunner, M J; Greene, A S; Sagawa, K; Shoukas, A A

    1983-09-01

    Thirteen pentobarbital-anesthetized dogs whose carotid sinuses were isolated and perfused at a constant pressure were placed on total cardiac bypass. With systemic venous pressure held at 0 mmHg (condition 1), arterial inflow was stopped for 20 s at intrasinus pressures of 50, 125, and 200 mmHg. Zero-flow arterial pressures under condition 1 were 16.2 +/- 1.3 (SE), 13.8 +/- 1.1, and 12.5 +/- 0.8 mmHg, respectively. In condition 2, the venous outflow tube was clamped at the instant of stopping the inflow, causing venous pressure to rise. The zero-flow arterial pressures were 19.7 +/- 1.3, 18.5 +/- 1.4, and 16.4 +/- 1.2 mmHg for intrasinus pressures of 50, 125, and 200 mmHg, respectively. At all levels of intrasinus pressure, the zero-flow arterial pressure in condition 2 was higher (P less than 0.005) than in condition 1. In seven dogs, at an intrasinus pressure of 125 mmHg, epinephrine increased the zero-flow arterial pressure by 3.0 mmHg, whereas hexamethonium and papaverine decreased the zero-flow arterial pressure by 2 mmHg. Reductions in the hematocrit from 52 to 11% resulted in statistically significant changes (P less than 0.01) in zero-flow arterial pressures. Thus zero-flow arterial pressure was found to be affected by changes in venous pressure, hematocrit, and vasomotor tone. The evidence does not support the literally interpreted concept of the vascular waterfall as the model for the finite arteriovenous pressure difference at zero flow.

  11. Numerical calculations of temperature dependence of dielectric constant for an ordered assembly of BaTiO3 nanocubes with small tilt angles

    NASA Astrophysics Data System (ADS)

    Yasui, Kyuichi; Mimura, Ken-ichi; Izu, Noriya; Kato, Kazumi

    2018-03-01

    The dielectric constant of an ordered assembly of BaTiO3 nanocubes is numerically calculated as a function of temperature assuming a distribution of tilt angles of attached nanocubes. As the phase transition temperature from the tetragonal crystal structure to the cubic crystal structure of a BaTiO3 nanocube decreases as the tilt angle increases, the temperature at the peak of the dielectric constant of an ordered assembly is considerably lower than the Curie temperature of a free-standing BaTiO3 crystal. The peak of the dielectric constant as a function of temperature for an ordered assembly becomes considerably broader than that for a single crystal owing to the contribution of nanocubes with various tilt angles.

  12. Nonlinear elastic response of strong solids: First-principles calculations of the third-order elastic constants of diamond

    DOE PAGES

    Hmiel, A.; Winey, J. M.; Gupta, Y. M.; ...

    2016-05-23

    Accurate theoretical calculations of the nonlinear elastic response of strong solids (e.g., diamond) constitute a fundamental and important scientific need for understanding the response of such materials and for exploring the potential synthesis and design of novel solids. However, without corresponding experimental data, it is difficult to select between predictions from different theoretical methods. Recently the complete set of third-order elastic constants (TOECs) for diamond was determined experimentally, and the validity of various theoretical approaches to calculate the same may now be assessed. We report on the use of density functional theory (DFT) methods to calculate the six third-order elasticmore » constants of diamond. Two different approaches based on homogeneous deformations were used: (1) an energy-strain fitting approach using a prescribed set of deformations, and (2) a longitudinal stress-strain fitting approach using uniaxial compressive strains along the [100], [110], and [111] directions, together with calculated pressure derivatives of the second-order elastic constants. The latter approach provides a direct comparison to the experimental results. The TOECs calculated using the energy-strain approach differ significantly from the measured TOECs. In contrast, calculations using the longitudinal stress-uniaxial strain approach show good agreement with the measured TOECs and match the experimental values significantly better than the TOECs reported in previous theoretical studies. Lastly, our results on diamond have demonstrated that, with proper analysis procedures, first-principles calculations can indeed be used to accurately calculate the TOECs of strong solids.« less

  13. A Discussion of Zero Spring Rate Mechanisms Used for the Active Isolation Mount Experiment

    NASA Technical Reports Server (NTRS)

    Teter, John E., Jr.

    1999-01-01

    In the summer of 1995 the Structural Dynamics Branch at NASA Langley Research Center set out to conceive a small, lightweight, low frequency isolation mount that could be used for spaceflight experiments. The Engineering Design Branch undertook the task of developing the isolation mount. This report describes the engineering process that led to three phases of a study entitled "Active Isolation Mounts" (AIM). A zero spring rate mechanism was used to achieve low fundamental frequencies for a payloads in the 1 to 10 pound range. It worked by balancing both a positive and a negative stiffness so that the net result was a small positive stiffness. The study demonstrated devices that could reduce the initial corner frequency by a factor of six for brief periods and a factor of two for extended periods. The designs were relatively simple and minimized weight, volume, and power. They could be scaled down and they were made of spaceflight compatible materials. All designs offered the ability to continuously vary the fundamental frequency. Yet, the goal of reducing the frequency by an order of magnitude was not achieved because the systems were too unstable at low frequencies. There was a trade between performance and stability.

  14. Structural zeroes and zero-inflated models.

    PubMed

    He, Hua; Tang, Wan; Wang, Wenjuan; Crits-Christoph, Paul

    2014-08-01

    In psychosocial and behavioral studies count outcomes recording the frequencies of the occurrence of some health or behavior outcomes (such as the number of unprotected sexual behaviors during a period of time) often contain a preponderance of zeroes because of the presence of 'structural zeroes' that occur when some subjects are not at risk for the behavior of interest. Unlike random zeroes (responses that can be greater than zero, but are zero due to sampling variability), structural zeroes are usually very different, both statistically and clinically. False interpretations of results and study findings may result if differences in the two types of zeroes are ignored. However, in practice, the status of the structural zeroes is often not observed and this latent nature complicates the data analysis. In this article, we focus on one model, the zero-inflated Poisson (ZIP) regression model that is commonly used to address zero-inflated data. We first give a brief overview of the issues of structural zeroes and the ZIP model. We then given an illustration of ZIP with data from a study on HIV-risk sexual behaviors among adolescent girls. Sample codes in SAS and Stata are also included to help perform and explain ZIP analyses.

  15. Title: Elucidation of Environmental Fate of Artificial Sweeteners (Aspartame, Acesulfame K and Saccharin) by Determining Bimolecular Rate Constants with Hydroxyl Radical at Various pH and Temperature Conditions and Possible Reaction By-Products

    NASA Astrophysics Data System (ADS)

    Teraji, T.; Arakaki, T.; Suzuka, T.

    2012-12-01

    Use of artificial sweeteners in beverages and food has been rapidly increasing because of their non-calorie nature. In Japan, aspartame, acesulfame K and sucralose are among the most widely used artificial sweeteners. Because the artificial sweeteners are not metabolized in human bodies, they are directly excreted into the environment without chemical transformations. We initiated a study to better understand the fate of artificial sweeteners in the marine environment. The hydroxyl radical (OH), the most potent reactive oxygen species, reacts with various compounds and determines the environmental oxidation capacity and the life-time of many compounds. The steady-state OH concentration and the reaction rate constants between the compound and OH are used to estimate the life-time of the compound. In this study, we determine the bimolecular rate constants between aspartame, acefulfame K and saccharin and OH at various pH and temperature conditions using a competition kinetics technique. We use hydrogen peroxide as a photochemical source of OH. Bimolecular rate constant we obtained so far for aspartame was (2.6±1.2)×109 M-1 s-1 at pH = 3.0 and (4.9±2.3)×109 M-1 s-1 at pH = 5.5. Little effect was seen by changing the temperatures between 15 and 40 oC. Activation energy (Ea) was calculated to be -1.0 kJ mol-1 at pH = 3.0, +8.5 kJ mol-1 at pH = 5.5, which could be regarded as zero. We will report bimolecular rate constants at different pHs and temperatures for acesulfame K and saccharin, as well. Possible reaction by-products for aspartame will be also reported. We will further discuss the fate of aspartame in the coastal environment.

  16. Determining the folding and unfolding rate constants of nucleic acids by biosensor. Application to telomere G-quadruplex.

    PubMed

    Zhao, Yong; Kan, Zhong-yuan; Zeng, Zhi-xiong; Hao, Yu-hua; Chen, Hua; Tan, Zheng

    2004-10-20

    Nucleic acid molecules may fold into secondary structures, and the formation of such structures is involved in many biological processes and technical applications. The folding and unfolding rate constants define the kinetics of conformation interconversion and the stability of these structures and is important in realizing their functions. We developed a method to determine these kinetic parameters using an optical biosensor based on surface plasmon resonance. The folding and unfolding of a nucleic acid is coupled with a hybridization reaction by immobilization of the target nucleic acid on a sensor chip surface and injection of a complementary probe nucleic acid over the sensor chip surface. By monitoring the time course of duplex formation, both the folding and unfolding rate constants for the target nucleic acid and the association and dissociation rate constants for the target-probe duplex can all be derived from the same measurement. We applied this method to determine the folding and unfolding rate constants of the G-quadruplex of human telomere sequence (TTAGGG)(4) and its association and dissociation rate constants with the complementary strand (CCCTAA)(4). The results show that both the folding and unfolding occur on the time scale of minutes at physiological concentration of K(+). We speculate that this property might be important for telomere elongation. A complete set of the kinetic parameters for both of the structures allows us to study the competition between the formation of the quadruplex and the duplex. Calculations indicate that the formation of both the quadruplex and the duplex is strand concentration-dependent, and the quadruplex can be efficiently formed at low strand concentration. This property may provide the basis for the formation of the quadruplex in vivo in the presence of a complementary strand.

  17. Estimate Of The Decay Rate Constant of Hydrogen Sulfide Generation From Landfilled Drywall

    EPA Science Inventory

    Research was conducted to investigate the impact of particle size on H2S gas emissions and estimate a decay rate constant for H2S gas generation from the anaerobic decomposition of drywall. Three different particle sizes of regular drywall and one particle size of paperless drywa...

  18. Effect of humic acid and transition metal ions on the debromination of decabromodiphenyl by nano zero-valent iron: kinetics and mechanisms

    NASA Astrophysics Data System (ADS)

    Tan, Lei; Liang, Bin; Fang, Zhanqiang; Xie, Yingying; Tsang, Eric Pokeung

    2014-12-01

    E-waste sites are one of the main sources of the pollutant decabromodiphenyl ether (BDE209); contaminated farmland and water bodies urgently need to be remediated. As a potential in situ remediation technology, nano zero-valent iron (nZVI) technology effectively removes PBDEs. However, the humic acid (HA) and heavy metals in the contaminated sites affect the remediation effects. In this study, we explored the influence of HA and transition metals on the removal of PBDEs by nZVI. The specific surface area and average size of the nZVI particles we prepared were 35 m2/g and 50-80 nm, respectively. The results showed that HA inhibited the removal of PBDEs; as the concentration of HA increased, its inhibitory effect intensified and the k obs decreased. However, the three metal ions (Cu2+, Co2+, and Ni2+) enhanced the removal of PBDEs. The enhancement effect was followed the order Ni2+ > Cu2+ > Co2+. As the concentration of metal ions increased, the promotion effect improved. The synergistic effect of HA and the metal ions was manifested in the combination of the inhibitory effect and the enhancement effect. The values of the first-order kinetic constants ( k obs) under the combined effect were between the values of the rate constants under the individual components. The inhibitory mechanism was the chemisorption of HA, i.e., the benzene carboxylic and phenolic hydroxyl groups in HA occupied the surfactant reactive sites of nZVI, thus inhibiting the removal of BDE209. The promotion mechanism of Cu2+, Co2+, and Ni2+ can be explained by their reduction to zero valence on the nZVI surface; furthermore, Ni2+ strongly affects the debromination and dehydrogenation of BDE209, leading to a stronger promotability than Cu2+or Co2+.

  19. High resolution study of magnetic ordering at absolute zero.

    PubMed

    Lee, M; Husmann, A; Rosenbaum, T F; Aeppli, G

    2004-05-07

    High resolution pressure measurements in the zero-temperature limit provide a unique opportunity to study the behavior of strongly interacting, itinerant electrons with coupled spin and charge degrees of freedom. Approaching the precision that has become the hallmark of experiments on classical critical phenomena, we characterize the quantum critical behavior of the model, elemental antiferromagnet chromium, lightly doped with vanadium. We resolve the sharp doubling of the Hall coefficient at the quantum critical point and trace the dominating effects of quantum fluctuations up to surprisingly high temperatures.

  20. Zero-profile integrated plate and spacer device reduces rate of adjacent-level ossification development and dysphagia compared to ACDF with plating and cage system.

    PubMed

    Yang, Haisong; Chen, Deyu; Wang, Xinwei; Yang, Lili; He, Hailong; Yuan, Wen

    2015-06-01

    Retrospective case-control study. To compare the safety and efficacy of the Zero-profile (Zero-p) integrated plate and spacer device to that of an anterior cervical plate and cage in patients undergoing anterior cervical discectomy and fusion (ACDF). Anterior cervical plating system has provided good results, including higher fusion rate and improved alignment since its use. However, adjacent-level ossification development (ALOD) and dysphagia have been usually reported associating with plates. This was a retrospective control study. Sixty-two patients with cervical radiculopathy or myelopathy were treated with an anterior plate and cage or Zero-p implant between January 2011 and December 2011. The mean follow-up was 33.1 months in the plate and cage group and 30.6 months in Zero-p group. Patient demographics, operative details and complications were reviewed. The clinical outcomes were evaluated using the Japanese Orthopaedic Association (JOA) scores and JOA recovery rate before and after operations. Incidence of cephalad and caudal ALOD on the lateral radiographs was studied at preoperation, immediate postoperation and last follow-up. Incidence of dysphagia was also recorded after operation according to Bazaz-Yoo dysphagia index. Thirty-two patients received an anterior plate and cage and 30 received the Zero-p implant. There were no statistical differences in patient demographics, operative details between the two groups. The JOA scores significantly increased compared with preoperational measurements in both groups (p < 0.05), but the JOA recovery rate was similar (72.2 % for plate and cage group and 77.0 % for Zero-p group, p > 0.05). ALOD occurred in 12 (18.8 %) of the 64 cephalad and caudal adjacent segments in plate with cage group, and only 1 (1.6 %) of 63 adjacent levels (including three noncontiguous cases) presented with ALOD in Zero-p group. The difference was significant (p < 0.01). The incidence of dysphagia in the Zero-p group was lower

  1. A direct comparison of U.S. Environmental Protection Agency's method 304B and batch tests for determining activated-sludge biodegradation rate constants for volatile organic compounds

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

    Cano, M.L.; Wilcox, M.E.; Compernolle, R. van

    Biodegradation rate constants for volatile organic compounds (VOCs) in activated-sludge systems are needed to quantify emissions. One current US environmental Protection Agency method for determining a biodegradation rate constant is Method 304B. In this approach, a specific activated-sludge unit is simulated by a continuous biological treatment system with a sealed headspace. Batch experiments, however, can be alternatives to Method 304B. Two of these batch methods are the batch test that uses oxygen addition (BOX) and the serum bottle test (SBT). In this study, Method 304B was directly compared to BOX and SBT experiments. A pilot-scale laboratory reactor was constructed tomore » serve as the Method 304B unit. Biomass from the unit was also used to conduct BOX and modified SBT experiments (modification involved use of a sealed draft-tube reactor with a headspace recirculation pump instead of a serum bottle) for 1,2-dichloroethane, diisopropyl ether, methyl tertiary butyl ether, and toluene. Three experimental runs--each consisting of one Method 304B experiment, one BOX experiment, and one modified SBT experiment--were completed. The BOX and SBT data for each run were analyzed using a Monod model, and best-fit biodegradation kinetic parameters were determined for each experiment, including a first-order biodegradation rate constant (K{sub 1}). Experimental results suggest that for readily biodegradable VOCs the two batch techniques can provide improved means of determining biodegradation rate constants compared with Method 304B. In particular, these batch techniques avoid the Method 304B problem associated with steady-state effluent concentrations below analytical detection limits. However, experimental results also suggest that the two batch techniques should not be used to determine biodegradation rate constants for slowly degraded VOCs (i.e., K{sub 1} {lt} 0.1 L/g VSS-h).« less

  2. BOILING HEAT TRANSFER IN ZERO GRAVITY

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

    Zara, E.A.

    1964-01-01

    The preliminary results of a research program to determine the effects of zero and near zero gravity on boiling heat transfer are presented. Zero gravity conditions were obtained on the ASD KC-135 zero gravity test aircraft, capable of providing 30-seconds of zero gravity. Results of the program to date indicate that nucleate (bubble) boiling heat transfer rates are not greatly affected by the absence of gravity forces. However, radical pressure increases were observed that will dictate special design considerations to space vehicle systems utilizing pool boiling processes, such as cryogenic or other fluid storage vessels where thermal input to themore » fluid is used for vessel pressurization. (auth)« less

  3. Atmospheric fate of a series of carbonyl nitrates: photolysis frequencies and OH-oxidation rate constants.

    PubMed

    Suarez-Bertoa, R; Picquet-Varrault, B; Tamas, W; Pangui, E; Doussin, J-F

    2012-11-20

    Multifunctional organic nitrates are potential NO(x) reservoirs whose atmospheric chemistry is somewhat little known. They could play an important role in the spatial distribution of reactive nitrogen species and consequently in ozone formation and distribution in remote areas. In this work, the rate constants for the reaction with OH radical and the photolysis frequencies of α-nitrooxyacetone, 3-nitrooxy-2-butanone, and 3-methyl-3-nitrooxy-2-butanone have been determined at room temperature at 1000 mbar total pressure of synthetic air. The rate constants for the OH oxidation were measured using the relative rate technique, with methanol as reference compound. The following rate constants were obtained for the reaction with OH: k(OH) = (6.7 ± 2.5) × 10(-13) cm(3) molecule(-1) s(-1) for α-nitrooxyacetone, (10.6 ± 4.1) × 10(-13) cm(3) molecule(-1) s(-1) for 3-nitrooxy-2-butanone, and (2.6 ± 0.9) × 10(-13) cm(3) molecule(-1) s(-1) for 3-methyl-3-nitrooxy-2-butanone. The corresponding photolysis frequencies extrapolated to typical atmospheric conditions for July first at noon at 40° latitude North were (4.8 ± 0.3) × 10(-5) s(-1), (5.7 ± 0.3) × 10(-5) s(-1), and (7.4 ± 0.2) × 10(-5) s(-1), respectively. The data show that photolysis is a major atmospheric sink for these organic nitrates.

  4. Experiments with the Skylab fire detectors in zero gravity

    NASA Technical Reports Server (NTRS)

    Linford, R. M. F.

    1972-01-01

    The Skylab fire detector was evaluated in a zero gravity environment. To conduct the test, small samples of spacecraft materials were ignited in a 5 psi oxygen-rich atmosphere inside a combustion chamber. The chamber free-floated in the cabin of a C-135 aircraft, as the aircraft executed a Keplerian parabola. Up to 10 seconds of zero-gravity combustion were achieved. The Skylab fire-detector tubes viewed the flames from a simulated distance of 3m, and color movies were taken to record the nature of the fire. The experiments established the unique form of zero-gravity fires for a wide range of materials. From the tube-output data, the alarm threshold and detector time constant were verified for the Skylab Fire Detection System.

  5. Analysis and development of fourth order LCLC resonant based capacitor charging power supply for pulse power applications.

    PubMed

    Naresh, P; Hitesh, C; Patel, A; Kolge, T; Sharma, Archana; Mittal, K C

    2013-08-01

    A fourth order (LCLC) resonant converter based capacitor charging power supply (CCPS) is designed and developed for pulse power applications. Resonant converters are preferred t utilize soft switching techniques such as zero current switching (ZCS) and zero voltage switching (ZVS). An attempt has been made to overcome the disadvantages in 2nd and 3rd resonant converter topologies; hence a fourth order resonant topology is used in this paper for CCPS application. In this paper a novel fourth order LCLC based resonant converter has been explored and mathematical analysis carried out to calculate load independent constant current. This topology provides load independent constant current at switching frequency (fs) equal to resonant frequency (fr). By changing switching condition (on time and dead time) this topology has both soft switching techniques such as ZCS and ZVS for better switching action to improve the converter efficiency. This novel technique has special features such as low peak current through switches, DC blocking for transformer, utilizing transformer leakage inductance as resonant component. A prototype has been developed and tested successfully to charge a 100 μF capacitor to 200 V.

  6. 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

  7. Nonadiabatic effects on the charge transfer rate constant: A numerical study of a simple model system

    NASA Astrophysics Data System (ADS)

    Shin, Seokmin; Metiu, Horia

    1995-06-01

    We use a minimal model to study the effects of the upper electronic states on the rate of a charge transfer reaction. The model consists of three ions and an electron, all strung on a line. The two ions at the ends of the structure are held fixed, but the middle ion and the electron are allowed to move in one dimension, along the line joining them. The system has two bound states, one in which the electron ties the movable ion to the fixed ion at the left, and the other in which the binding takes place to the fixed ion at the right. The transition between these bound states is a charge transfer reaction. We use the flux-flux correlation function theory to perform two calculations of the rate constant for this reaction. In one we obtain numerically the exact rate constant. In the other we calculate the exact rate constant for the case when the reaction proceeds exclusively on the ground adiabatic state. The difference between these calculations gives the magnitude of the nonadiabatic effects. We find that the nonadiabatic effects are fairly large even when the gap between the ground and the excited adiabatic state substantially exceeds the thermal energy. The rate in the nonadiabatic theory is always smaller than that of the adiabatic one. Both rate constants satisfy the Arrhenius formula. Their activation energies are very close but the nonadiabatic one is always higher. The nonadiabatic preexponential is smaller, due to the fact that the upper electronic state causes an early recrossing of the reactive flux. The description of this reaction in terms of two diabatic states, one for reactants and one for products, is not always adequate. In the limit when nonadiabaticity is small, we need to use a third diabatic state, in which the electron binds to the moving ion as the latter passes through the transition state; this is an atom transfer process. The reaction changes from an atom transfer to an electron transfer, as nonadiabaticity is increased.

  8. Rate constants for chemical reactions in high-temperature nonequilibrium air

    NASA Technical Reports Server (NTRS)

    Jaffe, R. L.

    1986-01-01

    In the nonequilibrium atmospheric chemistry regime that will be encountered by the proposed Aeroassisted Orbital Transfer Vehicle in the upper atmosphere, where air density is too low for thermal and chemical equilibrium to be maintained, the detailed high temperature air chemistry plays a critical role in defining radiative and convective heating loads. Although vibrational and electronic temperatures remain low (less than 15,000 K), rotational and translational temperatures may reach 50,000 K. Attention is presently given to the effects of multiple temperatures on the magnitudes of various chemical reaction rate constants, for the cases of both bimolecular exchange reactions and collisional excitation and dissociation reactions.

  9. DISSOCIATION OF ARSENITE-PEPTIDE COMPLEXES: TRIPHASIC NATURE, RATE CONSTANTS, HALF LIVES AND BIOLOGICAL IMPORTANCE

    EPA Science Inventory

    We determined the number and the dissociation rate constants of different complexes formed from arsenite and two peptides containing either one (RV AVGNDYASGYHYGV for peptide 20) or three cysteines (LE AWQGK VEGTEHLYSMK K for peptide 10) via radioactive 73As labeled arsenite and ...

  10. Oxygen uptake kinetics of constant-load work - Upright vs. supine exercise

    NASA Technical Reports Server (NTRS)

    Convertino, V. A.; Goldwater, D. J.; Sandler, H.

    1984-01-01

    Supine and upright positions were used in a comparitive study of the effects of constant load exercise on oxygen uptake (VO2), O2 deficit, steady-state VO2 and VO2 following recovery from constant load work. Ten male subjects (36-40 yr.) performed one submaximal exercise test in the supine and one test in the upright position consisting of 5 min rest and 5 min cycle ergometer exercise at 700 kg/min followed by ten minutes of recovery. It is found that the significant difference in VO2 kinetics during exercise in the upright compared to supine position resulted from changes in oxygen transport and utilization mechanisms rather than changes in mechanical efficiency. To the extent that data measured in the supine position can be used to estimate physiological responses to zero gravity, it is suggested that limitation of systemic O2 consumption may be the result of slow rates of oxygen uptake during transient periods of muscular work. Significant reductions in the rate of steady-state VO2 attainment at submaximal work intensities may produce an onset of muscle fatigue and exhaustion.

  11. Accelerated Testing Methodology in Constant Stress-Rate Testing for Advanced Structural Ceramics: A Preloading Technique

    NASA Technical Reports Server (NTRS)

    Choi, Sung R.; Gyekenyesi, John P.; Huebert, Dean; Bartlett, Allen; Choi, Han-Ho

    2001-01-01

    Preloading technique was used as a means of an accelerated testing methodology in constant stress-rate ('dynamic fatigue') testing for two different brittle materials. The theory developed previously for fatigue strength as a function of preload was further verified through extensive constant stress-rate testing for glass-ceramic and CRT glass in room temperature distilled water. The preloading technique was also used in this study to identify the prevailing failure mechanisms at elevated temperatures, particularly at lower test rate in which a series of mechanisms would be associated simultaneously with material failure, resulting in significant strength increase or decrease. Two different advanced ceramics including SiC whisker-reinforced composite silicon nitride and 96 wt% alumina were used at elevated temperatures. It was found that the preloading technique can be used as an additional tool to pinpoint the dominant failure mechanism that is associated with such a phenomenon of considerable strength increase or decrease.

  12. Accelerated Testing Methodology in Constant Stress-Rate Testing for Advanced Structural Ceramics: A Preloading Technique

    NASA Technical Reports Server (NTRS)

    Choi, Sung R.; Gyekenyesi, John P.; Huebert, Dean; Bartlett, Allen; Choi, Han-Ho

    2001-01-01

    Preloading technique was used as a means of an accelerated testing methodology in constant stress-rate (dynamic fatigue) testing for two different brittle materials. The theory developed previously for fatigue strength as a function of preload was further verified through extensive constant stress-rate testing for glass-ceramic and CRT glass in room temperature distilled water. The preloading technique was also used in this study to identify the prevailing failure mechanisms at elevated temperatures, particularly at lower test rates in which a series of mechanisms would be associated simultaneously with material failure, resulting in significant strength increase or decrease. Two different advanced ceramics including SiC whisker-reinforced composite silicon nitride and 96 wt% alumina were used at elevated temperatures. It was found that the preloading technique can be used as an additional tool to pinpoint the dominant failure mechanism that is associated with such a phenomenon of considerable strength increase or decrease.

  13. Dose equivalent rate constants and barrier transmission data for nuclear medicine facility dose calculations and shielding design.

    PubMed

    Kusano, Maggie; Caldwell, Curtis B

    2014-07-01

    A primary goal of nuclear medicine facility design is to keep public and worker radiation doses As Low As Reasonably Achievable (ALARA). To estimate dose and shielding requirements, one needs to know both the dose equivalent rate constants for soft tissue and barrier transmission factors (TFs) for all radionuclides of interest. Dose equivalent rate constants are most commonly calculated using published air kerma or exposure rate constants, while transmission factors are most commonly calculated using published tenth-value layers (TVLs). Values can be calculated more accurately using the radionuclide's photon emission spectrum and the physical properties of lead, concrete, and/or tissue at these energies. These calculations may be non-trivial due to the polyenergetic nature of the radionuclides used in nuclear medicine. In this paper, the effects of dose equivalent rate constant and transmission factor on nuclear medicine dose and shielding calculations are investigated, and new values based on up-to-date nuclear data and thresholds specific to nuclear medicine are proposed. To facilitate practical use, transmission curves were fitted to the three-parameter Archer equation. Finally, the results of this work were applied to the design of a sample nuclear medicine facility and compared to doses calculated using common methods to investigate the effects of these values on dose estimates and shielding decisions. Dose equivalent rate constants generally agreed well with those derived from the literature with the exception of those from NCRP 124. Depending on the situation, Archer fit TFs could be significantly more accurate than TVL-based TFs. These results were reflected in the sample shielding problem, with unshielded dose estimates agreeing well, with the exception of those based on NCRP 124, and Archer fit TFs providing a more accurate alternative to TVL TFs and a simpler alternative to full spectral-based calculations. The data provided by this paper should assist

  14. Ab initio rate constants from hyperspherical quantum scattering: Application to H+C2H6 and H+CH3OH

    NASA Astrophysics Data System (ADS)

    Kerkeni, Boutheïna; Clary, David C.

    2004-10-01

    The dynamics and kinetics of the abstraction reactions of H atoms with ethane and methanol have been studied using a quantum mechanical procedure. Bonds being broken and formed are treated with explicit hyperspherical quantum dynamics. The ab initio potential energy surfaces for these reactions have been developed from a minimal number of grid points (average of 48 points) and are given by analytical functionals. All the degrees of freedom except the breaking and forming bonds are optimized using the second order perturbation theory method with a correlation consistent polarized valence triple zeta basis set. Single point energies are calculated on the optimized geometries with the coupled cluster theory and the same basis set. The reaction of H with C2H6 is endothermic by 1.5 kcal/mol and has a vibrationally adiabatic barrier of 12 kcal/mol. The reaction of H with CH3OH presents two reactive channels: the methoxy and the hydroxymethyl channels. The former is endothermic by 0.24 kcal/mol and has a vibrationally adiabatic barrier of 13.29 kcal/mol, the latter reaction is exothermic by 7.87 kcal/mol and has a vibrationally adiabatic barrier of 8.56 kcal/mol. We report state-to-state and state-selected cross sections together with state-to-state rate constants for the title reactions. Thermal rate constants for these reactions exhibit large quantum tunneling effects when compared to conventional transition state theory results. For H+CH3OH, it is found that the CH2OH product is the dominant channel, and that the CH3O channel contributes just 2% at 500 K. For both reactions, rate constants are in good agreement with some measurements.

  15. Degradation of trichloroethylene (TCE) by nanoscale zero-valent iron (nZVI) immobilized in alginate bead.

    PubMed

    Kim, Hojeong; Hong, Hye-Jin; Jung, Juri; Kim, Seong-Hye; Yang, Ji-Won

    2010-04-15

    Nowadays, many researchers have studied the environmental application of the nanoscale zero-valent iron (nZVI) and several field applications for the groundwater remediation have been reported. Still, there are many concerns on the fate and transport of the nZVI and the corresponding risks. To avoid such concerns, it was investigated to immobilize nZVI in a support and then it was applied to degrade trichloroethylene (TCE). The nZVI and palladium-doped nZVI (Fe(0)- and Fe/Pd-alginate) were immobilized in the alginate bead where ferric and barium ions are used as the cross-linking cations of the bead. According to TEM (transmission electron microscopy), the size of the immobilized ZVI was as small as a few nanometers. From the surface analysis of the Fe/Pd-alginate, it is found that the immobilized nZVI has the core-shell structure. The core is composed of single crystal Fe(0), while most of irons on the surface are oxidized to Fe(3+). When 50 g/L of Fe/Pd-alginate (3.7 g Fe/L) was introduced to the aqueous solution, >99.8% of TCE was removed and the release of metal from the support was <3% of the loaded iron. The removal of TCE by Fe/Pd-alginate followed pseudo-first-order kinetics. The observed pseudo-first-order reaction constant (k(obs)) of Fe/Pd-alginate was 6.11 h(-1) and the mass normalized rate constant (k(m)) was 1.6 L h(-1) g(-1). The k(m) is the same order of magnitude with that of iron nanoparticles. In conclusion, it is considered that Fe/Pd-alginate can be used efficiently in the treatment of chlorinated solvent. 2009 Elsevier B.V. All rights reserved.

  16. Growth rate and trapping efficacy of nematode-trapping fungi under constant and fluctuating temperatures.

    PubMed

    Fernández, A S; Larsen, M; Wolstrup, J; Grønvold, J; Nansen, P; Bjørn, H

    1999-08-01

    The effect of temperature on radial growth and predatory activity of different isolates of nematode-trapping fungi was assessed. Four isolates of Duddingtonia flagrans and one isolate of Arthrobotrys oligospora were inoculated on petri dishes containing either cornmeal agar (CMA) or faecal agar and then incubated for 14 days under three different constant and fluctuating temperature regimes. The radial growth was similar on the two substrates at each temperature regime. All fungal isolates showed a higher growth rate at a constant 20 degrees C. At 10 degrees and 15 degrees C, all D. flagrans isolates showed very similar patterns of radial growth at both constant and fluctuating temperatures. At 20 degrees C, they grew significantly faster at constant than at fluctuating temperatures. A. oligospora grew significantly faster than all D. flagrans isolates except when incubated at a fluctuating 20 degrees C. Spores of each fungal isolate were added to faecal cultures containing eggs of Cooperia oncophora at a concentration of 6250 spores/g faeces. The cultures were incubated for 14 days at the same temperature regimes described above. Control faeces (without fungal material) were also cultured. More larvae were recovered from the fungus-treated cultures incubated at a constant 10 degrees or 15 degrees C than from those incubated at the respective fluctuating temperatures, except for one D. flagrans isolate. Incubation at 20 degrees C showed the opposite effect. The general reduction observed in the number of nematode larvae due to fungal trapping was 18-25% and 48-80% for a constant and fluctuating 10 degrees C, 70-96% and 93-95% for a constant and fluctuating 15 degrees C, and 63-98% and 0-25% for a constant and fluctuating 20 degrees C, respectively.

  17. Constant DI pacing suppresses cardiac alternans formation in numerical cable models

    NASA Astrophysics Data System (ADS)

    Zlochiver, S.; Johnson, C.; Tolkacheva, E. G.

    2017-09-01

    Cardiac repolarization alternans describe the sequential alternation of the action potential duration (APD) and can develop during rapid pacing. In the ventricles, such alternans may rapidly turn into life risking arrhythmias under conditions of spatial heterogeneity. Thus, suppression of alternans by artificial pacing protocols, or alternans control, has been the subject of numerous theoretical, numerical, and experimental studies. Yet, previous attempts that were inspired by chaos control theories were successful only for a short spatial extent (<2 cm) from the pacing electrode. Previously, we demonstrated in a single cell model that pacing with a constant diastolic interval (DI) can suppress the formation of alternans at high rates of activation. We attributed this effect to the elimination of feedback between the pacing cycle length and the last APD, effectively preventing restitution-dependent alternans from developing. Here, we extend this idea into cable models to study the extent by which constant DI pacing can control alternans during wave propagation conditions. Constant DI pacing was applied to ventricular cable models of up to 5 cm, using human kinetics. Our results show that constant DI pacing significantly shifts the onset of both cardiac alternans and conduction blocks to higher pacing rates in comparison to pacing with constant cycle length. We also demonstrate that constant DI pacing reduces the propensity of spatially discordant alternans, a precursor of wavebreaks. We finally found that the protective effect of constant DI pacing is stronger for increased electrotonic coupling along the fiber in the sense that the onset of alternans is further shifted to higher activation rates. Overall, these results support the potential clinical applicability of such type of pacing in improving protocols of implanted pacemakers, in order to reduce the risk of life-threatening arrhythmias. Future research should be conducted in order to experimentally validate

  18. 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

  19. Nothing to it: Precursors to a Zero Concept in Preschoolers

    PubMed Central

    Merritt, Dustin J.; Brannon, Elizabeth M.

    2013-01-01

    Do young children understand the numerical value of empty sets prior to developing a concept of symbolic zero? Are empty sets represented as mental magnitudes? In order to investigate these questions, we tested 4-year old children and adults with a numerical ordering task in which the goal was to select two stimuli in ascending numerical order with occasional empty set stimuli. Both children and adults showed distance effects for empty sets.. Children who were unable to order the symbol zero (e.g., 0 < 1), but who successfully ordered countable integers (e.g., 2 < 4) nevertheless showed distance effects with empty sets. These results suggest that empty sets are represented on the same numerical continuum as non-empty sets and that children represent empty sets numerically prior to understanding symbolic zero. PMID:23219980

  20. Estimation of Anaerobic Debromination Rate Constants of PBDE Pathways Using an Anaerobic Dehalogenation Model.

    PubMed

    Karakas, Filiz; Imamoglu, Ipek

    2017-04-01

    This study aims to estimate anaerobic debromination rate constants (k m ) of PBDE pathways using previously reported laboratory soil data. k m values of pathways are estimated by modifying a previously developed model as Anaerobic Dehalogenation Model. Debromination activities published in the literature in terms of bromine substitutions as well as specific microorganisms and their combinations are used for identification of pathways. The range of estimated k m values is between 0.0003 and 0.0241 d -1 . The median and maximum of k m values are found to be comparable to the few available biologically confirmed rate constants published in the literature. The estimated k m values can be used as input to numerical fate and transport models for a better and more detailed investigation of the fate of individual PBDEs in contaminated sediments. Various remediation scenarios such as monitored natural attenuation or bioremediation with bioaugmentation can be handled in a more quantitative manner with the help of k m estimated in this study.

  1. Cohesive Energy-Lattice Constant and Bulk Modulus-Lattice Constant Relationships: Alkali Halides, Ag Halides, Tl Halides

    NASA Technical Reports Server (NTRS)

    Schlosser, Herbert

    1992-01-01

    In this note we present two expressions relating the cohesive energy, E(sub coh), and the zero pressure isothermal bulk modulus, B(sub 0), of the alkali halides. Ag halides and TI halides, with the nearest neighbor distances, d(sub nn). First, we show that the product E(sub coh)d(sub 0) within families of halide crystals with common crystal structure is to a good approximation constant, with maximum rms deviation of plus or minus 2%. Secondly, we demonstrate that within families of halide crystals with a common cation and common crystal structure the product B(sub 0)d(sup 3.5)(sub nn) is a good approximation constant, with maximum rms deviation of plus or minus 1.36%.

  2. Pediatric zolpidem ingestion demonstrating zero-order kinetics treated with flumazenil.

    PubMed

    Thornton, Stephen L; Negus, Elezer; Carstairs, Shaun D

    2013-11-01

    Zolpidem is a widely prescribed anti-insomnia agent. Although most pediatric zolpidem ingestions are benign, large ingestions can cause significant central nervous system (CNS) depression. Flumazenil has been reported to reverse the CNS effects of zolpidem. We describe a case of a large pediatric zolpidem ingestion resulting in profound CNS depression that responded to flumazenil administration. Serial zolpidem serum levels confirmed the ingestion. A 10-year-old boy with trisomy 21 presented to the emergency department 1 hour after he was found sedate with several zolpidem 5-mg tablets in his mouth. Seventeen tables (85 mg) were unaccounted for from a prescription bottle. He became unarousable approximately 2 hours after his ingestion. Flumazenil 0.2 mg intravenously was given with rapid return to his baseline mental status. He became resedate 1 hour later but was arousable. Sixteen hours after his presentation, he was asymptomatic. Serial zolpidem serum levels were obtained, showed an initial level of 310 ng/mL, and demonstrated zero-order kinetics. Zolpidem is an imidazopyridine, which binds to the benzodiazepine receptor. It is rapidly absorbed and has a short-half life. Unintentional pediatric ingestions of zolpidem are typically well tolerated. However, this case demonstrates that large ingestions may cause significant and prolonged CNS depression. Flumazenil, a benzodiazepine receptor antagonist, has been described to reverse the effects of zolpidem in adult ingestions. There are few published reports describing flumazenil use in pediatric ingestion patients. This case suggests that flumazenil may be an effective treatment for zolpidem-induced CNS depression in the pediatric patient.

  3. Welfare analysis of a zero-smoking policy - A case study in Japan.

    PubMed

    Nakamura, Yuuki; Takahashi, Kenzo; Nomura, Marika; Kamei, Miwako

    2018-03-19

    Smoking cessation efforts in Japan reduce smoking rates. A future zero-smoking policy would completely prohibit smoking (0% rate). We therefore analyzed the social welfare of smokers and non-smokers under a hypothetical zero-smoking policy. The demand curve for smoking from 1990 to 2014 was estimated by defining quantity as the number of cigarettes smoked and price as total tobacco sales/total cigarettes smoked by the two-stage least squares method using the tax on tobacco as the instrumental variable. In the estimation equation (calculated using the ordinary least squares method), the price of tobacco was the dependent variable and tobacco quantity the explanatory variable. The estimated constant was 31.90, the estimated coefficient of quantity was - 0.0061 (both, p < 0.0004), and the determinant coefficient was 0.9187. Thus, the 2015 consumer surplus was 1.08 trillion yen (US$ 9.82 billion) (95% confidence interval (CI), 889 billion yen (US$ 8.08 billion) - 1.27 trillion yen (US$ 11.6 billion)). Because tax revenue from tobacco in 2011 was 2.38 trillion yen (US$ 21.6 billion), the estimated deadweight loss if smoking were prohibited in 2014 was 3.31 trillion yen (US$ 30.2 billion) (95% CI, 3.13 trillion yen (US$ 28.5 billion) - 3.50 trillion yen (US$ 31.8 billion)), representing a deadweight loss about 0.6 trillion yen (US$ 5.45 billion) below the 2014 disease burden (4.10-4.12 trillion yen (US$ 37.3-37.5 billion)). We conclude that a zero-smoking policy would improve social welfare in Japan.

  4. "Zeroing" in on mathematics in the monkey brain.

    PubMed

    Beran, Michael J

    2016-03-01

    A new study documented that monkeys showed selective neuronal responding to the concept of zero during a numerical task, and that there were two distinct classes of neurons that coded the absence of stimuli either through a discrete activation pattern (zero or not zero) or a continuous one for which zero was integrated with other numerosities in the relative rate of activity. These data indicate that monkeys, like humans, have a concept of zero that is part of their analog number line but that also may have unique properties compared to other numerosities.

  5. ["Getting to zero infections" in hemodialysis].

    PubMed

    Leonardi, Gianluca; Finotto, Giuseppe; Talaia, Marinella; Nappo, Angelo; Dolla, Caterina; Di Vico, Maria Cristina; Diena, Davide; Linsalata, Antonio; Guarena, Cesare; Barbaro, Silvana; Biancone, Luigi

    2015-01-01

    We describe two measures adopted in hemodialysis outpatient population in order to reduce Central Venous Catheter (CVC) related infections. The first is a nurse staff training in the field project and the second deals with the employment of chlorhexidine-impregnated dressing devices. These actions were performed after high infection rates were observed through a dedicated register. In the limited assistance dialysis center, direct observation (12/2012-02/2013) quantified the gap between the observed and expected health care behaviour. Training needs were defined and a 40 hours nurse staff training in the field was performed on two occasions. In the hospital dialysis center, we introduced alcoholic 2% chlorhexidine solution and chlorhexidine-impregnated dressing devices to the exit site (CHG-Tegaderm and BioPatch). Infections (cumulatively bacteremia/sepsis/skin exit/subcutaneous tunnel) were monitored continuously. Infection rates at the two locations were progressively reduced, reaching a value of zero at the limited assistance center. Nurse staff training in the field produced: two patient reports and three CVC management protocols, Italian language translation of the "The 5 moments of dialysis" WHO poster, alcoholic 2% chlorhexidine adoption to exit-site medication and improvement of environment cleaning/sanitation actions. Our experience shows that continuously monitoring infection rates represents the first step for timely corrective action. The continuous updating of health personnel, codified prevention measures and an ongoing commitment to raise awareness in a routine practice, allows us to obtain the goal of "getting to zero infections". The staff training produced equal or superior results compared to the isolated use of new chlorhexidine-impregnated dressing devices.

  6. Local tuning of the order parameter in superconducting weak links: A zero-inductance nanodevice

    NASA Astrophysics Data System (ADS)

    Winik, Roni; Holzman, Itamar; Dalla Torre, Emanuele G.; Buks, Eyal; Ivry, Yachin

    2018-03-01

    Controlling both the amplitude and the phase of the superconducting quantum order parameter (" separators="|ψ ) in nanostructures is important for next-generation information and communication technologies. The lack of electric resistance in superconductors, which may be advantageous for some technologies, hinders convenient voltage-bias tuning and hence limits the tunability of ψ at the microscopic scale. Here, we demonstrate the local tunability of the phase and amplitude of ψ, obtained by patterning with a single lithography step a Nb nano-superconducting quantum interference device (nano-SQUID) that is biased at its nanobridges. We accompany our experimental results by a semi-classical linearized model that is valid for generic nano-SQUIDs with multiple ports and helps simplify the modelling of non-linear couplings among the Josephson junctions. Our design helped us reveal unusual electric characteristics with effective zero inductance, which is promising for nanoscale magnetic sensing and quantum technologies.

  7. Impact of the differential fluence distribution of brachytherapy sources on the spectroscopic dose-rate constant

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

    Malin, Martha J.; Bartol, Laura J.; DeWerd, Larry A., E-mail: mmalin@wisc.edu, E-mail: ladewerd@wisc.edu

    2015-05-15

    Purpose: To investigate why dose-rate constants for {sup 125}I and {sup 103}Pd seeds computed using the spectroscopic technique, Λ{sub spec}, differ from those computed with standard Monte Carlo (MC) techniques. A potential cause of these discrepancies is the spectroscopic technique’s use of approximations of the true fluence distribution leaving the source, φ{sub full}. In particular, the fluence distribution used in the spectroscopic technique, φ{sub spec}, approximates the spatial, angular, and energy distributions of φ{sub full}. This work quantified the extent to which each of these approximations affects the accuracy of Λ{sub spec}. Additionally, this study investigated how the simplified water-onlymore » model used in the spectroscopic technique impacts the accuracy of Λ{sub spec}. Methods: Dose-rate constants as described in the AAPM TG-43U1 report, Λ{sub full}, were computed with MC simulations using the full source geometry for each of 14 different {sup 125}I and 6 different {sup 103}Pd source models. In addition, the spectrum emitted along the perpendicular bisector of each source was simulated in vacuum using the full source model and used to compute Λ{sub spec}. Λ{sub spec} was compared to Λ{sub full} to verify the discrepancy reported by Rodriguez and Rogers. Using MC simulations, a phase space of the fluence leaving the encapsulation of each full source model was created. The spatial and angular distributions of φ{sub full} were extracted from the phase spaces and were qualitatively compared to those used by φ{sub spec}. Additionally, each phase space was modified to reflect one of the approximated distributions (spatial, angular, or energy) used by φ{sub spec}. The dose-rate constant resulting from using approximated distribution i, Λ{sub approx,i}, was computed using the modified phase space and compared to Λ{sub full}. For each source, this process was repeated for each approximation in order to determine which approximations

  8. The Multicenter Aerobic Iron Respiratory Chain of Acidithiobacillus ferrooxidans Functions as an Ensemble with a Single Macroscopic Rate Constant

    DOE PAGES

    Li, Ting-Feng; Painter, Richard G.; Ban, Bhupal; ...

    2015-06-03

    Electron transfer reactions among three prominent colored proteins in intact cells of Acidithiobacillus ferrooxidans were monitored using an integrating cavity absorption meter that permitted the acquisition of accurate absorbance data in suspensions of cells that scattered light. The concentrations of proteins in the periplasmic space were estimated to be 350 and 25 mg/ml for rusticyanin and cytochrome c, respectively; cytochrome a was present as one molecule for every 91 nm2 in the cytoplasmic membrane. All three proteins were rapidly reduced to the same relative extent when suspensions of live bacteria were mixed with different concentrations of ferrous ions at pHmore » 1.5. The subsequent molecular oxygen-dependent oxidation of the multicenter respiratory chain occurred with a single macroscopic rate constant, regardless of the proteins' in vitro redox potentials or their putative positions in the aerobic iron respiratory chain. The crowded electron transport proteins in the periplasm of the organism constituted an electron conductive medium where the network of protein interactions functioned in a concerted fashion as a single ensemble with a standard reduction potential of 650 mV. The appearance of product ferric ions was correlated with the reduction levels of the periplasmic electron transfer proteins; the limiting first-order catalytic rate constant for aerobic respiration on iron was 7,400 s -1. The ability to conduct direct spectrophotometric studies under noninvasive physiological conditions represents a new and powerful approach to examine the extent and rates of biological events in situ without disrupting the complexity of the live cellular environment.« less

  9. Traversable wormholes satisfying the weak energy condition in third-order Lovelock gravity

    NASA Astrophysics Data System (ADS)

    Zangeneh, Mahdi Kord; Lobo, Francisco S. N.; Dehghani, Mohammad Hossein

    2015-12-01

    In this paper, we consider third-order Lovelock gravity with a cosmological constant term in an n -dimensional spacetime M4×Kn -4, where Kn -4 is a constant curvature space. We decompose the equations of motion to four and higher dimensional ones and find wormhole solutions by considering a vacuum Kn -4 space. Applying the latter constraint, we determine the second- and third-order Lovelock coefficients and the cosmological constant in terms of specific parameters of the model, such as the size of the extra dimensions. Using the obtained Lovelock coefficients and Λ , we obtain the four-dimensional matter distribution threading the wormhole. Furthermore, by considering the zero tidal force case and a specific equation of state, given by ρ =(γ p -τ )/[ω (1 +γ )], we find the exact solution for the shape function which represents both asymptotically flat and nonflat wormhole solutions. We show explicitly that these wormhole solutions in addition to traversibility satisfy the energy conditions for suitable choices of parameters and that the existence of a limited spherically symmetric traversable wormhole with normal matter in a four-dimensional spacetime implies a negative effective cosmological constant.

  10. Kinetic Analysis for the Multistep Profiles of Organic Reactions: Significance of the Conformational Entropy on the Rate Constants of the Claisen Rearrangement.

    PubMed

    Sumiya, Yosuke; Nagahata, Yutaka; Komatsuzaki, Tamiki; Taketsugu, Tetsuya; Maeda, Satoshi

    2015-12-03

    The significance of kinetic analysis as a tool for understanding the reactivity and selectivity of organic reactions has recently been recognized. However, conventional simulation approaches that solve rate equations numerically are not amenable to multistep reaction profiles consisting of fast and slow elementary steps. Herein, we present an efficient and robust approach for evaluating the overall rate constants of multistep reactions via the recursive contraction of the rate equations to give the overall rate constants for the products and byproducts. This new method was applied to the Claisen rearrangement of allyl vinyl ether, as well as a substituted allyl vinyl ether. Notably, the profiles of these reactions contained 23 and 84 local minima, and 66 and 278 transition states, respectively. The overall rate constant for the Claisen rearrangement of allyl vinyl ether was consistent with the experimental value. The selectivity of the Claisen rearrangement reaction has also been assessed using a substituted allyl vinyl ether. The results of this study showed that the conformational entropy in these flexible chain molecules had a substantial impact on the overall rate constants. This new method could therefore be used to estimate the overall rate constants of various other organic reactions involving flexible molecules.

  11. Reaction Order Ambiguity in Integrated Rate Plots

    ERIC Educational Resources Information Center

    Lee, Joe

    2008-01-01

    Integrated rate plots are frequently used in reaction kinetics to determine orders of reactions. It is often emphasised, when using this methodology in practice, that it is necessary to monitor the reaction to a substantial fraction of completion for these plots to yield unambiguous orders. The present article gives a theoretical and statistical…

  12. Zero-inflated count models for longitudinal measurements with heterogeneous random effects.

    PubMed

    Zhu, Huirong; Luo, Sheng; DeSantis, Stacia M

    2017-08-01

    Longitudinal zero-inflated count data arise frequently in substance use research when assessing the effects of behavioral and pharmacological interventions. Zero-inflated count models (e.g. zero-inflated Poisson or zero-inflated negative binomial) with random effects have been developed to analyze this type of data. In random effects zero-inflated count models, the random effects covariance matrix is typically assumed to be homogeneous (constant across subjects). However, in many situations this matrix may be heterogeneous (differ by measured covariates). In this paper, we extend zero-inflated count models to account for random effects heterogeneity by modeling their variance as a function of covariates. We show via simulation that ignoring intervention and covariate-specific heterogeneity can produce biased estimates of covariate and random effect estimates. Moreover, those biased estimates can be rectified by correctly modeling the random effects covariance structure. The methodological development is motivated by and applied to the Combined Pharmacotherapies and Behavioral Interventions for Alcohol Dependence (COMBINE) study, the largest clinical trial of alcohol dependence performed in United States with 1383 individuals.

  13. Variable dose rate single-arc IMAT delivered with a constant dose rate and variable angular spacing

    NASA Astrophysics Data System (ADS)

    Tang, Grace; Earl, Matthew A.; Yu, Cedric X.

    2009-11-01

    Single-arc intensity-modulated arc therapy (IMAT) has gained worldwide interest in both research and clinical implementation due to its superior plan quality and delivery efficiency. Single-arc IMAT techniques such as the Varian RapidArc™ deliver conformal dose distributions to the target in one single gantry rotation, resulting in a delivery time in the order of 2 min. The segments in these techniques are evenly distributed within an arc and are allowed to have different monitor unit (MU) weightings. Therefore, a variable dose-rate (VDR) is required for delivery. Because the VDR requirement complicates the control hardware and software of the linear accelerators (linacs) and prevents most existing linacs from delivering IMAT, we propose an alternative planning approach for IMAT using constant dose-rate (CDR) delivery with variable angular spacing. We prove the equivalence by converting VDR-optimized RapidArc plans to CDR plans, where the evenly spaced beams in the VDR plan are redistributed to uneven spacing such that the segments with larger MU weighting occupy a greater angular interval. To minimize perturbation in the optimized dose distribution, the angular deviation of the segments was restricted to <=± 5°. This restriction requires the treatment arc to be broken into multiple sectors such that the local MU fluctuation within each sector is reduced, thereby lowering the angular deviation of the segments during redistribution. The converted CDR plans were delivered with a single gantry sweep as in the VDR plans but each sector was delivered with a different value of CDR. For four patient cases, including two head-and-neck, one brain and one prostate, all CDR plans developed with the variable spacing scheme produced similar dose distributions to the original VDR plans. For plans with complex angular MU distributions, the number of sectors increased up to four in the CDR plans in order to maintain the original plan quality. Since each sector was delivered

  14. Theoretical Discussion of Electron Transport Rate Constant at TCNQ / Ge and TiO2 System

    NASA Astrophysics Data System (ADS)

    Al-agealy, Hadi J. M.; Alshafaay, B.; Hassooni, Mohsin A.; Ashwiekh, Ahmed M.; Sadoon, Abbas K.; Majeed, Raad H.; Ghadhban, Rawnaq Q.; Mahdi, Shatha H.

    2018-05-01

    We have been studying and estimation the electronic transport constant at TCNQ / Ge and Tio2 interface by means of tunneling potential (TP), transport energy reorientation (TER), driving transition energy DTE and coupling coefficient constant. A simple quantum model for the transition processes was adapted to estimation and analysis depending on the quantum state for donor state |α D > and acceptor stated |α A > and assuming continuum levels of the system. Evaluation results were performed for the surfaces of Ge and Tio2 as best as for multilayer TCNQ. The results show an electronic transfer feature for electronic TCNQ density of states and a semiconductor behavior. The electronic rate constant result for both systems shows a good tool to election system in applied devices. All these results indicate the

  15. Zero-gravity open-type urine receptacle

    NASA Technical Reports Server (NTRS)

    Girala, A. S.

    1972-01-01

    The development of the zero-gravity open-type urine receptacle used in the Apollo command module is described. This type receptacle eliminates the need for a cuff-type urine collector or for the penis to circumferentially contact the receptacle in order to urinate. This device may be used in a gravity environment, varying from zero gravity to earth gravity, such as may be experienced in a space station or space base.

  16. Development of a zero-order sustained-release tablet containing mesalazine and budesonide intended to treat the distal gastrointestinal tract in inflammatory bowel disease.

    PubMed

    Gareb, Bahez; Eissens, Anko C; Kosterink, Jos G W; Frijlink, Hendrik W

    2016-06-01

    Ulcerative colitis (UC) and Crohn's disease (CD) are diseases affecting the gastrointestinal tract. Treatment depends on the severity of the disease, site of inflammation, and patient's response. The aim of this study was to develop a zero-order sustained-release tablet containing both the anti-inflammatory drugs mesalazine and budesonide as a new treatment option for ileo-colonic CD and UC. Tablets were attained by wet granulation with hydroxypropyl methylcellulose and direct compression. Our newly developed tablet core was coated with different ColoPulse® coating thicknesses and the mesalazine and budesonide release profiles were investigated in a 600-min gastrointestinal simulation system (GISS) experiment, together with commercially available MMX®-mesalazine and MMX®-budesonide. Lag-time, release rate (k0), completeness of release, and zero-order correlation coefficient (R(2)0) could be manipulated by varying ColoPulse® coating thickness. Our newly developed combination preparation (C[4.92]) complied with all conducted European Pharmacopoeia tests as well as an accelerated 6-month stability test and had a lag-time of 250min (simulated ileum targeted), a linear release profile (mesalazine R(2)0=0.9002; budesonide R(2)0=0.9481), and drug release of 100% mesalazine and 77% budesonide. Like C[4.92], MMX®-mesalazine had a linear (R(2)0=0.9883) and complete release profile (96%). However, C[4.92] lag-time was longer (250 vs. 210min), assuring simulated ileum specificity. Remarkably, MMX®-budesonide lag-time was 480min and release was only 7% with a linear character (R(2)0=0.9906). The in vitro results suggest that MMX®-budesonide effectiveness may be improved if budesonide release in the aqueous phase would be increased and that C[4.92] is a potential, new treatment option for ileo-colonic CD and UC. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Reaction rate constants and mean population percentage for nitrifiers in an alternating oxidation ditch system.

    PubMed

    Mantziaras, I D; Katsiri, A

    2011-01-01

    This paper presents a methodology for the determination of reaction rate constants for nitrifying bacteria and their mean population percentage in biomass in an alternating oxidation ditch system. The method used is based on the growth rate equations of the ASM1 model (IWA) (Henze et al. in Activated sludge models ASM1, ASM2, ASM2d, and ASM3. IWA Scientific and Technical Report no. 9, IWA Publishing, London, UK, 2000) and the application of mass balance equations for nitrifiers and ammonium nitrogen in an operational cycle of the ditch system. The system consists of two ditches operating in four phases. Data from a large-scale oxidation ditch pilot plant with a total volume of 120 m(3) within an experimental period of 8 months was used. Maximum specific growth rate for autotrophs (μ(A)) and the half-saturation constant for ammonium nitrogen (K(NH)) were found to be 0.36 day(-1) and 0.65 mgNH(4)-N/l, respectively. Additionally, the average population percentage of the nitrifiers in the biomass was estimated to be around 3%.

  18. Continuous preparation of nanoscale zero-valent iron using impinging stream-rotating packed bed reactor and their application in reduction of nitrobenzene

    NASA Astrophysics Data System (ADS)

    Jiao, Weizhou; Qin, Yuejiao; Luo, Shuai; Feng, Zhirong; Liu, Youzhi

    2017-02-01

    Nanoscale zero-valent iron (nZVI) was continuously prepared by high-gravity reaction precipitation through a novel impinging stream-rotating packed bed (IS-RPB). Reactant solutions of FeSO4 and NaBH4 were conducted into the IS-RPB with flow rates of 60 L/h and rotating speed of 1000 r/min for the preparation of nZVI. As-prepared nZVI obtained by IS-RPB were quasi-spherical morphology and almost uniformly distributed with a particle size of 10-20 nm. The reactivity of nZVI was estimated by the degradation of 100 ml nitrobenzene (NB) with initial concentration of 250 mg/L. The optimum dosage of nZVI obtained by IS-RPB was 4.0 g/L as the NB could be completely removed within 10 min, which reduced 20% compared with nZVI obtained by stirred tank reactor (STR). The reduction of NB and production of aniline (AN) followed pseudo-first-order kinetics, and the pseudo-first-order rate constants were 0.0147 and 0.0034 s-1, respectively. Furthermore, the as-prepared nZVI using IS-RPB reactor in this work can be used within a relatively wide range pH of 1-9.

  19. 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

  20. Tunneling Rate Constants for H2CO+H on Amorphous Solid Water Surfaces

    NASA Astrophysics Data System (ADS)

    Song, Lei; Kästner, Johannes

    2017-12-01

    Formaldehyde (H2CO) is one of the most abundant molecules observed in the icy mantle covering interstellar grains. Studying its evolution can contribute to our understanding of the formation of complex organic molecules in various interstellar environments. In this work, we investigated the hydrogenation reactions of H2CO yielding CH3O, CH2OH, and the hydrogen abstraction resulting in H2+HCO on an amorphous solid water (ASW) surface using a quantum mechanics/molecular mechanics (QM/MM) model. The binding energies of H2CO on the ASW surface vary broadly, from 1000 to 9370 K. No correlation was found between binding energies and activation energies of hydrogenation reactions. Combining instanton theory with QM/MM modeling, we calculated rate constants for the Langmuir-Hinshelwood and the Eley-Rideal mechanisms for the three product channels of H+H2CO surface reactions down to 59 K. We found that the channel producing CH2OH can be ignored, owing to its high activation barrier leading to significantly lower rates than the other two channels. The ASW surface influences the reactivity in favor of formation of CH3O (branching ratio ˜80%) and hinders the H2CO dissociation into H2+HCO. In addition, kinetic isotope effects are strong in all reaction channels and vary strongly between the channels. Finally, we provide fits of the rate constants to be used in astrochemical models.

  1. 15 CFR 700.12 - Elements of a rated order.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 15 Commerce and Foreign Trade 2 2010-01-01 2010-01-01 false Elements of a rated order. 700.12 Section 700.12 Commerce and Foreign Trade Regulations Relating to Commerce and Foreign Trade (Continued... DEFENSE PRIORITIES AND ALLOCATIONS SYSTEM Industrial Priorities § 700.12 Elements of a rated order. Each...

  2. 15 CFR 700.12 - Elements of a rated order.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 15 Commerce and Foreign Trade 2 2014-01-01 2014-01-01 false Elements of a rated order. 700.12 Section 700.12 Commerce and Foreign Trade Regulations Relating to Commerce and Foreign Trade (Continued... DEFENSE PRIORITIES AND ALLOCATIONS SYSTEM Industrial Priorities § 700.12 Elements of a rated order. Each...

  3. 15 CFR 700.12 - Elements of a rated order.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 15 Commerce and Foreign Trade 2 2012-01-01 2012-01-01 false Elements of a rated order. 700.12 Section 700.12 Commerce and Foreign Trade Regulations Relating to Commerce and Foreign Trade (Continued... DEFENSE PRIORITIES AND ALLOCATIONS SYSTEM Industrial Priorities § 700.12 Elements of a rated order. Each...

  4. 15 CFR 700.12 - Elements of a rated order.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 15 Commerce and Foreign Trade 2 2011-01-01 2011-01-01 false Elements of a rated order. 700.12 Section 700.12 Commerce and Foreign Trade Regulations Relating to Commerce and Foreign Trade (Continued... DEFENSE PRIORITIES AND ALLOCATIONS SYSTEM Industrial Priorities § 700.12 Elements of a rated order. Each...

  5. 15 CFR 700.12 - Elements of a rated order.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 15 Commerce and Foreign Trade 2 2013-01-01 2013-01-01 false Elements of a rated order. 700.12 Section 700.12 Commerce and Foreign Trade Regulations Relating to Commerce and Foreign Trade (Continued... DEFENSE PRIORITIES AND ALLOCATIONS SYSTEM Industrial Priorities § 700.12 Elements of a rated order. Each...

  6. A Unified Kinetics and Equilibrium Experiment: Rate Law, Activation Energy, and Equilibrium Constant for the Dissociation of Ferroin

    ERIC Educational Resources Information Center

    Sattar, Simeen

    2011-01-01

    Tris(1,10-phenanthroline)iron(II) is the basis of a suite of four experiments spanning 5 weeks. Students determine the rate law, activation energy, and equilibrium constant for the dissociation of the complex ion in acid solution and base dissociation constant for phenanthroline. The focus on one chemical system simplifies a daunting set of…

  7. Rate constant for reaction of vitamin C with protein radicals in γ-irradiated aqueous albumin solution at 295 K

    NASA Astrophysics Data System (ADS)

    Miyazaki, Tetsuo; Yoshimura, Toru; Mita, Kazuya; Suzuki, Keiji; Watanabe, Masami

    1995-02-01

    When an aqueous solution of albumin (0.1 kg dm -3) is irradiated by γ-rays at 295 K, albumin radicals with a long lifetime are observed by ESR. The reaction of vitamin C with the albumin radicals has been studied at 295 K in the albumin solution, which is considered as a model of cells. The rate constant for the reaction of vitamin C with the albumin radicals was measured as 0.014 dm 3 mol -1 s -1, which is much smaller than the reported rate constants (10 6-10 10 dm 3 mol -1 s -1) for the reaction of vitamin C with radicals in a dilute aqueous solution. The small rate constant for the reaction of vitamin C is ascribed to the reaction in polymer coils in the albumin solution, since vitamin C and albumin radicals diffuse very slowly in the coils.

  8. Exact sum rules for inhomogeneous systems containing a zero mode

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

    Amore, Paolo, E-mail: paolo.amore@gmail.com

    2014-10-15

    We show that the formulas for the sum rules for the eigenvalues of inhomogeneous systems that we have obtained in two recent papers are incomplete when the system contains a zero mode. We prove that there are finite contributions of the zero mode to the sum rules and we explicitly calculate the expressions for the sum rules of order one and two. The previous results for systems that do not contain a zero mode are unaffected. - Highlights: • We discuss the sum rules of the eigenvalues of inhomogeneous systems containing a zero mode. • We derive the explicit expressionsmore » for sum rules of order one and two. • We perform accurate numerical tests of these results for three examples.« less

  9. Arsenic(V) removal from groundwater using nano scale zero-valent iron as a colloidal reactive barrier material.

    PubMed

    Kanel, Sushil Raj; Greneche, Jean-Mark; Choi, Heechul

    2006-03-15

    The removal of As(V), one of the most poisonous groundwater pollutants, by synthetic nanoscale zero-valent iron (NZVI) was studied. Batch experiments were performed to investigate the influence of pH, adsorption kinetics, sorption mechanism, and anionic effects. Field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mossbauer spectroscopy were used to characterize the particle size, surface morphology, and corrosion layer formation on pristine NZVI and As(V)-treated NZVI. The HR-TEM study of pristine NZVI showed a core-shell-like structure, where more than 90% of the nanoparticles were under 30 nm in diameter. Mössbauer spectroscopy further confirmed its structure in which 19% were in zero-valent state with a coat of 81% iron oxides. The XRD results showed that As(V)-treated NZVI was gradually converted into magnetite/maghemite corrosion products over 90 days. The XPS study confirmed that 25% As(V) was reduced to As(III) by NZVI after 90 days. As(V) adsorption kinetics were rapid and occurred within minutes following a pseudo-first-order rate expression with observed reaction rate constants (Kobs) of 0.02-0.71 min(-1) at various NZVI concentrations. Laser light scattering analysis confirmed that NZVI-As(V) forms an inner-sphere surface complexation. The effects of competing anions revealed that HCO3-, H4SiO4(0), and H2PO4(2-) are potential interfering agents in the As(V) adsorption reaction. Our results suggest that NZVI is a suitable candidate for As(V) remediation.

  10. Constant Communities in Complex Networks

    NASA Astrophysics Data System (ADS)

    Chakraborty, Tanmoy; Srinivasan, Sriram; Ganguly, Niloy; Bhowmick, Sanjukta; Mukherjee, Animesh

    2013-05-01

    Identifying community structure is a fundamental problem in network analysis. Most community detection algorithms are based on optimizing a combinatorial parameter, for example modularity. This optimization is generally NP-hard, thus merely changing the vertex order can alter their assignments to the community. However, there has been less study on how vertex ordering influences the results of the community detection algorithms. Here we identify and study the properties of invariant groups of vertices (constant communities) whose assignment to communities are, quite remarkably, not affected by vertex ordering. The percentage of constant communities can vary across different applications and based on empirical results we propose metrics to evaluate these communities. Using constant communities as a pre-processing step, one can significantly reduce the variation of the results. Finally, we present a case study on phoneme network and illustrate that constant communities, quite strikingly, form the core functional units of the larger communities.

  11. Ruthenium(VI)-Catalyzed Oxidation of Alcohols by Hexacyanoferrate(III): An Example of Mixed Order

    ERIC Educational Resources Information Center

    Mucientes, Antonio E.; de la Pena, Maria A.

    2006-01-01

    The absorbance decay of hexacyanoferrate(III) as a function of time shows a progressive deviation from zero to first order. This variation follows an experimental rate law that has been analyzed. The change in reaction order is due to a change in the relative rate of substrate oxidation with respect to that of catalyst regeneration. (Contains 2…

  12. 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.

  13. Magnetic irreversibility: An important amendment in the zero-field-cooling and field-cooling method

    NASA Astrophysics Data System (ADS)

    Teixeira Dias, Fábio; das Neves Vieira, Valdemar; Esperança Nunes, Sabrina; Pureur, Paulo; Schaf, Jacob; Fernanda Farinela da Silva, Graziele; de Paiva Gouvêa, Cristol; Wolff-Fabris, Frederik; Kampert, Erik; Obradors, Xavier; Puig, Teresa; Roa Rovira, Joan Josep

    2016-02-01

    The present work reports about experimental procedures to correct significant deviations of magnetization data, caused by magnetic relaxation, due to small field cycling by sample transport in the inhomogeneous applied magnetic field of commercial magnetometers. The extensively used method for measuring the magnetic irreversibility by first cooling the sample in zero field, switching on a constant applied magnetic field and measuring the magnetization M(T) while slowly warming the sample, and subsequently measuring M(T) while slowly cooling it back in the same field, is very sensitive even to small displacement of the magnetization curve. In our melt-processed YBaCuO superconducting sample we observed displacements of the irreversibility limit up to 7 K in high fields. Such displacements are detected only on confronting the magnetic irreversibility limit with other measurements, like for instance zero resistance, in which the sample remains fixed and so is not affected by such relaxation. We measured the magnetic irreversibility, Tirr(H), using a vibrating sample magnetometer (VSM) from Quantum Design. The zero resistance data, Tc0(H), were obtained using a PPMS from Quantum Design. On confronting our irreversibility lines with those of zero resistance, we observed that the Tc0(H) data fell several degrees K above the Tirr(H) data, which obviously contradicts the well known properties of superconductivity. In order to get consistent Tirr(H) data in the H-T plane, it was necessary to do a lot of additional measurements as a function of the amplitude of the sample transport and extrapolate the Tirr(H) data for each applied field to zero amplitude.

  14. (In)validity of the constant field and constant currents assumptions in theories of ion transport.

    PubMed Central

    Syganow, A; von Kitzing, E

    1999-01-01

    Constant electric fields and constant ion currents are often considered in theories of ion transport. Therefore, it is important to understand the validity of these helpful concepts. The constant field assumption requires that the charge density of permeant ions and flexible polar groups is virtually voltage independent. We present analytic relations that indicate the conditions under which the constant field approximation applies. Barrier models are frequently fitted to experimental current-voltage curves to describe ion transport. These models are based on three fundamental characteristics: a constant electric field, negligible concerted motions of ions inside the channel (an ion can enter only an empty site), and concentration-independent energy profiles. An analysis of those fundamental assumptions of barrier models shows that those approximations require large barriers because the electrostatic interaction is strong and has a long range. In the constant currents assumption, the current of each permeating ion species is considered to be constant throughout the channel; thus ion pairing is explicitly ignored. In inhomogeneous steady-state systems, the association rate constant determines the strength of ion pairing. Among permeable ions, however, the ion association rate constants are not small, according to modern diffusion-limited reaction rate theories. A mathematical formulation of a constant currents condition indicates that ion pairing very likely has an effect but does not dominate ion transport. PMID:9929480

  15. Quantum calculations of the rate constant for the O(3P)+HCl reaction on new ab initio 3A″ and 3A' surfaces

    NASA Astrophysics Data System (ADS)

    Xie, Tiao; Bowman, Joel M.; Peterson, K. A.; Ramachandran, B.

    2003-11-01

    We report the thermal rate constant of the O(3P)+HCl→OH+Cl reaction calculated from 200 to 3200 K, using new fits to extensive ab initio calculations [B. Ramachandran and K. A. Peterson, J. Chem. Phys. 119, 9590 (2003), preceding paper]. The rate constants are obtained for both the 3A″ and 3A' surfaces using exact quantum reactive scattering calculations for selected values of the total angular momentum and the J-shifting approximation for both the 3A″ and 3A' surfaces. The results are compared with the ICVT/μOMT rate constants calculated by the POLYRATE program and all available experimental data. Other related high-energy reaction channels are also studied qualitatively for their contribution to the total thermal rate constant at high temperature.

  16. Kinetics of exchange between zero-, one-, and two-hydrogen-bonded states of methyl and ethyl acetate in methanol.

    PubMed

    Chuntonov, Lev; Pazos, Ileana M; Ma, Jianqiang; Gai, Feng

    2015-03-26

    It has recently been shown that the ester carbonyl stretching vibration can be used as a sensitive probe of local electrostatic field in molecular systems. To further characterize this vibrational probe and extend its potential applications, we studied the kinetics of chemical exchange between differently hydrogen-bonded (H-bonded) ester carbonyl groups of methyl acetate (MA) and ethyl acetate (EA) in methanol. We found that, while both MA and EA can form zero, one, or two H-bonds with the solvent, the population of the 2hb state in MA is significantly smaller than that in EA. Using a combination of linear and nonlinear infrared measurements and numerical simulations, we further determined the rate constants for the exchange between these differently H-bonded states. We found that for MA the chemical exchange reaction between the two dominant states (i.e., 0hb and 1hb states) has a relaxation rate constant of 0.14 ps(-1), whereas for EA the three-state chemical exchange reaction occurs in a predominantly sequential manner with the following relaxation rate constants: 0.11 ps(-1) for exchange between 0hb and 1hb states and 0.12 ps(-1) for exchange between 1hb and 2hb states.

  17. Tenth-order QED contribution to the electron g-2 and an improved value of the fine structure constant.

    PubMed

    Aoyama, Tatsumi; Hayakawa, Masashi; Kinoshita, Toichiro; Nio, Makiko

    2012-09-14

    This letter presents the complete QED contribution to the electron g-2 up to the tenth order. With the help of the automatic code generator, we evaluate all 12,672 diagrams of the tenth-order diagrams and obtain 9.16 (58)(α/π)(5). We also improve the eighth-order contribution obtaining -1.9097 (20)(α/π)(4), which includes the mass-dependent contributions. These results lead to a(e)(theory)=1,159,652,181.78(77)×10(-12). The improved value of the fine-structure constant α(-1)=137.035999173 (35) [0.25 ppb] is also derived from the theory and measurement of a(e).

  18. Decay constants of the charmed tensor mesons at finite temperature

    NASA Astrophysics Data System (ADS)

    Azizi, K.; Sundu, H.; Türkan, A.; Veliev, E. Veli

    2016-01-01

    Investigation of the thermal properties of the mesons with higher spin is one of the important problems in the hadron physics. At finite temperature, the Lorentz invariance is broken by the choice of a preferred frame of reference and some new operators appear in the Wilson expansion. Taking into account these additional operators, we calculate the thermal two-point correlation function for D2*(2460 ) and Ds2 *(2573 ) tensor mesons. In order to perform the numerical analysis, we use the fermionic part of the energy density obtained both from lattice QCD and Chiral perturbation theory. We also use the temperature dependent continuum threshold and show that the values of the decay constants decrease considerably near to the critical temperature compared to their values in the vacuum. Our results at zero temperature are in good consistency with predictions of other nonperturbative models.

  19. Discovery of a Significant Acetone•Hydroperoxy Adduct Chaperone Effect and Its Impact on the Determination of Room Temperature Rate Constants for Acetonylperoxy/Hydroperoxy Self-Reactions and Cross Reaction Via Infrared Kinetic Spectroscopy.

    NASA Astrophysics Data System (ADS)

    Grieman, F. J.; Hui, A. O.; Okumura, M.; Sander, S. P.

    2017-12-01

    In order to model the upper troposphere/lower stratosphere in regions containing acetone properly, the kinetics of the acetonylperoxy/hydroperoxy self-reactions and cross reaction have been studied over a wide temperature range using Infrared Kinetic Spectroscopy. We report here the determination of different rate constants for the acetonylperoxy chemistry that we obtained at 298 K compared to currently accepted values. A considerable increase in the observed HO2 self-reaction rate constant due to rate enhancement via the chaperone effect from the reaction between HO2 and the (CH3)2CO•HO2 hydrogen-bonded adduct, even at room temperature, was discovered that was previously ignored. Correct determination of the acetonylperoxy and hydroperoxy kinetics must include this dependence of the HO2 self-reaction rate on acetone concentration. Via excimer laser flash photolysis to create the radical reactants, HO2 absorption was monitored in the infrared by diode laser wavelength modulation detection simultaneously with CH3C(O)CH2O2absorption monitored in the ultraviolet at 300 nm as a function of time. Resulting decay curves were fit concurrently first over a short time scale to obtain the rate constants minimizing subsequent product reactions. Modeling/fitting with a complete reaction scheme was then performed to refine the rate constants and test their veracity. Experiments were carried out over a variety of concentrations of acetone and methanol. Although no effect due to methanol concentration was found at room temperature, the rate constant for the hydroperoxy self-reaction was found to increase linearly with acetone concentration which is interpreted as the adduct being formed and resulting in a chaperone mechanism that enhances the self-reaction rate: (CH3)2CO·HO2 + HO2 → H2O2 + O2 + (CH3)2CO Including this effect, the resulting room temperature rate constants for the cross reaction and the acetonylperoxy self-reaction were found to be 2-3 times smaller than

  20. USE OF ROUGH SETS AND SPECTRAL DATA FOR BUILDING PREDICTIVE MODELS OF REACTION RATE CONSTANTS

    EPA Science Inventory

    A model for predicting the log of the rate constants for alkaline hydrolysis of organic esters has been developed with the use of gas-phase min-infrared library spectra and a rule-building software system based on the mathematical theory of rough sets. A diverse set of 41 esters ...

  1. Equivalent formulations of the Riemann hypothesis based on lines of constant phase

    NASA Astrophysics Data System (ADS)

    Schleich, W. P.; Bezděková, I.; Kim, M. B.; Abbott, P. C.; Maier, H.; Montgomery, H. L.; Neuberger, J. W.

    2018-06-01

    We prove the equivalence of three formulations of the Riemann hypothesis for functions f defined by the four assumptions: (a 1) f satisfies the functional equation f(1 ‑ s) = f(s) for the complex argument s ≡ σ + iτ, (a2) f is free of any pole, (a3) for large positive values of σ the phase θ of f increases in a monotonic way without a bound as τ increases, and (a4) the zeros of f as well as of the first derivative f ‧ of f are simple zeros. The three equivalent formulations are: (R1) All zeros of f are located on the critical line σ = 1/2, (R2) All lines of constant phase of f corresponding to +/- π ,+/- 2π ,+/- 3π , ... merge with the critical line, and (R3) All points where f ‧ vanishes are located on the critical line, and the phases of f at two consecutive zeros of f ‧ differ by π. Our proof relies on the topology of the lines of constant phase of f dictated by complex analysis and the assumptions (a1)–(a4). Moreover, we show that (R2) implies (R1) even in the absence of (a4). In this case (a4) is a consequence of (R2).

  2. Evaluation and comparison of diffusion MR methods for measuring apparent transcytolemmal water exchange rate constant

    NASA Astrophysics Data System (ADS)

    Tian, Xin; Li, Hua; Jiang, Xiaoyu; Xie, Jingping; Gore, John C.; Xu, Junzhong

    2017-02-01

    Two diffusion-based approaches, CG (constant gradient) and FEXI (filtered exchange imaging) methods, have been previously proposed for measuring transcytolemmal water exchange rate constant kin, but their accuracy and feasibility have not been comprehensively evaluated and compared. In this work, both computer simulations and cell experiments in vitro were performed to evaluate these two methods. Simulations were done with different cell diameters (5, 10, 20 μm), a broad range of kin values (0.02-30 s-1) and different SNR's, and simulated kin's were directly compared with the ground truth values. Human leukemia K562 cells were cultured and treated with saponin to selectively change cell transmembrane permeability. The agreement between measured kin's of both methods was also evaluated. The results suggest that, without noise, the CG method provides reasonably accurate estimation of kin especially when it is smaller than 10 s-1, which is in the typical physiological range of many biological tissues. However, although the FEXI method overestimates kin even with corrections for the effects of extracellular water fraction, it provides reasonable estimates with practical SNR's and more importantly, the fitted apparent exchange rate AXR showed approximately linear dependence on the ground truth kin. In conclusion, either CG or FEXI method provides a sensitive means to characterize the variations in transcytolemmal water exchange rate constant kin, although the accuracy and specificity is usually compromised. The non-imaging CG method provides more accurate estimation of kin, but limited to large volume-of-interest. Although the accuracy of FEXI is compromised with extracellular volume fraction, it is capable of spatially mapping kin in practice.

  3. Determination of Bimolecular Rate Constants for Reactions of Hydroxyl Radical with Pharmaceutical and Cosmetics Chemicals - Implications to the Fate in the Aquatic Environment

    NASA Astrophysics Data System (ADS)

    Nakajima, H.; Arakaki, T.; Anastasio, C.

    2008-12-01

    Large organic compounds such as hyaluronic acid and chondroitin sulfate are often used in pharmaceutical and cosmetics products, but their chemical degradation pathways are not well understood. To better elucidate their fate in the aquatic environment, we initiated a study to determine bimolecular rate constants between these organic compounds and hydroxyl radical (OH), which is a potent oxidant in the environment. The lifetimes of many organic compounds are determined by reactions with OH radicals, and the lifetime of OH is often controlled by reactions with organic compounds. To determine these bimolecular rate constants we used a competition kinetics technique with either hydrogen peroxide or nitrate as a source of OH and benzoate as the competing sink. Since the molecular weights of some of the large organic compounds we studied were not known, we used dissolved organic carbon (DOC) concentrations to determine mole-carbon based bimolecular rate constants, instead of the commonly used molar-based bimolecular rate constants. We will report the mole-carbon based bimolecular rate constants of OH, determined at room temperature, with hyaluronic acid, chondroitin sulfate and some other large organic compounds.

  4. Slow Crack Growth Analysis of Brittle Materials with Finite Thickness Subjected to Constant Stress-Rate Flexural Loading

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

    A two-dimensional, numerical analysis of slow crack growth (SCG) was performed for brittle materials with finite thickness subjected to constant stress-rate ("dynamic fatigue") loading in flexure. The numerical solution showed that the conventional, simple, one-dimensional analytical solution can be used with a maximum error of about 5% in determining the SCG parameters of a brittle material with the conditions of a normalized thickness (a ratio of specimen thickness to initial crack size) T > 3.3 and of a SCG parameter n > 10. The change in crack shape from semicircular to elliptical configurations was significant particularly at both low stress rate and low T, attributed to predominant difference in stress intensity factor along the crack front. The numerical solution of SCG parameters was supported within the experimental range by the data obtained from constant stress-rate flexural testing for soda-lime glass microslides at ambient temperature.

  5. Gravity and Zero Point Energy

    NASA Astrophysics Data System (ADS)

    Massie, U. W.

    When Planck introduced the 1/2 hv term to his 1911 black body equation he showed that there is a residual energy remaining at zero degree K after all thermal energy ceased. Other investigators, including Lamb, Casimir, and Dirac added to this information. Today zero point energy (ZPE) is accepted as an established condition. The purpose of this paper is to demonstrate that the density of the ZPE is given by the gravity constant (G) and the characteristics of its particles are revealed by the cosmic microwave background (CMB). Eddies of ZPE particles created by flow around mass bodies reduce the pressure normal to the eddy flow and are responsible for the force of gravity. Helium atoms resonate with ZPE particles at low temperature to produce superfluid helium. High velocity micro vortices of ZPE particles about a basic particle or particles are responsible for electromagnetic forces. The speed of light is the speed of the wave front in the ZPE and its value is a function of the temperature and density of the ZPE.

  6. Constant Flux Proxies and Pleistocene Sediment Accumulation Rates on the Juan de Fuca Ridge in the Northeast Pacific

    NASA Astrophysics Data System (ADS)

    Middleton, J. L.; Mukhopadhyay, S.; Langmuir, C. H.; Costa, K.; McManus, J. F.; d'Almeida, M.; Huybers, P. J.; Winckler, G.

    2016-12-01

    Mass accumulation rates of marine sediments are often employed to constrain deposition rates of important proxies such as terrigenous dust, carbonate, and biogenic opal to quantitatively examine variations in continental aridity, atmospheric transport, and biologic productivity across changing climatic conditions. However, deposition rates that are estimated using traditional mass accumulation rates calculated from sediment core age models can be subject to bias from lateral sediment transport and limited age model resolution. Constant flux proxies, such as extraterrestrial helium-3 (3HeET) and excess thorium-230 (230ThXS), can be used to calculate vertical sediment accumulation rates that are independent of age model uncertainties and the effects of lateral sediment transport. While a short half-life limits analyses of 230ThXS to the past 500 ka, 3HeET is stable and could be used to constrain sedimentary fluxes during much of the Cenozoic. Despite the vast paleoceanographic potential of constant flux proxies, few studies have directly compared the behavior of 230ThXS and 3HeET using measurements from the same samples. Sediment grain size fractionation and local scavenging effects may differentially bias one or both proxy systems and complicate the interpretation of 230ThXS or 3HeET data. We will present a new record of vertical sediment accumulation rates spanning the past 600 ka in the Northeast Pacific constrained using analyses of both 3HeET and 230ThXS in two sediment cores from cruise AT26-19 on the Juan de Fuca Ridge. Such a record allows for intercomparison of both constant flux proxies in the mid-ocean ridge environment and examination of sedimentary behavior across multiple glacial cycles. The 230ThXS-derived accumulation rates typically range from 0.5 to 2 g cm-2 ka-1 over the past 450 ka, with periods of maximum deposition coinciding with glacial maxima. Preliminary results of samples analyzed with both 3HeET and 230ThXS indicate relative consistency

  7. System selects framing rate for spectrograph camera

    NASA Technical Reports Server (NTRS)

    1965-01-01

    Circuit using zero-order light is reflected to a photomultiplier in the incoming radiation of a spectrograph monitor to provide an error signal which controls the advancing and driving rate of the film through the camera.

  8. 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.

  9. High-level theoretical study of the reaction between hydroxyl and ammonia: Accurate rate constants from 200 to 2500 K

    NASA Astrophysics Data System (ADS)

    Nguyen, Thanh Lam; Stanton, John F.

    2017-10-01

    Hydrogen abstraction from NH3 by OH to produce H2O and NH2—an important reaction in combustion of NH3 fuel—was studied with a theoretical approach that combines high level quantum chemistry and advanced chemical kinetics methods. Thermal rate constants calculated from first principles agree well (within 5%-20%) with available experimental data over a temperature range that extends from 200 to 2500 K. Quantum mechanical tunneling effects were found to be important; they lead to a decided curvature and non-Arrhenius behavior for the rate constant.

  10. High-level theoretical study of the reaction between hydroxyl and ammonia: Accurate rate constants from 200 to 2500 K.

    PubMed

    Nguyen, Thanh Lam; Stanton, John F

    2017-10-21

    Hydrogen abstraction from NH 3 by OH to produce H 2 O and NH 2 -an important reaction in combustion of NH 3 fuel-was studied with a theoretical approach that combines high level quantum chemistry and advanced chemical kinetics methods. Thermal rate constants calculated from first principles agree well (within 5%-20%) with available experimental data over a temperature range that extends from 200 to 2500 K. Quantum mechanical tunneling effects were found to be important; they lead to a decided curvature and non-Arrhenius behavior for the rate constant.

  11. High-level theoretical study of the reaction between hydroxyl and ammonia: Accurate rate constants from 200 to 2500 K

    DOE PAGES

    Nguyen, Thanh Lam; Stanton, John F.

    2017-06-02

    Hydrogen abstraction from NH 3 by OH to produce H 2O and NH 2 — an important reaction in combustion of NH 3 fuel — was studied with a theoretical approach that combines high level quantum chemistry and advanced chemical kinetics methods. Thermal rate constants calculated from first principles agree well (within 5 to 20%) with available experimental data over a temperature range that extends from 200 to 2500 K. Here, quantum mechanical tunneling effects were found to be important; they lead to a decided curvature and non-Arrhenius behavior for the rate constant.

  12. Sequential Metabolic Phases as a Means to Optimize Cellular Output in a Constant Environment

    PubMed Central

    Bockmayr, Alexander; Holzhütter, Hermann-Georg

    2015-01-01

    Temporal changes of gene expression are a well-known regulatory feature of all cells, which is commonly perceived as a strategy to adapt the proteome to varying external conditions. However, temporal (rhythmic and non-rhythmic) changes of gene expression are also observed under virtually constant external conditions. Here we hypothesize that such changes are a means to render the synthesis of the metabolic output more efficient than under conditions of constant gene activities. In order to substantiate this hypothesis, we used a flux-balance model of the cellular metabolism. The total time span spent on the production of a given set of target metabolites was split into a series of shorter time intervals (metabolic phases) during which only selected groups of metabolic genes are active. The related flux distributions were calculated under the constraint that genes can be either active or inactive whereby the amount of protein related to an active gene is only controlled by the number of active genes: the lower the number of active genes the more protein can be allocated to the enzymes carrying non-zero fluxes. This concept of a predominantly protein-limited efficiency of gene expression clearly differs from other concepts resting on the assumption of an optimal gene regulation capable of allocating to all enzymes and transporters just that fraction of protein necessary to prevent rate limitation. Applying this concept to a simplified metabolic network of the central carbon metabolism with glucose or lactate as alternative substrates, we demonstrate that switching between optimally chosen stationary flux modes comprising different sets of active genes allows producing a demanded amount of target metabolites in a significantly shorter time than by a single optimal flux mode at fixed gene activities. Our model-based findings suggest that temporal expression of metabolic genes can be advantageous even under conditions of constant external substrate supply. PMID:25786979

  13. Experimental and computational results on exciton/free-carrier ratio, hot/thermalized carrier diffusion, and linear/nonlinear rate constants affecting scintillator proportionality

    NASA Astrophysics Data System (ADS)

    Williams, R. T.; Grim, Joel Q.; Li, Qi; Ucer, K. B.; Bizarri, G. A.; Kerisit, S.; Gao, Fei; Bhattacharya, P.; Tupitsyn, E.; Rowe, E.; Buliga, V. M.; Burger, A.

    2013-09-01

    Models of nonproportional response in scintillators have highlighted the importance of parameters such as branching ratios, carrier thermalization times, diffusion, kinetic order of quenching, associated rate constants, and radius of the electron track. For example, the fraction ηeh of excitations that are free carriers versus excitons was shown by Payne and coworkers to have strong correlation with the shape of electron energy response curves from Compton-coincidence studies. Rate constants for nonlinear quenching are implicit in almost all models of nonproportionality, and some assumption about track radius must invariably be made if one is to relate linear energy deposition dE/dx to volume-based excitation density n (eh/cm3) in terms of which the rates are defined. Diffusion, affecting time-dependent track radius and thus density of excitations, has been implicated as an important factor in nonlinear light yield. Several groups have recently highlighted diffusion of hot electrons in addition to thermalized carriers and excitons in scintillators. However, experimental determination of many of these parameters in the insulating crystals used as scintillators has seemed difficult. Subpicosecond laser techniques including interband z scan light yield, fluence-dependent decay time, and transient optical absorption are now yielding experimental values for some of the missing rates and ratios needed for modeling scintillator response. First principles calculations and Monte Carlo simulations can fill in additional parameters still unavailable from experiment. As a result, quantitative modeling of scintillator electron energy response from independently determined material parameters is becoming possible on an increasingly firmer data base. This paper describes recent laser experiments, calculations, and numerical modeling of scintillator response.

  14. Experimental and computational results on exciton/free-carrier ratio, hot/thermalized carrier diffusion, and linear/nonlinear rate constants affecting scintillator proportionality

    DOE PAGES

    Williams, R. T.; Grim, Joel Q.; Li, Qi; ...

    2013-09-26

    Models of nonproportional response in scintillators have highlighted the importance of parameters such as branching ratios, carrier thermalization times, diffusion, kinetic order of quenching, associated rate constants, and radius of the electron track. For example, the fraction ηeh of excitations that are free carriers versus excitons was shown by Payne and coworkers to have strong correlation with the shape of electron energy response curves from Compton-coincidence studies. Rate constants for nonlinear quenching are implicit in almost all models of nonproportionality, and some assumption about track radius must invariably be made if one is to relate linear energy deposition dE/dx tomore » volume-based excitation density n (eh/cm 3) in terms of which the rates are defined. Diffusion, affecting time-dependent track radius and thus density of excitations, has been implicated as an important factor in nonlinear light yield. Several groups have recently highlighted diffusion of hot electrons in addition to thermalized carriers and excitons in scintillators. However, experimental determination of many of these parameters in the insulating crystals used as scintillators has seemed difficult. Subpicosecond laser techniques including interband z scan light yield, fluence-dependent decay time, and transient optical absorption are now yielding experimental values for some of the missing rates and ratios needed for modeling scintillator response. First principles calculations and Monte Carlo simulations can fill in additional parameters still unavailable from experiment. As a result, quantitative modeling of scintillator electron energy response from independently determined material parameters is becoming possible on an increasingly firmer data base. This study describes recent laser experiments, calculations, and numerical modeling of scintillator response.« less

  15. Quantitation of Bone Growth Rate Variability in Rats Exposed to Micro-(near zero G) and Macrogravity (2G)

    NASA Technical Reports Server (NTRS)

    Bromage, Timothy G.; Doty, Stephen B.; Smolyar, Igor; Holton, Emily

    1997-01-01

    Our stated primary objective is to quantify the growth rate variability of rat lamellar bone exposed to micro- (near zero G: e.g., Cosmos 1887 & 2044; SLS-1 & SLS-2) and macrogravity (2G). The primary significance of the proposed work is that an elegant method will be established that unequivocally characterizes the morphological consequences of gravitational factors on developing bone. The integrity of this objective depends upon our successful preparation of thin sections suitable for imaging individual bone lamellae, and our imaging and quantitation of growth rate variability in populations of lamellae from individual bone samples.

  16. Predictive Rate-Distortion for Infinite-Order Markov Processes

    NASA Astrophysics Data System (ADS)

    Marzen, Sarah E.; Crutchfield, James P.

    2016-06-01

    Predictive rate-distortion analysis suffers from the curse of dimensionality: clustering arbitrarily long pasts to retain information about arbitrarily long futures requires resources that typically grow exponentially with length. The challenge is compounded for infinite-order Markov processes, since conditioning on finite sequences cannot capture all of their past dependencies. Spectral arguments confirm a popular intuition: algorithms that cluster finite-length sequences fail dramatically when the underlying process has long-range temporal correlations and can fail even for processes generated by finite-memory hidden Markov models. We circumvent the curse of dimensionality in rate-distortion analysis of finite- and infinite-order processes by casting predictive rate-distortion objective functions in terms of the forward- and reverse-time causal states of computational mechanics. Examples demonstrate that the resulting algorithms yield substantial improvements.

  17. Kinetic rate laws as derived from order parameter theory I: Theoretical concepts

    NASA Astrophysics Data System (ADS)

    Salje, Ekhard

    1988-03-01

    A theoretical concept is outlined, which links the kinetics of structural transformations with thermodynamic theories of structural phase transitions. Starting from Landau theory and Markovian processes, the general rate laws for crystals with long correlation lengths are derived. The rate laws in Ginzburg-Landau theory are 269_2004_Article_BF00311038_TeX2GIFE1.gif 1{text{n }}Δ Q - 1{text{n }}fleft( Q right) ∝ - t/tau {text{ for }}T ≪ T_c {text{ and }}T ≫ T_c and Q 2∝ for T ≈ T c . The physical meaning of the time constant τ and the correction term f( Q) are explained. Fluctuations of the order parameter lead to damping behaviour with explicit dependence on the wavelength of the fluctuation wave and modulation-dependent variations of the lattice strain. Lattice relaxations and activation processes are discussed. Typical rate laws are found to follow 269_2004_Article_BF00311038_TeX2GIFE2.gif begin{gathered} ln Δ Q = rlnΔ t, \\ lnQ/Q + {1\\varepsilon }/{2k_B T}left( {Q^2 - Q_0^2 } right) = {Δ t}/{tau *} \\ which leads for short time intervals to a linear rate law 269_2004_Article_BF00311038_TeX2GIFE3.gif Δ Q ∝ Δ t It is shown that linear terms in the Landau potential are equivalent to a logarithmic decay of the excess entropy Δ S ∝ ln Δ t which is also expected to be the dominant rate law in field-induced pseudo-spin glasses: 269_2004_Article_BF00311038_TeX2GIFE4.gif Δ Q ∝ 1{text{n }}Δ t{text{ and }}1{text{n}}left( {Δ {text{Q}} \\cdot Δ {text{t}}} right) = A{text{ }}Δ t + B Fluctuations lead to spatially heterogeneous distributions of the order parameter. A two phase field is found in this case where the nucleation energy is overcome by fluctuation processes. Random fields, arising, for example, from lattice imperfections, lead also to spacially inhomogeneous material. The dominant microstructure is the lattice modulation mostly in the form of a cross hatched pattern (tweed) but also in the form of incommensurate modulations.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  19. 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.

  20. Full-order observer for direct torque control of induction motor based on constant V/F control technique.

    PubMed

    Pimkumwong, Narongrit; Wang, Ming-Shyan

    2018-02-01

    This paper presents another control method for the three-phase induction motor that is direct torque control based on constant voltage per frequency control technique. This method uses the magnitude of stator flux and torque errors to generate the stator voltage and phase angle references for controlling the induction motor by using constant voltage per frequency control method. Instead of hysteresis comparators and optimum switching table, the PI controllers and space vector modulation technique are used to reduce torque and stator-flux ripples and achieve constant switching frequency. Moreover, the coordinate transformations are not required. To implement this control method, a full-order observer is used to estimate stator flux and overcome the problems from drift and saturation in using pure integrator. The feedback gains are designed by simple manner to improve the convergence of stator flux estimation, especially in low speed range. Furthermore, the necessary conditions to maintain the stability for feedback gain design are introduced. The simulation and experimental results show accurate and stable operation of the introduced estimator and good dynamic response of the proposed control method. Copyright © 2017 ISA. Published by Elsevier Ltd. All rights reserved.

  1. First-principles calculation of photo-induced electron transfer rate constants in phthalocyanine-C60 organic photovoltaic materials: Beyond Marcus theory

    NASA Astrophysics Data System (ADS)

    Lee, Myeong H.; Dunietz, Barry D.; Geva, Eitan

    2014-03-01

    Classical Marcus theory is commonly adopted in solvent-mediated charge transfer (CT) process to obtain the CT rate constant, but it can become questionable when the intramolecular vibrational modes dominate the CT process as in OPV devices because Marcus theory treats these modes classically and therefore nuclear tunneling is not accounted for. We present a computational scheme to obtain the electron transfer rate constant beyond classical Marcus theory. Within this approach, the nuclear vibrational modes are treated quantum-mechanically and a short-time approximation is avoided. Ab initio calculations are used to obtain the basic parameters needed for calculating the electron transfer rate constant. We apply our methodology to phthalocyanine(H2PC)-C60 organic photovoltaic system where one C60 acceptor and one or two H2PC donors are included to model the donor-acceptor interface configuration. We obtain the electron transfer and recombination rate constants for all accessible charge transfer (CT) states, from which the CT exciton dynamics is determined by employing a master equation. The role of higher lying excited states in CT exciton dynamics is discussed. This work is pursued as part of the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US Department of Energy Office of Science, Office of Basic Energy Sciences under 390 Award No. DE-SC0000957.

  2. KABAM Version 1.0 User's Guide and Technical Documentation - Appendix H - Methods for Estimating Metabolism Rate Constant

    EPA Pesticide Factsheets

    Appendix H of KABAM Version 1.0 documentation related to estimating the metabolism rate constant. KABAM is a simulation model used to predict pesticide concentrations in aquatic regions for use in exposure assessments.

  3. Flare cue symbology and EVS for zero-zero weather landing

    NASA Astrophysics Data System (ADS)

    French, Guy A.; Murphy, David M.; Ercoline, William R.

    2006-05-01

    When flying an airplane, landing is arguably the most difficult task a pilot can do. This applies to pilots of all skill levels particularly as the level of complexity in both the aircraft and environment increase. Current navigational aids, such as an instrument landing system (ILS), do a good job of providing safe guidance for an approach to an airfield. These aids provide data to primary flight reference (PFR) displays on-board the aircraft depicting through symbology what the pilot's eyes should be seeing. Piloting an approach under visual meteorological conditions (VMC) is relatively easy compared to the various complex instrument approaches under instrument meteorological conditions (IMC) which may include flying in zero-zero weather. Perhaps the most critical point in the approach is the transition to landing where the rate of closure between the wheels and the runway is critical to a smooth, accurate landing. Very few PFR's provide this flare cue information. In this study we will evaluate examples of flare cueing symbology for use in landing an aircraft in the most difficult conditions. This research is a part of a larger demonstration effort using sensor technology to land in zero-zero weather at airfields that offer no or unreliable approach guidance. Several problems exist when landing without visual reference to the outside world. One is landing with a force greater than desired at touchdown and another is landing on a point of the runway other than desired. We compare different flare cueing systems to one another and against a baseline for completing this complex approach task.

  4. Real-time method and apparatus for measuring the decay-time constant of a fluorescing phosphor

    DOEpatents

    Britton, Jr., Charles L.; Beshears, David L.; Simpson, Marc L.; Cates, Michael R.; Allison, Steve W.

    1999-01-01

    A method for determining the decay-time constant of a fluorescing phosphor is provided, together with an apparatus for performing the method. The apparatus includes a photodetector for detecting light emitted by a phosphor irradiated with an excitation pulse and for converting the detected light into an electrical signal. The apparatus further includes a differentiator for differentiating the electrical signal and a zero-crossing discrimination circuit that outputs a pulse signal having a pulse width corresponding to the time period between the start of the excitation pulse and the time when the differentiated electrical signal reaches zero. The width of the output pulse signal is proportional to the decay-time constant of the phosphor.

  5. Effects of Cooling Rate on 6.5% Silicon Steel Ordering

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

    Cui, Jun; Macziewski, Chad; Jensen, Brandt

    Increasing Si content improves magnetic and electrical properties of electrical steel, with 6.5% Si as the optimum. Unfortunately, when Si content approaches 5.7%, the Fe-Si alloy becomes brittle. At 6.5%, the steel conventional cold rolling process is no longer applicable. The heterogeneous formation of B2 and D03 ordered phases is responsible for the embrittlement. The formation of these ordered phases can be impeded by rapid cooling. However, only the cooling rates of water and brine water were investigated. A comprehensive study of the effect of rapid cooling rate on the formation of the ordered phases was carried out by varyingmore » wheel speed and melt-injection rate. Thermal imaging employed to measure cooling rates while microstructures of the obtained ribbons are characterized using X-ray diffraction and TEM. The electrical, magnetic and mechanical properties are characterized using 4-pt probe, VSM, and macro-indentation methods. The relations between physical properties and ordered phases are established.« less

  6. Detection of exudates in fundus imagery using a constant false-alarm rate (CFAR) detector

    NASA Astrophysics Data System (ADS)

    Khanna, Manish; Kapoor, Elina

    2014-05-01

    Diabetic retinopathy is the leading cause of blindness in adults in the United States. The presence of exudates in fundus imagery is the early sign of diabetic retinopathy so detection of these lesions is essential in preventing further ocular damage. In this paper we present a novel technique to automatically detect exudates in fundus imagery that is robust against spatial and temporal variations of background noise. The detection threshold is adjusted dynamically, based on the local noise statics around the pixel under test in order to maintain a pre-determined, constant false alarm rate (CFAR). The CFAR detector is often used to detect bright targets in radar imagery where the background clutter can vary considerably from scene to scene and with angle to the scene. Similarly, the CFAR detector addresses the challenge of detecting exudate lesions in RGB and multispectral fundus imagery where the background clutter often exhibits variations in brightness and texture. These variations present a challenge to common, global thresholding detection algorithms and other methods. Performance of the CFAR algorithm is tested against a publicly available, annotated, diabetic retinopathy database and preliminary testing suggests that performance of the CFAR detector proves to be superior to techniques such as Otsu thresholding.

  7. Ultra High Strain Rate Nanoindentation Testing.

    PubMed

    Sudharshan Phani, Pardhasaradhi; Oliver, Warren Carl

    2017-06-17

    Strain rate dependence of indentation hardness has been widely used to study time-dependent plasticity. However, the currently available techniques limit the range of strain rates that can be achieved during indentation testing. Recent advances in electronics have enabled nanomechanical measurements with very low noise levels (sub nanometer) at fast time constants (20 µs) and high data acquisition rates (100 KHz). These capabilities open the doors for a wide range of ultra-fast nanomechanical testing, for instance, indentation testing at very high strain rates. With an accurate dynamic model and an instrument with fast time constants, step load tests can be performed which enable access to indentation strain rates approaching ballistic levels (i.e., 4000 1/s). A novel indentation based testing technique involving a combination of step load and constant load and hold tests that enables measurement of strain rate dependence of hardness spanning over seven orders of magnitude in strain rate is presented. A simple analysis is used to calculate the equivalent uniaxial response from indentation data and compared to the conventional uniaxial data for commercial purity aluminum. Excellent agreement is found between the indentation and uniaxial data over several orders of magnitude of strain rate.

  8. Effect of Phenol Molecular Structure on Bacterial Transformation Rate Constants in Pond and River Samples

    PubMed Central

    Paris, Doris F.; Wolfe, N. Lee; Steen, William C.; Baughman, George L.

    1983-01-01

    Microbial transformation rate constants for a series of phenols were correlated with a property of the substituents, van der Waal's radius. Transformation products were the corresponding catechols, with the exception of p-hydroxybenzoic acid, the product of p-acetylphenol. A different product suggested a different pathway; p-acetylphenol, therefore, was deleted from the data base. PMID:16346236

  9. The paradoxical zero reflection at zero energy

    NASA Astrophysics Data System (ADS)

    Ahmed, Zafar; Sharma, Vibhu; Sharma, Mayank; Singhal, Ankush; Kaiwart, Rahul; Priyadarshini, Pallavi

    2017-03-01

    Usually, the reflection probability R(E) of a particle of zero energy incident on a potential which converges to zero asymptotically is found to be 1: R(0)=1. But earlier, a paradoxical phenomenon of zero reflection at zero energy (R(0)=0) has been revealed as a threshold anomaly. Extending the concept of half-bound state (HBS) of 3D, here we show that in 1D when a symmetric (asymmetric) attractive potential well possesses a zero-energy HBS, R(0)=0 (R(0)\\ll 1). This can happen only at some critical values q c of an effective parameter q of the potential well in the limit E\\to {0}+. We demonstrate this critical phenomenon in two simple analytically solvable models: square and exponential wells. However, in numerical calculations, even for these two models R(0)=0 is observed only as extrapolation to zero energy from low energies, close to a precise critical value q c. By numerical investigation of a variety of potential wells, we conclude that for a given potential well (symmetric or asymmetric), we can adjust the effective parameter q to have a low reflection at a low energy.

  10. Dynamics in copy numbers of five plasmids of a dairy Lactococcus lactis in dairy-related conditions including near-zero growth rates.

    PubMed

    van Mastrigt, Oscar; Lommers, Marcel M A N; de Vries, Yorick C; Abee, Tjakko; Smid, Eddy J

    2018-03-23

    Lactic acid bacteria can carry multiple plasmids affecting their performance in dairy fermentations. The expression of plasmid-encoded genes and the activity of the corresponding proteins is severely affected by changes in the number of plasmid copies. We studied the impact of growth rate on dynamics of plasmid copy numbers at high growth rates in chemostat cultures and down to near-zero growth rates in retentostat cultures. Five plasmids of the dairy strain Lactococcus lactis FM03-V1 were selected which varied in size (3 to 39 kb), in replication mechanism (theta or rolling-circle) and in putative (dairy-associated) functions. Copy numbers ranged from 1.5 to 40.5 and the copy number of theta-type replicating plasmids were negatively correlated to the plasmid size. Despite the extremely wide range of growth rates (0.0003 h -1 to 0.6 h -1 ), copy numbers of the five plasmids were stable and only slightly increased at near-zero growth rates showing that the plasmid replication rate was strictly controlled. One low-copy number plasmid, carrying a large exopolysaccharide gene cluster, was segregationally unstable during retentostat cultivations reflected in complete loss of the plasmid in one of the retentostat cultures. The copy number of the five plasmids was also hardly affected by varying the pH value, nutrient limitation or presence of citrate (maximum 2.2-fold) signifying the stability in copy number of the plasmids. Importance Lactococcus lactis is extensively used in starter cultures for dairy fermentations. Important traits for growth and survival of L. lactis in dairy fermentations are encoded by genes located on plasmids, such as genes involved in lactose and citrate metabolism, protein degradation and oligopeptide uptake and bacteriophage resistance. Because the number of plasmid copies could affect the expression of plasmid-encoded genes, it is important to know the factors that influence the plasmid copy numbers. We monitored plasmid copy numbers of L

  11. Global Kinetic Constants for Thermal Oxidative Degradation of a Cellulosic Paper

    NASA Technical Reports Server (NTRS)

    Kashiwagi, Takashi; Nambu, Hidesaburo

    1992-01-01

    Values of global kinetic constants for pyrolysis, thermal oxidative degradation, and char oxidation of a cellulosic paper were determined by a derivative thermal gravimetric study. The study was conducted at heating rates of 0.5, 1, 1.5, 3, and 5 C/min in ambient atmospheres of nitrogen, 0.28, 1.08, 5.2 percent oxygen concentrations, and air. Sample weight loss rate, concentrations of CO, CO2, and H2O in the degradation products, and oxygen consumption were continuously measured during the experiment. Values of activation energy, preexponential factor, orders of reaction, and yields of CO, CO2, H2O, total hydrocarbons, and char for each degradation reaction were derived from the results. Heat of reaction for each reaction was determined by differential scanning calorimetry. A comparison of the calculated CO, CO2, H2O, total hydrocarbons, sample weight loss rate, and oxygen consumption was made with the measured results using the derived kinetic constants, and the accuracy of the values of kinetic constants was discussed.

  12. Optimization of High-Throughput Sequencing Kinetics for determining enzymatic rate constants of thousands of RNA substrates

    PubMed Central

    Niland, Courtney N.; Jankowsky, Eckhard; Harris, Michael E.

    2016-01-01

    Quantification of the specificity of RNA binding proteins and RNA processing enzymes is essential to understanding their fundamental roles in biological processes. High Throughput Sequencing Kinetics (HTS-Kin) uses high throughput sequencing and internal competition kinetics to simultaneously monitor the processing rate constants of thousands of substrates by RNA processing enzymes. This technique has provided unprecedented insight into the substrate specificity of the tRNA processing endonuclease ribonuclease P. Here, we investigate the accuracy and robustness of measurements associated with each step of the HTS-Kin procedure. We examine the effect of substrate concentration on the observed rate constant, determine the optimal kinetic parameters, and provide guidelines for reducing error in amplification of the substrate population. Importantly, we find that high-throughput sequencing, and experimental reproducibility contribute their own sources of error, and these are the main sources of imprecision in the quantified results when otherwise optimized guidelines are followed. PMID:27296633

  13. Robust PI and PID design for first- and second-order processes with zeros, time-delay and structured uncertainties

    NASA Astrophysics Data System (ADS)

    Parada, M.; Sbarbaro, D.; Borges, R. A.; Peres, P. L. D.

    2017-01-01

    The use of robust design techniques such as the one based on ? and ? for tuning proportional integral (PI) and proportional integral derivative (PID) controllers have been limited to address a small set of processes. This work addresses the problem by considering a wide set of possible plants, both first- and second-order continuous-time systems with time delays and zeros, leading to PI and PID controllers. The use of structured uncertainties to handle neglected dynamics allows to expand the range of processes to be considered. The proposed approach takes into account the robustness of the controller with respect to these structured uncertainties by using the small-gain theorem. In addition, improved performance is sought through the minimisation of an upper bound to the closed-loop system ? norm. A Lyapunov-Krasovskii-type functional is used to obtain delay-dependent design conditions. The controller design is accomplished by means of a convex optimisation procedure formulated using linear matrix inequalities. In order to illustrate the flexibility of the approach, several examples considering recycle compensation, reduced-order controller design and a practical implementation are addressed. Numerical experiments are provided in each case to highlight the main characteristics of the proposed design method.

  14. 20 CFR 345.302 - Definition of terms and phrases used in experience-rating.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... pooled charge ratio thus picks up the cost of benefits paid to employees of employers whose rate of... raised in order to bring that rate to the minimum rate of zero is multiplied by the employer's 1-year...

  15. Zero-block mode decision algorithm for H.264/AVC.

    PubMed

    Lee, Yu-Ming; Lin, Yinyi

    2009-03-01

    In the previous paper , we proposed a zero-block intermode decision algorithm for H.264 video coding based upon the number of zero-blocks of 4 x 4 DCT coefficients between the current macroblock and the co-located macroblock. The proposed algorithm can achieve significant improvement in computation, but the computation performance is limited for high bit-rate coding. To improve computation efficiency, in this paper, we suggest an enhanced zero-block decision algorithm, which uses an early zero-block detection method to compute the number of zero-blocks instead of direct DCT and quantization (DCT/Q) calculation and incorporates two adequate decision methods into semi-stationary and nonstationary regions of a video sequence. In addition, the zero-block decision algorithm is also applied to the intramode prediction in the P frame. The enhanced zero-block decision algorithm brings out a reduction of average 27% of total encoding time compared to the zero-block decision algorithm.

  16. Absolute protein-protein association rate constants from flexible, coarse-grained Brownian dynamics simulations: the role of intermolecular hydrodynamic interactions in barnase-barstar association.

    PubMed

    Frembgen-Kesner, Tamara; Elcock, Adrian H

    2010-11-03

    Theory and computation have long been used to rationalize the experimental association rate constants of protein-protein complexes, and Brownian dynamics (BD) simulations, in particular, have been successful in reproducing the relative rate constants of wild-type and mutant protein pairs. Missing from previous BD studies of association kinetics, however, has been the description of hydrodynamic interactions (HIs) between, and within, the diffusing proteins. Here we address this issue by rigorously including HIs in BD simulations of the barnase-barstar association reaction. We first show that even very simplified representations of the proteins--involving approximately one pseudoatom for every three residues in the protein--can provide excellent reproduction of the absolute association rate constants of wild-type and mutant protein pairs. We then show that simulations that include intermolecular HIs also produce excellent estimates of association rate constants, but, for a given reaction criterion, yield values that are decreased by ∼35-80% relative to those obtained in the absence of intermolecular HIs. The neglect of intermolecular HIs in previous BD simulation studies, therefore, is likely to have contributed to the somewhat overestimated absolute rate constants previously obtained. Consequently, intermolecular HIs could be an important component to include in accurate modeling of the kinetics of macromolecular association events. Copyright © 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  17. Viscoelastic optical nonlocality of low-loss epsilon-near-zero nanofilms.

    PubMed

    de Ceglia, Domenico; Scalora, Michael; Vincenti, Maria A; Campione, Salvatore; Kelley, Kyle; Runnerstrom, Evan L; Maria, Jon-Paul; Keeler, Gordon A; Luk, Ting S

    2018-06-19

    Optical nonlocalities are elusive and hardly observable in traditional plasmonic materials like noble and alkali metals. Here we report experimental observation of viscoelastic nonlocalities in the infrared optical response of epsilon-near-zero nanofilms made of low-loss doped cadmium-oxide. The nonlocality is detectable thanks to the low damping rate of conduction electrons and the virtual absence of interband transitions at infrared wavelengths. We describe the motion of conduction electrons using a hydrodynamic model for a viscoelastic fluid, and find excellent agreement with experimental results. The electrons' elasticity blue-shifts the infrared plasmonic resonance associated with the main epsilon-near-zero mode, and triggers the onset of higher-order resonances due to the excitation of electron-pressure modes above the bulk plasma frequency. We also provide evidence of the existence of nonlocal damping, i.e., viscosity, in the motion of optically-excited conduction electrons using a combination of spectroscopic ellipsometry data and predictions based on the viscoelastic hydrodynamic model.

  18. Hydrology of a zero-order Southern Piedmont watershed through 45 years of changing agricultural land use. Part 1. Monthly and seasonal rainfall-runoff relationships

    NASA Astrophysics Data System (ADS)

    Endale, Dinku M.; Fisher, Dwight S.; Steiner, Jean L.

    2006-01-01

    Few studies have reported runoff from small agricultural watersheds over sufficiently long period so that the effect of different cover types on runoff can be examined. We analyzed 45-yrs of monthly and annual rainfall-runoff characteristics of a small (7.8 ha) zero-order typical Southern Piedmont watershed in southeastern United States. Agricultural land use varied as follows: 1. Row cropping (5-yrs); 2. Kudzu ( Pueraria lobata; 5-yrs); 3. Grazed kudzu and rescuegrass ( Bromus catharticus; 7-yrs); and 4. Grazed bermudagrass and winter annuals ( Cynodon dactylon; 28-yrs). Land use and rainfall variability influenced runoff characteristics. Row cropping produced the largest runoff amount, percentage of the rainfall partitioned into runoff, and peak flow rates. Kudzu reduced spring runoff and almost eliminated summer runoff, as did a mixture of kudzu and rescuegrass (KR) compared to row cropping. Peak flow rates were also reduced during the kudzu and KR. Peak flow rates increased under bermudagrass but were lower than during row cropping. A simple process-based 'tanh' model modified to take the previous month's rainfall into account produced monthly rainfall and runoff correlations with coefficient of determination ( R2) of 0.74. The model was tested on independent data collected during drought. Mean monthly runoff was 1.65 times the observed runoff. Sustained hydrologic monitoring is essential to understanding long-term rainfall-runoff relationships in agricultural watersheds.

  19. Three-part joint modeling methods for complex functional data mixed with zero-and-one-inflated proportions and zero-inflated continuous outcomes with skewness.

    PubMed

    Li, Haocheng; Staudenmayer, John; Wang, Tianying; Keadle, Sarah Kozey; Carroll, Raymond J

    2018-02-20

    We take a functional data approach to longitudinal studies with complex bivariate outcomes. This work is motivated by data from a physical activity study that measured 2 responses over time in 5-minute intervals. One response is the proportion of time active in each interval, a continuous proportions with excess zeros and ones. The other response, energy expenditure rate in the interval, is a continuous variable with excess zeros and skewness. This outcome is complex because there are 3 possible activity patterns in each interval (inactive, partially active, and completely active), and those patterns, which are observed, induce both nonrandom and random associations between the responses. More specifically, the inactive pattern requires a zero value in both the proportion for active behavior and the energy expenditure rate; a partially active pattern means that the proportion of activity is strictly between zero and one and that the energy expenditure rate is greater than zero and likely to be moderate, and the completely active pattern means that the proportion of activity is exactly one, and the energy expenditure rate is greater than zero and likely to be higher. To address these challenges, we propose a 3-part functional data joint modeling approach. The first part is a continuation-ratio model to reorder the ordinal valued 3 activity patterns. The second part models the proportions when they are in interval (0,1). The last component specifies the skewed continuous energy expenditure rate with Box-Cox transformations when they are greater than zero. In this 3-part model, the regression structures are specified as smooth curves measured at various time points with random effects that have a correlation structure. The smoothed random curves for each variable are summarized using a few important principal components, and the association of the 3 longitudinal components is modeled through the association of the principal component scores. The difficulties in

  20. Evolution of the Carter constant for inspirals into a black hole: Effect of the black hole quadrupole

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

    Flanagan, Eanna E.; Laboratory for Elementary Particle Physics, Cornell University, Ithaca, New York 14853; Hinderer, Tanja

    2007-06-15

    We analyze the effect of gravitational radiation reaction on generic orbits around a body with an axisymmetric mass quadrupole moment Q to linear order in Q, to the leading post-Newtonian order, and to linear order in the mass ratio. This system admits three constants of the motion in absence of radiation reaction: energy, angular momentum along the symmetry axis, and a third constant analogous to the Carter constant. We compute instantaneous and time-averaged rates of change of these three constants. For a point particle orbiting a black hole, Ryan has computed the leading order evolution of the orbit's Carter constant,more » which is linear in the spin. Our result, when combined with an interaction quadratic in the spin (the coupling of the black hole's spin to its own radiation reaction field), gives the next to leading order evolution. The effect of the quadrupole, like that of the linear spin term, is to circularize eccentric orbits and to drive the orbital plane towards antialignment with the symmetry axis. In addition we consider a system of two point masses where one body has a single mass multipole or current multipole of order l. To linear order in the mass ratio, to linear order in the multipole, and to the leading post-Newtonian order, we show that there does not exist an analog of the Carter constant for such a system (except for the cases of an l=1 current moment and an l=2 mass moment). Thus, the existence of the Carter constant in Kerr depends on interaction effects between the different multipoles. With mild additional assumptions, this result falsifies the conjecture that all vacuum, axisymmetric spacetimes possess a third constant of the motion for geodesic motion.« less

  1. Constant strain accumulation rate between major earthquakes on the North Anatolian Fault.

    PubMed

    Hussain, Ekbal; Wright, Tim J; Walters, Richard J; Bekaert, David P S; Lloyd, Ryan; Hooper, Andrew

    2018-04-11

    Earthquakes are caused by the release of tectonic strain accumulated between events. Recent advances in satellite geodesy mean we can now measure this interseismic strain accumulation with a high degree of accuracy. But it remains unclear how to interpret short-term geodetic observations, measured over decades, when estimating the seismic hazard of faults accumulating strain over centuries. Here, we show that strain accumulation rates calculated from geodetic measurements around a major transform fault are constant for its entire 250-year interseismic period, except in the ~10 years following an earthquake. The shear strain rate history requires a weak fault zone embedded within a strong lower crust with viscosity greater than ~10 20  Pa s. The results support the notion that short-term geodetic observations can directly contribute to long-term seismic hazard assessment and suggest that lower-crustal viscosities derived from postseismic studies are not representative of the lower crust at all spatial and temporal scales.

  2. A test of inflated zeros for Poisson regression models.

    PubMed

    He, Hua; Zhang, Hui; Ye, Peng; Tang, Wan

    2017-01-01

    Excessive zeros are common in practice and may cause overdispersion and invalidate inference when fitting Poisson regression models. There is a large body of literature on zero-inflated Poisson models. However, methods for testing whether there are excessive zeros are less well developed. The Vuong test comparing a Poisson and a zero-inflated Poisson model is commonly applied in practice. However, the type I error of the test often deviates seriously from the nominal level, rendering serious doubts on the validity of the test in such applications. In this paper, we develop a new approach for testing inflated zeros under the Poisson model. Unlike the Vuong test for inflated zeros, our method does not require a zero-inflated Poisson model to perform the test. Simulation studies show that when compared with the Vuong test our approach not only better at controlling type I error rate, but also yield more power.

  3. Zero-crossing statistics for non-Markovian time series.

    PubMed

    Nyberg, Markus; Lizana, Ludvig; Ambjörnsson, Tobias

    2018-03-01

    In applications spanning from image analysis and speech recognition to energy dissipation in turbulence and time-to failure of fatigued materials, researchers and engineers want to calculate how often a stochastic observable crosses a specific level, such as zero. At first glance this problem looks simple, but it is in fact theoretically very challenging, and therefore few exact results exist. One exception is the celebrated Rice formula that gives the mean number of zero crossings in a fixed time interval of a zero-mean Gaussian stationary process. In this study we use the so-called independent interval approximation to go beyond Rice's result and derive analytic expressions for all higher-order zero-crossing cumulants and moments. Our results agree well with simulations for the non-Markovian autoregressive model.

  4. Zero-crossing statistics for non-Markovian time series

    NASA Astrophysics Data System (ADS)

    Nyberg, Markus; Lizana, Ludvig; Ambjörnsson, Tobias

    2018-03-01

    In applications spanning from image analysis and speech recognition to energy dissipation in turbulence and time-to failure of fatigued materials, researchers and engineers want to calculate how often a stochastic observable crosses a specific level, such as zero. At first glance this problem looks simple, but it is in fact theoretically very challenging, and therefore few exact results exist. One exception is the celebrated Rice formula that gives the mean number of zero crossings in a fixed time interval of a zero-mean Gaussian stationary process. In this study we use the so-called independent interval approximation to go beyond Rice's result and derive analytic expressions for all higher-order zero-crossing cumulants and moments. Our results agree well with simulations for the non-Markovian autoregressive model.

  5. Atypical transitions in material response during constant strain rate, hot deformation of austenitic steel

    NASA Astrophysics Data System (ADS)

    Borah, Utpal; Aashranth, B.; Samantaray, Dipti; Kumar, Santosh; Davinci, M. Arvinth; Albert, Shaju K.; Bhaduri, A. K.

    2017-10-01

    Work hardening, dynamic recovery and dynamic recrystallization (DRX) occurring during hot working of austenitic steel have been extensively studied. Various empirical models describe the nature and effects of these phenomena in a typical framework. However, the typical model is sometimes violated following atypical transitions in deformation mechanisms of the material. To ascertain the nature of these atypical transitions, researchers have intentionally introduced discontinuities in the deformation process, such as interrupting the deformation as in multi-step rolling and abruptly changing the rate of deformation. In this work, we demonstrate that atypical transitions are possible even in conventional single-step, constant strain rate deformation of austenitic steel. Towards this aim, isothermal, constant true strain rate deformation of austenitic steel has been carried out in a temperature range of 1173-1473 K and strain rate range of 0.01-100 s-1. The microstructural response corresponding to each deformation condition is thoroughly investigated. The conventional power-law variation of deformation grain size (D) with peak stress (σp) during DRX is taken as a typical model and experimental data is tested against it. It is shown that σp-D relations exhibit an atypical two-slope linear behaviour rather than a continuous power law relation. Similarly, the reduction in σp with temperature (T) is found to consist of two discrete linear segments. In practical terms, the two linear segments denote two distinct microstructural responses to deformation. As a consequence of this distinction, the typical model breaks down and is unable to completely relate microstructural evolution to flow behaviour. The present work highlights the microstructural mechanisms responsible for this atypical behavior and suggests strategies to incorporate the two-slope behaviour in the DRX model.

  6. 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

  7. 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; Hammes-Schiffer, Sharon

    2015-11-17

    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 regimes for the proton donor-acceptor vibrational mode. 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 does not significantly impact the rate constants derived using the cumulant expansion approachmore » in any of the regimes studied. The effects of the quadratic term may become significant when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant, however, particularly at high temperatures and for proton transfer interfaces with extremely soft proton donor-acceptor modes that are associated with extraordinarily weak hydrogen bonds. Even with the thermal averaging procedure, 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, and the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances. 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. We are grateful for support from National Institutes of Health Grant GM056207 (applications to enzymes) and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of

  8. Mittag-Leffler stability of fractional-order neural networks in the presence of generalized piecewise constant arguments.

    PubMed

    Wu, Ailong; Liu, Ling; Huang, Tingwen; Zeng, Zhigang

    2017-01-01

    Neurodynamic system is an emerging research field. To understand the essential motivational representations of neural activity, neurodynamics is an important question in cognitive system research. This paper is to investigate Mittag-Leffler stability of a class of fractional-order neural networks in the presence of generalized piecewise constant arguments. To identify neural types of computational principles in mathematical and computational analysis, the existence and uniqueness of the solution of neurodynamic system is the first prerequisite. We prove that the existence and uniqueness of the solution of the network holds when some conditions are satisfied. In addition, self-active neurodynamic system demands stable internal dynamical states (equilibria). The main emphasis will be then on several sufficient conditions to guarantee a unique equilibrium point. Furthermore, to provide deeper explanations of neurodynamic process, Mittag-Leffler stability is studied in detail. The established results are based on the theories of fractional differential equation and differential equation with generalized piecewise constant arguments. The derived criteria improve and extend the existing related results. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Photonic zero mode in a non-Hermitian photonic lattice.

    PubMed

    Pan, Mingsen; Zhao, Han; Miao, Pei; Longhi, Stefano; Feng, Liang

    2018-04-03

    Zero-energy particles (such as Majorana fermions) are newly predicted quasiparticles and are expected to play an important role in fault-tolerant quantum computation. In conventional Hermitian quantum systems, however, such zero states are vulnerable and even become vanishing if couplings with surroundings are of the same topological nature. Here we demonstrate a robust photonic zero mode sustained by a spatial non-Hermitian phase transition in a parity-time (PT) symmetric lattice, despite the same topological order across the entire system. The non-Hermitian-enhanced topological protection ensures the reemergence of the zero mode at the phase transition interface when the two semi-lattices under different PT phases are decoupled effectively in their real spectra. Residing at the midgap level of the PT symmetric spectrum, the zero mode is topologically protected against topological disorder. We experimentally validated the robustness of the zero-energy mode by ultrafast heterodyne measurements of light transport dynamics in a silicon waveguide lattice.

  10. Evaluating the Radiation Damage to Quartz Rods in the ATLAS Zero Degree Calorimeter

    NASA Astrophysics Data System (ADS)

    Goodale, Kathryn

    2017-09-01

    At the Large Hadron Collider, the ATLAS experiment studies particle collisions to explore the fundamental particles of nature. A key instrumentation technology used by the ATLAS experiment are calorimeters for particle energy measurements. UIUC is developing a new Zero-Degree Calorimeter; a hadronic calorimeter located at zero-degrees from the collision axis. It consists of alternating layers of tungsten and oil; passive and active layers, respectively. The passive layers cause intense showers of secondary particles. These particles then produce Cherenkov radiation in the active layer. The oil in the active layer is replaced at a constant rate allowing for very high radiation doses in the detector without deteriorating the radiator material. The active layer includes wavelength shifters that absorb and re-emit isotropically the Cherenkov radiation. In this way, some of the photons arrive at two, hollow quartz rods which are filled by a second stage wavelength shifter. Here the light is absorbed and re-directed to a Silicon Photomultiplier for detection. In this paper, the impact of ionizing radiation on quartz rods will be discussed and the results from attenuation measurements will be presented.

  11. Fast, Computer Supported Experimental Determination of Absolute Zero Temperature at School

    ERIC Educational Resources Information Center

    Bogacz, Bogdan F.; Pedziwiatr, Antoni T.

    2014-01-01

    A simple and fast experimental method of determining absolute zero temperature is presented. Air gas thermometer coupled with pressure sensor and data acquisition system COACH is applied in a wide range of temperature. By constructing a pressure vs temperature plot for air under constant volume it is possible to obtain--by extrapolation to zero…

  12. A Robust Zero-Watermarking Algorithm for Audio

    NASA Astrophysics Data System (ADS)

    Chen, Ning; Zhu, Jie

    2007-12-01

    In traditional watermarking algorithms, the insertion of watermark into the host signal inevitably introduces some perceptible quality degradation. Another problem is the inherent conflict between imperceptibility and robustness. Zero-watermarking technique can solve these problems successfully. Instead of embedding watermark, the zero-watermarking technique extracts some essential characteristics from the host signal and uses them for watermark detection. However, most of the available zero-watermarking schemes are designed for still image and their robustness is not satisfactory. In this paper, an efficient and robust zero-watermarking technique for audio signal is presented. The multiresolution characteristic of discrete wavelet transform (DWT), the energy compression characteristic of discrete cosine transform (DCT), and the Gaussian noise suppression property of higher-order cumulant are combined to extract essential features from the host audio signal and they are then used for watermark recovery. Simulation results demonstrate the effectiveness of our scheme in terms of inaudibility, detection reliability, and robustness.

  13. Relationship between reaction rate constants of organic pollutants and their molecular descriptors during Fenton oxidation and in situ formed ferric-oxyhydroxides.

    PubMed

    Jia, Lijuan; Shen, Zhemin; Su, Pingru

    2016-05-01

    Fenton oxidation is a promising water treatment method to degrade organic pollutants. In this study, 30 different organic compounds were selected and their reaction rate constants (k) were determined for the Fenton oxidation process. Gaussian09 and Material Studio software sets were used to carry out calculations and obtain values of 10 different molecular descriptors for each studied compound. Ferric-oxyhydroxide coagulation experiments were conducted to determine the coagulation percentage. Based upon the adsorption capacity, all of the investigated organic compounds were divided into two groups (Group A and Group B). The percentage adsorption of organic compounds in Group A was less than 15% (wt./wt.) and that in the Group B was higher than 15% (wt./wt.). For Group A, removal of the compounds by oxidation was the dominant process while for Group B, removal by both oxidation and coagulation (as a synergistic process) took place. Results showed that the relationship between the rate constants (k values) and the molecular descriptors of Group A was more pronounced than for Group B compounds. For the oxidation-dominated process, EHOMO and Fukui indices (f(0)x, f(-)x, f(+)x) were the most significant factors. The influence of bond order was more significant for the synergistic process of oxidation and coagulation than for the oxidation-dominated process. The influences of all other molecular descriptors on the synergistic process were weaker than on the oxidation-dominated process. Copyright © 2015. Published by Elsevier B.V.

  14. Rate constants and mechanisms for the crystallization of Al nano-goethite under environmentally relevant conditions

    NASA Astrophysics Data System (ADS)

    Bazilevskaya, Ekaterina; Archibald, Douglas D.; Martínez, Carmen Enid

    2012-07-01

    Mobile inorganic and organic nanocolloidal particles originate-from and interact-with bulk solid phases in soil and sediment environments, and as such, they contribute to the dynamic properties of environmental systems. In particular, ferrihydrite and (nano)goethite are the most abundant of nanocolloidal Fe oxy(hydr)oxides in these environments. We therefore investigated the ferrihydrite to goethite phase transformation using experimental reaction conditions that mimicked environmental conditions where the formation of nanocolloidal Fe oxy(hydr)oxides may occur: slow titration of dilute solutions to pH 5 at 25 °C with and without 2 mol% Al. Subsequently, the rate constants from 54-d nano-goethite aging/crystallization experiments at 50 °C were determined using aliquots pulled for vibrational spectroscopy (including multivariate curve resolution, MCR, analyses of infrared spectra) and synchrotron-based X-ray diffraction (XRD). We also present a mechanistic model that accounts for the nano-goethite crystallization observed by the aforementioned techniques, and particle structural characteristics observed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). In contrast to the common assumption that metastable ferrihydrite precipitates first, before it transforms to goethite, the presence of characteristic infrared bands in freshly synthesized nanoparticle suspensions indicate goethite can precipitate directly from solution under environmentally relevant conditions: low Fe concentration, ambient temperature, and pH maintained at 5. However, the presence of 2 mol% Al prevented direct goethite precipitation. Rate constants obtained by fitting the contributions from the MCR-derived goethite-like component to the OH-stretching region were (7.4 ± 1.1) × 10-7 s-1 for 0% Al and (4.2 ± 0.4) × 10-7 s-1 for 2 mol% Al suspensions. Rate constants derived from intensities of OH-bending infrared vibrations (795 and 895 cm-1) showed similar values

  15. 15 CFR 700.17 - Use of rated orders.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ...) BUREAU OF INDUSTRY AND SECURITY, DEPARTMENT OF COMMERCE NATIONAL SECURITY INDUSTRIAL BASE REGULATIONS DEFENSE PRIORITIES AND ALLOCATIONS SYSTEM Industrial Priorities § 700.17 Use of rated orders. (a) A person...

  16. Extensions to the instantaneous normal mode analysis of cluster dynamics: Diffusion constants and the role of rotations in clusters

    NASA Astrophysics Data System (ADS)

    Adams, John E.; Stratt, Richard M.

    1990-08-01

    For the instantaneous normal mode analysis method to be generally useful in studying the dynamics of clusters of arbitrary size, it ought to yield values of atomic self-diffusion constants which agree with those derived directly from molecular dynamics calculations. The present study proposes that such agreement indeed can be obtained if a sufficiently sophisticated formalism for computing the diffusion constant is adopted, such as the one suggested by Madan, Keyes, and Seeley [J. Chem. Phys. 92, 7565 (1990)]. In order to implement this particular formalism, however, we have found it necessary to pay particular attention to the removal from the computed spectra of spurious rotational contributions. The utility of the formalism is demonstrated via a study of small argon clusters, for which numerous results generated using other approaches are available. We find the same temperature dependence of the Ar13 self-diffusion constant that Beck and Marchioro [J. Chem. Phys. 93, 1347 (1990)] do from their direct calculation of the velocity autocorrelation function: The diffusion constant rises quickly from zero to a liquid-like value as the cluster goes through (the finite-size equivalent of) the melting transition.

  17. Estimation of uptake rate constants for PCB congeners accumulated by semipermeable membrane devices and brown treat (Salmo trutta)

    USGS Publications Warehouse

    Meadows, J.C.; Echols, K.R.; Huckins, J.N.; Borsuk, F.A.; Carline, R.F.; Tillitt, D.E.

    1998-01-01

    The triolein-filled semipermeable membrane device (SPMD) is a simple and effective method of assessing the presence of waterborne hydrophobic chemicals. Uptake rate constants for individual chemicals are needed to accurately relate the amounts of chemicals accumulated by the SPMD to dissolved water concentrations. Brown trout and SPMDs were exposed to PCB- contaminated groundwater in a spring for 28 days to calculate and compare uptake rates of specific PCB congeners by the two matrixes. Total PCB congener concentrations in water samples from the spring were assessed and corrected for estimated total organic carbon (TOC) sorption to estimate total dissolved concentrations. Whole and dissolved concentrations averaged 4.9 and 3.7 ??g/L, respectively, during the exposure. Total concentrations of PCBs in fish rose from 0.06 to 118.3 ??g/g during the 28-day exposure, while concentrations in the SPMD rose from 0.03 to 203.4 ??g/ g. Uptake rate constants (k1) estimated for SPMDs and brown trout were very similar, with k1 values for SPMDs ranging from one to two times those of the fish. The pattern of congener uptake by the fish and SPMDs was also similar. The rates of uptake generally increased or decreased with increasing K(ow), depending on the assumption of presence or absence of TOC.The triolein-filled semipermeable membrane device (SPMD) is a simple and effective method of assessing the presence of waterborne hydrophobic chemicals. Uptake rate constants for individual chemicals are needed to accurately relate the amounts of chemicals accumulated by the SPMB to dissolved water concentrations. Brown trout and SPMDs were exposed to PCB-contaminated groundwater in a spring for 28 days to calculate and compare uptake rates of specific PCB congeners by the two matrixes. Total PCB congener concentrations in water samples from the spring were assessed and corrected for estimated total organic carbon (TOC) sorption to estimate total dissolved concentrations. Whole and

  18. 78 FR 25264 - Washoe Project-Rate Order No. WAPA-160

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-04-30

    ... DEPARTMENT OF ENERGY Western Area Power Administration Washoe Project-Rate Order No. WAPA-160... existing Washoe Project formula rate through September 30, 2017. The existing Non-Firm Power Formula Rate... the existing formula rate for the Washoe Project, Stampede Division (Project), Non-Firm Power [[Page...

  19. Rate constants for the quenching of metastable O2 (1Sigma g +) molecules

    NASA Technical Reports Server (NTRS)

    Kwang, Y. C.; Leu, M.-T.

    1985-01-01

    The O2 (1Sigma g +) rates for CO2, H2, N2, Cl2, CO, O3, and 2,3 DMB-2 are determined by monitoring the 762-nm emission in a fast-flow-discharge chemiluminescence detection system (Leu, 1984; Leu and Smith, 1981). The results are presented in tables and graphs and briefly characterized. The rate constants (in cu cm/s x 10 to the -16th) are 4600 + or - 500 for CO2, 7000 + or - 300 for H2, 17 + or - 1 for N2, 4.5 + or - 0.8 for Cl2, 45 + or - 5 for CO, 220,000 + or - 30,000 for O3, and 6000 + or - 100 for 2,3 DMB-2. The temperature dependence of the CO2 and O3 quenching reactions at 245-362 K is found to be negligible.

  20. Sedative and cardiorespiratory effects of detomidine constant rate infusion in sheep.

    PubMed

    de Moura, Rauane Sousa; Bittar, Isabela Plazza; da Silva, Luiz Henrique; Villela, Ana Carolina Vasquez; Dos Santos Júnior, Marcelo Borges; Borges, Naida Cristina; Franco, Leandro Guimarães

    2018-02-01

    The use of sheep in experiments is widespread and is increasing worldwide, and so is the need to develop species-specific anaesthetic techniques to ensure animal safety. Previous studies have mentioned several protocols involving the administration of alpha-2 adrenergic agonists in sheep; however, assessment of the efficacy and safety of these infusion techniques is still relatively new. Thus, the aim of the present study is to assess the effectiveness of detomidine constant rate infusion (CRI) in sheep by measuring the cardiovascular and respiratory parameters, blood gas variables and sedation scores. Eight adult female Santa Inês sheep received 20 µg/kg of detomidine hydrochloride intravenously as a bolus loading dose, followed by an infusion rate of 60 µg/kg/h. The heart rates and respiratory rates changed continuously during the CRI period. No arrhythmias were observed. The reduction in arterial partial pressure of oxygen (PaO 2 ) was not significant, but one animal showed signs of hypoxaemia (minimum PaO 2 of 66.9 mmHg). The arterial partial pressure of carbon dioxide (PaCO 2 ) increased, but the animals did not become hypercapnic. The bicarbonate (HCO 3- ), pH and base excess (BE) tended towards metabolic alkalosis. The cardiac output (CO), stroke volume (SV), cardiac index (CI) and ejection fraction (EF%) showed no significant changes. The fractional shortening (FS%) decreased slightly, starting at T 45min . Sedation scores varied between 3 (0/10) after sedation and during recovery and 7 (0/10) during CRI. We concluded that administering detomidine at an infusion rate of 60 µg/kg/h in Santa Inês sheep is a simple technique that produces satisfactory sedation for minimally invasive procedures.

  1. The Influence of Uncompensated Solution Resistance on the Determination and Standard Electrochemical Rate Constants Using Cyclic Voltammetry, and Some Comparisons with AC Voltammetry.

    DTIC Science & Technology

    1987-09-25

    rate constants, k2r using cyclic voltametry . The res tss are expressed in terms of systematic deviations oP sapparent measured" rate constants, k~b(app...concentration was taken to be lum unless otherwise noted. The voltammetric sweep rate was set at 20 V sŕ unless specified otherwise. The general procedure...peaks for the negative- and positive-going potential sweeps have opposite signs, the measured cathodic-anodic peak separation, AEp, will clearly be

  2. Constraints on texture zero and cofactor zero models for neutrino mass

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

    Whisnant, K.; Liao, Jiajun; Marfatia, D.

    2014-06-24

    Imposing a texture or cofactor zero on the neutrino mass matrix reduces the number of independent parameters from nine to seven. Since five parameters have been measured, only two independent parameters would remain in such models. We find the allowed regions for single texture zero and single cofactor zero models. We also find strong similarities between single texture zero models with one mass hierarchy and single cofactor zero models with the opposite mass hierarchy. We show that this correspondence can be generalized to texture-zero and cofactor-zero models with the same homogeneous costraints on the elements and cofactors.

  3. Reduction of Iron-Oxide-Carbon Composites: Part I. Estimation of the Rate Constants

    NASA Astrophysics Data System (ADS)

    Halder, S.; Fruehan, R. J.

    2008-12-01

    A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO2 and wüstite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wüstite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wüstite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wüstite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (>1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

  4. 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.

  5. Probing topological order with Rényi entropy

    NASA Astrophysics Data System (ADS)

    Halász, Gábor B.; Hamma, Alioscia

    2012-12-01

    We present an analytical study of the quantum phase transition between the topologically ordered toric-code-model ground state and the disordered spin-polarized state. The phase transition is induced by applying an external magnetic field, and the variation in topological order is detected via two nonlocal quantities: the Wilson loop and the topological Rényi entropy of order 2. By exploiting an equivalence with the transverse-field Ising model and considering two different variants of the problem, we investigate the field dependence of these quantities by means of an exact treatment in the exactly solvable variant and complementary perturbation theories around the limits of zero and infinite fields in both variants. We find strong evidence that the phase transition point between topological order and disorder is marked by a discontinuity in the topological Rényi entropy and that the two phases around the phase transition point are characterized by its different constant values. Our results therefore indicate that the topological Rényi entropy is a proper topological invariant: its allowed values are discrete and can be used to distinguish between different phases of matter.

  6. Rate constant for the reaction of OH with CH3CCl2F (HCFC-141b) determined by relative rate measurements with CH4 and CH3CCl3

    NASA Technical Reports Server (NTRS)

    Huder, Karin; Demore, William B.

    1993-01-01

    Determination of accurate rate constants for OH abstraction is of great importance for the calculation of lifetimes for HCFCs and their impact on the atmosphere. For HCFC-141b there has been some disagreement in the literature for absolute measurements of this rate constant. In the present work rate constant ratios for HCFC-141b were measured at atmospheric pressure in the temperature range of 298-358 K, with CH4 and CH3CCl3 as reference gases. Ozone was photolyzed at 254 nm in the presence of water vapor to produce OH radicals. Relative depletions of 141b and the reference gases were measured by FTIR. Arrhenius expressions for 141b were derived from each reference gas and found to be in good agreement with each other. The combined expression for HCFC-141b which we recommend is 1.4 x 10 exp -12 exp(-1630/T) with k at 298 K being 5.9 x 10 exp -15 cu cm/molec-s. This value is in excellent agreement with the JPL 92-20 recommendation.

  7. Cancer radiotherapy based on femtosecond IR laser-beam filamentation yielding ultra-high dose rates and zero entrance dose.

    PubMed

    Meesat, Ridthee; Belmouaddine, Hakim; Allard, Jean-François; Tanguay-Renaud, Catherine; Lemay, Rosalie; Brastaviceanu, Tiberius; Tremblay, Luc; Paquette, Benoit; Wagner, J Richard; Jay-Gerin, Jean-Paul; Lepage, Martin; Huels, Michael A; Houde, Daniel

    2012-09-18

    Since the invention of cancer radiotherapy, its primary goal has been to maximize lethal radiation doses to the tumor volume while keeping the dose to surrounding healthy tissues at zero. Sadly, conventional radiation sources (γ or X rays, electrons) used for decades, including multiple or modulated beams, inevitably deposit the majority of their dose in front or behind the tumor, thus damaging healthy tissue and causing secondary cancers years after treatment. Even the most recent pioneering advances in costly proton or carbon ion therapies can not completely avoid dose buildup in front of the tumor volume. Here we show that this ultimate goal of radiotherapy is yet within our reach: Using intense ultra-short infrared laser pulses we can now deposit a very large energy dose at unprecedented microscopic dose rates (up to 10(11) Gy/s) deep inside an adjustable, well-controlled macroscopic volume, without any dose deposit in front or behind the target volume. Our infrared laser pulses produce high density avalanches of low energy electrons via laser filamentation, a phenomenon that results in a spatial energy density and temporal dose rate that both exceed by orders of magnitude any values previously reported even for the most intense clinical radiotherapy systems. Moreover, we show that (i) the type of final damage and its mechanisms in aqueous media, at the molecular and biomolecular level, is comparable to that of conventional ionizing radiation, and (ii) at the tumor tissue level in an animal cancer model, the laser irradiation method shows clear therapeutic benefits.

  8. Effect of zero magnetic field on cardiovascular system and microcirculation

    NASA Astrophysics Data System (ADS)

    Gurfinkel, Yu. I.; At'kov, O. Yu.; Vasin, A. L.; Breus, T. K.; Sasonko, M. L.; Pishchalnikov, R. Yu.

    2016-02-01

    The effects of zero magnetic field conditions on cardiovascular system of healthy adults have been studied. In order to generate zero magnetic field, the facility for magnetic fields modeling ;ARFA; has been used. Parameters of the capillary blood flow, blood pressure, and the electrocardiogram (ECG) monitoring were measured during the study. All subjects were tested twice: in zero magnetic field and, for comparison, in sham condition. The obtained results during 60 minutes of zero magnetic field exposure demonstrate a clear effect on cardiovascular system and microcirculation. The results of our experiments can be used in studies of long-term stay in hypo-magnetic conditions during interplanetary missions.

  9. Rate constant for the reaction NH2 + NO from 216 to 480 K

    NASA Technical Reports Server (NTRS)

    Stief, L. J.; Brobst, W. D.; Nava, D. F.; Borkowski, R. P.; Michael, J. V.

    1982-01-01

    The absolute rate constant was measured by the technique of flash photolysis-laser induced fluorescence (FP-LIF). NH2 radicals were produced by the flash photolysis of ammonia and the fluorescent NH2 photons were measured by multiscaling techniques. At each temperature, the results were independent of variations in total pressure, and flash intensity. The results are compared with previous determinations using the techniques of mass spectrometry, absorption spectroscopy, laser absorption spectroscopy, and laser induced fluorescence. The implications of the results are discussed with regard to combustion, post combustion, and atmospheric chemistry. The results are also discussed theoretically.

  10. Inflation with a smooth constant-roll to constant-roll era transition

    NASA Astrophysics Data System (ADS)

    Odintsov, S. D.; Oikonomou, V. K.

    2017-07-01

    In this paper, we study canonical scalar field models, with a varying second slow-roll parameter, that allow transitions between constant-roll eras. In the models with two constant-roll eras, it is possible to avoid fine-tunings in the initial conditions of the scalar field. We mainly focus on the stability of the resulting solutions, and we also investigate if these solutions are attractors of the cosmological system. We shall calculate the resulting scalar potential and, by using a numerical approach, we examine the stability and attractor properties of the solutions. As we show, the first constant-roll era is dynamically unstable towards linear perturbations, and the cosmological system is driven by the attractor solution to the final constant-roll era. As we demonstrate, it is possible to have a nearly scale-invariant power spectrum of primordial curvature perturbations in some cases; however, this is strongly model dependent and depends on the rate of the final constant-roll era. Finally, we present, in brief, the essential features of a model that allows oscillations between constant-roll eras.

  11. Zero/zero rotorcraft certification issues. Volume 2: Plenary session presentations

    NASA Technical Reports Server (NTRS)

    Adams, Richard J.

    1988-01-01

    This report analyzes the Zero/Zero Rotorcraft Certification Issues from the perspectives of manufacturers, operators, researchers and the FAA. The basic premise behind this analysis is that zero/zero, or at least extremely low visibility, rotorcraft operations are feasible today from both a technological and an operational standpoint. The questions and issues that need to be resolved are: What certification requirements do we need to ensure safety. Can we develop procedures which capitalize on the performance and maneuvering capabilities unique to rotorcraft. Will extremely low visibility operations be economically feasible. This is Volume 2 of three. It presents the operator perspectives (system needs), applicable technology and zero/zero concepts developed in the first 12 months of research of this project.

  12. Using Maximum Likelihood Statistical Methods and Pigment Flux Data to Constrain Particle Exchange and Organic Matter Remineralization Rate Constants in the Mediterranean Sea

    NASA Astrophysics Data System (ADS)

    Wang, W.; Lee, C.; Cochran, K. K.; Armstrong, R. A.

    2016-02-01

    Sinking particles play a pivotal role transferring material from the surface to the deeper ocean via the "biological pump". To quantify the extent to which these particles aggregate and disaggregate, and thus affect particle settling velocity, we constructed a box model to describe organic matter cycling. The box model was fit to chloropigment data sampled in the 2005 MedFlux project using Indented Rotating Sphere sediment traps operating in Settling Velocity (SV) mode. Because of the very different pigment compositions of phytoplankton and fecal pellets, chloropigments are useful as proxies to record particle exchange. The maximum likelihood statistical method was used to estimate particle aggregation, disaggregation, and organic matter remineralization rate constants. Eleven settling velocity categories collected by SV sediment traps were grouped into two sinking velocity classes (fast- and slow-sinking) to decrease the number of parameters that needed to be estimated. Organic matter degradation rate constants were estimated to be 1.2, 1.6, and 1.1 y^-1, which are equivalent to degradation half-lives of 0.60, 0.45, and 0.62 y^-1, at 313, 524, and 1918 m, respectively. Rate constants of chlorophyll a degradation to pheopigments (pheophorbide, pheophytin, and pyropheophorbide) were estimated to be 0.88, 0.93, and 1.2 y^-1, at 313, 524, and 1918 m, respectively. Aggregation rate constants varied little with depth, with the highest value being 0.07 y^-1 at 524 m. Disaggregation rate constants were highest at 524 m (14 y^-1) and lowest at 1918 m (9.6 y^-1)

  13. Determination of ionization constants by paper electrophoresis.

    PubMed Central

    Tate, M E

    1981-01-01

    Dimensionless apparent ionization constants of charged low-molecular-weight species may be obtained from paper-electrophoretic data at 20-25 degrees C with buffers (I0.1-0.5) of measured pH (1.5-12.5) containing oxalate ions. Relative mobilities rather than absolute mobilities were measured by using glycerol and m-nitrobenzenesulphonate respectively as standards of zero and unit mobility. Application of the procedure to ionizations of adenine, adenosine, 2'-deoxyadenosine, 3'-deoxyadenosine, 3':5'-cyclic AMP, ADP, ADP-glucose-agrocin 84 and ATP is described. PMID:6976169

  14. Estimation of absorption rate constant (ka) following oral administration by Wagner-Nelson, Loo-Riegelman, and statistical moments in the presence of a secondary peak.

    PubMed

    Mahmood, Iftekhar

    2004-01-01

    The objective of this study was to evaluate the performance of Wagner-Nelson, Loo-Reigelman, and statistical moments methods in determining the absorption rate constant(s) in the presence of a secondary peak. These methods were also evaluated when there were two absorption rates without a secondary peak. Different sets of plasma concentration versus time data for a hypothetical drug following one or two compartment models were generated by simulation. The true ka was compared with the ka estimated by Wagner-Nelson, Loo-Riegelman and statistical moments methods. The results of this study indicate that Wagner-Nelson, Loo-Riegelman and statistical moments methods may not be used for the estimation of absorption rate constants in the presence of a secondary peak or when absorption takes place with two absorption rates.

  15. EFFECTS OF MICROCOSM PREPARATION ON RATES OF TOLUENE BIODEGRADATION UNDER DENITRIFYING CONDITIONS

    EPA Science Inventory

    Microcosms were prepared with subsurface material from two aquifers to examine the effects of preparation methods on rates of toluene biodegradation under denitrifying conditions. In both cases, the data fit a zero-order kinetics plot. However, rates of removal were generally pro...

  16. 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

  17. A two force-constant model for complexes B⋯M-X (B is a Lewis base and MX is any diatomic molecule): Intermolecular stretching force constants from centrifugal distortion constants D(J) or Δ(J).

    PubMed

    Bittner, Dror M; Walker, Nicholas R; Legon, Anthony C

    2016-02-21

    A two force-constant model is proposed for complexes of the type B⋯MX, in which B is a simple Lewis base of at least C2v symmetry and MX is any diatomic molecule lying along a Cn axis (n ≥ 2) of B. The model assumes a rigid subunit B and that force constants beyond quadratic are negligible. It leads to expressions that allow, in principle, the determination of three quadratic force constants F11, F12, and F22 associated with the r(B⋯M) = r2 and r(M-X) = r1 internal coordinates from the equilibrium centrifugal distortion constants DJ (e) or ΔJ (e), the equilibrium principal axis coordinates a1 and a2, and equilibrium principal moments of inertia. The model can be applied generally to complexes containing different types of intermolecular bond. For example, the intermolecular bond of B⋯MX can be a hydrogen bond if MX is a hydrogen halide, a halogen-bond if MX is a dihalogen molecule, or a stronger, coinage-metal bond if MX is a coinage metal halide. The equations were tested for BrCN, for which accurate equilibrium spectroscopic constants and a complete force field are available. In practice, equilibrium values of DJ (e) or ΔJ (e) for B⋯MX are not available and zero-point quantities must be used instead. The effect of doing so has been tested for BrCN. The zero-point centrifugal distortion constants DJ (0) or ΔJ (0) for all B⋯MX investigated so far are of insufficient accuracy to allow F11 and F22 to be determined simultaneously, even under the assumption F12 = 0 which is shown to be reasonable for BrCN. The calculation of F22 at a series of fixed values of F11 reveals, however, that in cases for which F11 is sufficiently larger than F22, a good approximation to F22 is obtained. Plots of F22 versus F11 have been provided for Kr⋯CuCl, Xe⋯CuCl, OC⋯CuCl, and C2H2⋯AgCl as examples. Even in cases where F22 ∼ F11 (e.g., OC⋯CuCl), such plots will yield either F22 or F11 if the other becomes available.

  18. A two force-constant model for complexes B⋯M-X (B is a Lewis base and MX is any diatomic molecule): Intermolecular stretching force constants from centrifugal distortion constants DJ or ΔJ

    NASA Astrophysics Data System (ADS)

    Bittner, Dror M.; Walker, Nicholas R.; Legon, Anthony C.

    2016-02-01

    A two force-constant model is proposed for complexes of the type B⋯MX, in which B is a simple Lewis base of at least C2v symmetry and MX is any diatomic molecule lying along a Cn axis (n ≥ 2) of B. The model assumes a rigid subunit B and that force constants beyond quadratic are negligible. It leads to expressions that allow, in principle, the determination of three quadratic force constants F11, F12, and F22 associated with the r(B⋯M) = r2 and r(M-X) = r1 internal coordinates from the equilibrium centrifugal distortion constants DJ e or ΔJ e , the equilibrium principal axis coordinates a1 and a2, and equilibrium principal moments of inertia. The model can be applied generally to complexes containing different types of intermolecular bond. For example, the intermolecular bond of B⋯MX can be a hydrogen bond if MX is a hydrogen halide, a halogen-bond if MX is a dihalogen molecule, or a stronger, coinage-metal bond if MX is a coinage metal halide. The equations were tested for BrCN, for which accurate equilibrium spectroscopic constants and a complete force field are available. In practice, equilibrium values of DJ e or ΔJ e for B⋯MX are not available and zero-point quantities must be used instead. The effect of doing so has been tested for BrCN. The zero-point centrifugal distortion constants DJ 0 or ΔJ 0 for all B⋯MX investigated so far are of insufficient accuracy to allow F11 and F22 to be determined simultaneously, even under the assumption F12 = 0 which is shown to be reasonable for BrCN. The calculation of F22 at a series of fixed values of F11 reveals, however, that in cases for which F11 is sufficiently larger than F22, a good approximation to F22 is obtained. Plots of F22 versus F11 have been provided for Kr⋯CuCl, Xe⋯CuCl, OC⋯CuCl, and C2H2⋯AgCl as examples. Even in cases where F22 ˜ F11 (e.g., OC⋯CuCl), such plots will yield either F22 or F11 if the other becomes available.

  19. Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Nava, D. F.; Borokowski, R. P.; Payne, W. A.; Stief, L. J.

    1980-01-01

    The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has been examined at five temperatures ranging from 228 to 413 K. The experimental techniques which was used is flash photolysis-resonance fluoresence. OH was produced by water photolysis and hydroxyl resonance fluorescent photons were measured by multiscaling techniques. The results indicate that the low pressure bimolecular rate constant is 4 x 10 the the minus 13th power cu cm molecule (-1) s(-1) over the temperature range studied. A substantial increase in the bimolecular rate constant with an increase in pressure was observed at all temperatures except 228 K. This indicates the importance of initial adduct formation and subsequent stablization. The high pressure results are well represented by the Arrhenius expression (k sub bi) sub infinity = (6.83 + or - 1.19) x 10 to the minus 12th power exp(-646 + or - 47/T)cu cm molecule (-1) s(-1). The results are compared to previous investigated and are theoretically discussed. The implications of these results on modeling of terrestrial and planetary atmospheres and also in combustion chemistry are discussed.

  20. First-order dissolution rate law and the role of surface layers in glass performance assessment

    NASA Astrophysics Data System (ADS)

    Grambow, B.; Müller, R.

    2001-09-01

    The first-order dissolution rate law is used for nuclear waste glass performance predictions since 1984. A first discussion of the role of saturation effects was initiated at the MRS conference that year. In paper (1) it was stated that "For glass dissolution A* (the reaction affinity) cannot become zero since saturation only involves the reacting surface while soluble elements still might be extracted from the glass" [B. Grambow, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 15]. Saturation of silica at the surface and condensation of surface silanol groups was considered as being responsible for the slow down of reaction rates by as much as a factor of 1000. Precipitation of Si containing secondary phases such as quartz was invoked as a mechanism for keeping final dissolution affinities higher than zero. Another (2) paper [A.B. Barkatt, P.B. Macedo, B.C. Gibson, C.J. Montrose, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 3] stated that "… under repository conditions the extent of glass dissolution will be moderate due to saturation with respect to certain major elements (in particular, Si, Al and Ca). Consequently, the concentration levels of the more soluble glass constituents in the aqueous medium are expected to fall appreciable below their solubility limit." The formation of dense surface layers was considered responsible for explaining the saturation effect. The mathematical model assumed stop of reaction in closed systems, once solubility limits were achieved. For more than 15 years the question of the correctness of one or the other concept has seldom been posed and has not yet been resolved. The need of repository performance assessment for validated rate laws demands a solution, particularly since the consequences of the two concepts and research requirements for the long-term glass behavior are quite different. In concept (1) the stability of the `equilibrium surface region' is not relevant because, by definition, this region is stable chemically and after a

  1. Dechlorination of short chain chlorinated paraffins by nanoscale zero-valent iron.

    PubMed

    Zhang, Zhi-Yong; Lu, Mang; Zhang, Zhong-Zhi; Xiao, Meng; Zhang, Min

    2012-12-01

    In this study, nanoscale zero-valent iron (NZVI) particles were synthesized and used for the reductive dehalogenation of short chain chlorinated paraffins (SCCPs) in the laboratory. The results show that the dechlorination rate of chlorinated n-decane (CP(10)) by NZVI increased with decreased solution pH. Increasing the loading of NZVI enhanced the dechlorination rate of CP(10). With an increase in temperature, the degradation rate increased. The reduction of CP(10) by NZVI was accelerated with increasing the concentration of humic acid up to 15 mg/L but then was inhibited. The dechlorination of CP(10) within the initial 18 h followed pseudo-first order rate model. The formation of intermediate products indicates a stepwise dechlorination pathway of SCCPs by NZVI. The carbon chain length and chlorination degree of SCCPs have a polynominal impact on dechlorination reactions. Copyright © 2012 Elsevier B.V. All rights reserved.

  2. Room-temperature and temperature-dependent QSRR modelling for predicting the nitrate radical reaction rate constants of organic chemicals using ensemble learning methods.

    PubMed

    Gupta, S; Basant, N; Mohan, D; Singh, K P

    2016-07-01

    Experimental determinations of the rate constants of the reaction of NO3 with a large number of organic chemicals are tedious, and time and resource intensive; and the development of computational methods has widely been advocated. In this study, we have developed room-temperature (298 K) and temperature-dependent quantitative structure-reactivity relationship (QSRR) models based on the ensemble learning approaches (decision tree forest (DTF) and decision treeboost (DTB)) for predicting the rate constant of the reaction of NO3 radicals with diverse organic chemicals, under OECD guidelines. Predictive powers of the developed models were established in terms of statistical coefficients. In the test phase, the QSRR models yielded a correlation (r(2)) of >0.94 between experimental and predicted rate constants. The applicability domains of the constructed models were determined. An attempt has been made to provide the mechanistic interpretation of the selected features for QSRR development. The proposed QSRR models outperformed the previous reports, and the temperature-dependent models offered a much wider applicability domain. This is the first report presenting a temperature-dependent QSRR model for predicting the nitrate radical reaction rate constant at different temperatures. The proposed models can be useful tools in predicting the reactivities of chemicals towards NO3 radicals in the atmosphere, hence, their persistence and exposure risk assessment.

  3. Experimental Determination of Dynamical Lee-Yang Zeros

    NASA Astrophysics Data System (ADS)

    Brandner, Kay; Maisi, Ville F.; Pekola, Jukka P.; Garrahan, Juan P.; Flindt, Christian

    2017-05-01

    Statistical physics provides the concepts and methods to explain the phase behavior of interacting many-body systems. Investigations of Lee-Yang zeros—complex singularities of the free energy in systems of finite size—have led to a unified understanding of equilibrium phase transitions. The ideas of Lee and Yang, however, are not restricted to equilibrium phenomena. Recently, Lee-Yang zeros have been used to characterize nonequilibrium processes such as dynamical phase transitions in quantum systems after a quench or dynamic order-disorder transitions in glasses. Here, we experimentally realize a scheme for determining Lee-Yang zeros in such nonequilibrium settings. We extract the dynamical Lee-Yang zeros of a stochastic process involving Andreev tunneling between a normal-state island and two superconducting leads from measurements of the dynamical activity along a trajectory. From the short-time behavior of the Lee-Yang zeros, we predict the large-deviation statistics of the activity which is typically difficult to measure. Our method paves the way for further experiments on the statistical mechanics of many-body systems out of equilibrium.

  4. A photon spectrometric dose-rate constant determination for the Advantage Pd-103 brachytherapy source

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

    Chen, Zhe Jay; Bongiorni, Paul; Nath, Ravinder

    Purpose: Although several dosimetric characterizations using Monte Carlo simulation and thermoluminescent dosimetry (TLD) have been reported for the new Advantage Pd-103 source (IsoAid, LLC, Port Richey, FL), no AAPM consensus value has been established for the dosimetric parameters of the source. The aim of this work was to perform an additional dose-rate constant ({Lambda}) determination using a recently established photon spectrometry technique (PST) that is independent of the published TLD and Monte Carlo techniques. Methods: Three Model IAPD-103A Advantage Pd-103 sources were used in this study. The relative photon energy spectrum emitted by each source along the transverse axis wasmore » measured using a high-resolution germanium spectrometer designed for low-energy photons. For each source, the dose-rate constant was determined from its emitted energy spectrum. The PST-determined dose-rate constant ({sub PST}{Lambda}) was then compared to those determined by TLD ({sub TLD}{Lambda}) and Monte Carlo ({sub MC}{Lambda}) techniques. A likely consensus {Lambda} value was estimated as the arithmetic mean of the average {Lambda} values determined by each of three different techniques. Results: The average {sub PST}{Lambda} value for the three Advantage sources was found to be (0.676{+-}0.026) cGyh{sup -1} U{sup -1}. Intersource variation in {sub PST}{Lambda} was less than 0.01%. The {sub PST}{Lambda} was within 2% of the reported {sub MC}{Lambda} values determined by PTRAN, EGSnrc, and MCNP5 codes. It was 3.4% lower than the reported {sub TLD}{Lambda}. A likely consensus {Lambda} value was estimated to be (0.688{+-}0.026) cGyh{sup -1} U{sup -1}, similar to the AAPM consensus values recommended currently for the Theragenics (Buford, GA) Model 200 (0.686{+-}0.033) cGyh{sup -1} U{sup -1}, the NASI (Chatsworth, CA) Model MED3633 (0.688{+-}0.033) cGyh{sup -1} U{sup -1}, and the Best Medical (Springfield, VA) Model 2335 (0.685{+-}0.033) cGyh{sup -1} U{sup -1} {sup 103

  5. Equivalent formulae of stress Green's functions for a constant slip rate on a triangular fault

    NASA Astrophysics Data System (ADS)

    Feng, Xi; Zhang, Haiming

    2017-06-01

    We present an equivalent form of the expressions first obtained by Tada (Geophys J Int 164:653-669, 2006. doi: 10.1111/j.1365-246X.2006.03868.x), which represents the transient stress response of an infinite, homogeneous and isotropic medium to a constant slip rate on a triangular fault that continues perpetually after the slip onset. Our results are simpler than Tada's, and the corresponding codes have a higher running speed.

  6. Two-dimensional electron density characterisation of arc interruption phenomenon in current-zero phase

    NASA Astrophysics Data System (ADS)

    Inada, Yuki; Kamiya, Tomoki; Matsuoka, Shigeyasu; Kumada, Akiko; Ikeda, Hisatoshi; Hidaka, Kunihiko

    2018-01-01

    Two-dimensional electron density imaging over free burning SF6 arcs and SF6 gas-blast arcs was conducted at current zero using highly sensitive Shack-Hartmann type laser wavefront sensors in order to experimentally characterise electron density distributions for the success and failure of arc interruption in the thermal reignition phase. The experimental results under an interruption probability of 50% showed that free burning SF6 arcs with axially asymmetric electron density profiles were interrupted with a success rate of 88%. On the other hand, the current interruption of SF6 gas-blast arcs was reproducibly achieved under locally reduced electron densities and the interruption success rate was 100%.

  7. Quantification of in Situ Biodegradation Rate Constants Using a Novel Combined Isotope Approach

    NASA Astrophysics Data System (ADS)

    Blum, P.; Sültenfuß, J.; Martus, P.

    2014-12-01

    Numerous studies have shown the enormous potential of the compound-specific isotope analysis (CSIA) for studying the biodegradation of organic compounds such as monoaromatic hydrocarbons (BTEX), polyaromatic hydrocarbons (PAH), chlorinated solvents and other organic contaminants and environmental transformation mechanisms in groundwater. In addition, two-dimensional isotope analysis such as carbon and hydrogen have been successfully studied indicating the potential to also investigate site-specific reaction mechanisms. The main objective of the current study however is to quantify real effective in situ biodegradation rate constants in a coal-tar contaminated aquifer by combining compound-specific isotope analysis (CSIA) and tracer-based (3H-3He) ground-water dating (TGD). Hence, groundwater samples are used to determine groundwater residence times, and carbon and hydrogen stable isotopes are analyzed for selected BTEX and PAH. The results of the hydrogen stable isotopes surprisingly indicate no isotope fractionation and therefore no biodegradation. In contrast, for stable carbon isotopes of selected BTEX such as o-xylene and toluene, isotope shifts are detected indicating active biodegradation under sulfate-reducing conditions. These and previous results of stable carbon isotopes show that only for o-xylene a clear evidence for biodegradation is possible for the studied site. Nevertheless, in combining these results with the groundwater residence times, which range between 1 year for the shallow wells (20 m below surface) and 41 years for the deeper wells (40 m below surface), it is feasible to effectively determine in situ biodegradation rate constants for o-xylene. Conversely, the outcome also evidently demonstrate the major limitations of the novel combined isotope approach for a successful implementation of monitored natural attenuation (MNA) at such field sites.

  8. 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.

  9. Rate constant for the H˙ + H2O → ˙OH + H2 reaction at elevated temperatures measured by pulse radiolysis.

    PubMed

    Muroya, Y; Yamashita, S; Lertnaisat, P; Sanguanmith, S; Meesungnoen, J; Jay-Gerin, J-P; Katsumura, Y

    2017-11-22

    Maintaining the structural integrity of materials in nuclear power plants is an essential issue associated with safe operation. Hydrogen (H 2 ) addition or injection to coolants is a powerful technique that has been widely applied such that the reducing conditions in the coolant water avoid corrosion and stress corrosion cracking (SCC). Because the radiation-induced reaction of ˙OH + H 2 → H˙ + H 2 O plays a crucial role in these systems, the rate constant has been measured at operation temperatures of the reactors (285-300 °C) by pulse radiolysis, generating sufficient data for analysis. The reverse reaction H˙ + H 2 O → ˙OH + H 2 is negligibly slow at ambient temperature; however, it accelerates considerably quickly at elevated temperatures. Although the reverse reaction reduces the effectiveness of H 2 addition, reliable rate constants have not yet been measured. In this study, the rate constants have been determined in a temperature range of 250-350 °C by pulse radiolysis in an aqueous I - solution.

  10. Zero-profile implant (Zero-p) versus plate cage benezech implant (PCB) in the treatment of single-level cervical spondylotic myelopathy.

    PubMed

    Wang, ZhiDong; Zhu, RuoFu; Yang, HuiLin; Shen, MinJie; Wang, Genlin; Chen, Kangwu; Gan, Minfeng; Li, Mao

    2015-10-12

    Anterior cervical discectomy and fusion is the golden standard for anterior surgery treating elderly cervical degenerative disease, but the previous implant has some problems such as looseness, translocation, sinking and dysphagia, So Zero-p implant and PCB implant have been developed to decrease the complications. The clinical data of 57 patients with single level cervical spondylotic myelopathy were retrospectively analyzed. 27 patients adopting Zero-p interbody fusion cage as implant (Zero-p group) and 30 patients adopting integrated plate cage benezech (PCB) as implant (PCB group) from January 2010 to October 2012. Observe whether are differences between the two groups of patients on operation time, intraoperatve blood loss,Japanese Orthopaedic Association (JOA) scores before and after operation, intervertebral height, cervical physiological curvature, fusion rate, Postoperative dysphagia rate and complications. Zero-p group's operation time is 98.2 + 15.2 min and its intraoperatve blood loss is 88.2 + 12.9 ml, both of which are lower than those of PCB group (109.8 + 16.9 min,95.2 + 11.6 ml ), so their differences are statistically significant (P < 0.05). The two groups' JOA scores 3 months after operation and in the last follow-up are significantly higher than those before operation, so the differences are statistically significant (P < 0.05). Coob angle 3 months after operation and in the last follow-up improves obviously compared with before operation, so the difference is statistically significant (P < 0.05). The two groups' operation segments intervertebral height 3 months after operation and in the last follow-up improves obviously compared with before operation, so the difference is statistically significant (P < 0.05) Zero-p group has one patient with dysphagia after operation and PCB group has four patients with dysphagia after operation, so there is no statistical differences between the two groups on dysphagia

  11. FRET enhancement in aluminum zero-mode waveguides.

    PubMed

    de Torres, Juan; Ghenuche, Petru; Moparthi, Satish Babu; Grigoriev, Victor; Wenger, Jérôme

    2015-03-16

    Zero-mode waveguides (ZMWs) can confine light into attoliter volumes, which enables single molecule fluorescence experiments at physiological micromolar concentrations. Of the fluorescence spectroscopy techniques that can be enhanced by ZMWs, Förster resonance energy transfer (FRET) is one of the most widely used in life sciences. Combining zero-mode waveguides with FRET provides new opportunities to investigate biochemical structures or follow interaction dynamics at micromolar concentrations with single-molecule resolution. However, prior to any quantitative FRET analysis on biological samples, it is crucial to establish first the influence of the ZMW on the FRET process. Here, we quantify the FRET rates and efficiencies between individual donor-acceptor fluorophore pairs that diffuse into aluminum zero-mode waveguides. Aluminum ZMWs are important structures thanks to their commercial availability and the large amount of literature that describe their use for single-molecule fluorescence spectroscopy. We also compared the results between ZMWs milled in gold and aluminum, and found that although gold has a stronger influence on the decay rates, the lower losses of aluminum in the green spectral region provide larger fluorescence brightness enhancement factors. For both aluminum and gold ZMWs, we observed that the FRET rate scales linearly with the isolated donor decay rate and the local density of optical states. Detailed information about FRET in ZMWs unlocks their application as new devices for enhanced single-molecule FRET at physiological concentrations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Inflation Rates, Car Devaluation, and Chemical Kinetics.

    ERIC Educational Resources Information Center

    Pogliani, Lionello; Berberan-Santos, Mario N.

    1996-01-01

    Describes the inflation rate problem and offers an interesting analogy with chemical kinetics. Presents and solves the car devaluation problem as a normal chemical kinetic problem where the order of the rate law and the value of the rate constant are derived. (JRH)

  13. Normal forms for Hopf-Zero singularities with nonconservative nonlinear part

    NASA Astrophysics Data System (ADS)

    Gazor, Majid; Mokhtari, Fahimeh; Sanders, Jan A.

    In this paper we are concerned with the simplest normal form computation of the systems x˙=2xf(x,y2+z2), y˙=z+yf(x,y2+z2), z˙=-y+zf(x,y2+z2), where f is a formal function with real coefficients and without any constant term. These are the classical normal forms of a larger family of systems with Hopf-Zero singularity. Indeed, these are defined such that this family would be a Lie subalgebra for the space of all classical normal form vector fields with Hopf-Zero singularity. The simplest normal forms and simplest orbital normal forms of this family with nonzero quadratic part are computed. We also obtain the simplest parametric normal form of any non-degenerate perturbation of this family within the Lie subalgebra. The symmetry group of the simplest normal forms is also discussed. This is a part of our results in decomposing the normal forms of Hopf-Zero singular systems into systems with a first integral and nonconservative systems.

  14. Probing the rate-limiting step for intramolecular transfer of a transcription factor between specific sites on the same DNA molecule by (15)Nz-exchange NMR spectroscopy.

    PubMed

    Ryu, Kyoung-Seok; Tugarinov, Vitali; Clore, G Marius

    2014-10-15

    The kinetics of translocation of the homeodomain transcription factor HoxD9 between specific sites of the same or opposite polarities on the same DNA molecule have been studied by (15)Nz-exchange NMR spectroscopy. We show that exchange occurs by two facilitated diffusion mechanisms: a second-order intermolecular exchange reaction between specific sites located on different DNA molecules without the protein dissociating into free solution that predominates at high concentrations of free DNA, and a first-order intramolecular process involving direct transfer between specific sites located on the same DNA molecule. Control experiments using a mixture of two DNA molecules, each possessing only a single specific site, indicate that transfer between specific sites by full dissociation of HoxD9 into solution followed by reassociation is too slow to measure by z-exchange spectroscopy. Intramolecular transfer with comparable rate constants occurs between sites of the same and opposing polarity, indicating that both rotation-coupled sliding and hopping/flipping (analogous to geminate recombination) occur. The half-life for intramolecular transfer (0.5-1 s) is many orders of magnitude larger than the calculated transfer time (1-100 μs) by sliding, leading us to conclude that the intramolecular transfer rates measured by z-exchange spectroscopy represent the rate-limiting step for a one-base-pair shift from the specific site to the immediately adjacent nonspecific site. At zero concentration of added salt, the intramolecular transfer rate constants between sites of opposing polarity are smaller than those between sites of the same polarity, suggesting that hopping/flipping may become rate-limiting at very low salt concentrations.

  15. Collisional excitation of CO by H2O - An astrophysicist's guide to obtaining rate constants from coherent anti-Stokes Raman line shape data

    NASA Technical Reports Server (NTRS)

    Green, Sheldon

    1993-01-01

    Rate constants for excitation of CO by collisions with H2O are needed to understand recent observations of comet spectra. These collision rates are closely related to spectral line shape parameters, especially those for Raman Q-branch spectra. Because such spectra have become quite important for thermometry applications, much effort has been invested in understanding this process. Although it is not generally possible to extract state-to-state rate constants directly from the data as there are too many unknowns, if the matrix of state-to-state rates can be expressed in terms of a rate-law model which depends only on rotational quantum numbers plus a few parameters, the parameters can be determined from the data; this has been done with some success for many systems, especially those relevant to combustion processes. Although such an analysis has not yet been done for CO-H2O, this system is expected to behave similarly to N2-H2O which has been well studies; modifications of parameters for the latter system are suggested which should provide a reasonable description of rate constants for the former.

  16. Computational study of scattering of a zero-order Bessel beam by large nonspherical homogeneous particles with the multilevel fast multipole algorithm

    NASA Astrophysics Data System (ADS)

    Yang, Minglin; Wu, Yueqian; Sheng, Xinqing; Ren, Kuan Fang

    2017-12-01

    Computation of scattering of shaped beams by large nonspherical particles is a challenge in both optics and electromagnetics domains since it concerns many research fields. In this paper, we report our new progress in the numerical computation of the scattering diagrams. Our algorithm permits to calculate the scattering of a particle of size as large as 110 wavelengths or 700 in size parameter. The particle can be transparent or absorbing of arbitrary shape, smooth or with a sharp surface, such as the Chebyshev particles or ice crystals. To illustrate the capacity of the algorithm, a zero order Bessel beam is taken as the incident beam, and the scattering of ellipsoidal particles and Chebyshev particles are taken as examples. Some special phenomena have been revealed and examined. The scattering problem is formulated with the combined tangential formulation and solved iteratively with the aid of the multilevel fast multipole algorithm, which is well parallelized with the message passing interface on the distributed memory computer platform using the hybrid partitioning strategy. The numerical predictions are compared with the results of the rigorous method for a spherical particle to validate the accuracy of the approach. The scattering diagrams of large ellipsoidal particles with various parameters are examined. The effect of aspect ratios, as well as half-cone angle of the incident zero-order Bessel beam and the off-axis distance on scattered intensity, is studied. Scattering by asymmetry Chebyshev particle with size parameter larger than 700 is also given to show the capability of the method for computing scattering by arbitrary shaped particles.

  17. Preferential emission into epsilon-near-zero metamaterial [Invited

    DOE PAGES

    Galfsky, Tal; Sun, Zheng; Jacob, Zubin; ...

    2015-11-23

    We report the use of epsilon near zero (ENZ) metamaterial to control spontaneous emission from Zinc-Oxide (ZnO) excitons. The ENZ material consists of alternating layers of silver and alumina with subwavelength thicknesses, resulting in an effective medium where one of the components of the dielectric constant approach zero between 370nm-440nm wavelength range. Bulk ZnO with photoluminescence maximum in the ENZ regime was deposited via atomic layer deposition to obtain a smooth film with near field coupling to the ENZ metamaterial. Preferential emission from the ZnO layer into the metamaterial with suppression of forward emission by 90% in comparison to ZnOmore » on silicon is observed. We attribute this observation to the presence of dispersionless plasmonic modes in the ENZ regime as shown by the results of theoretical modeling presented here. Integration of ENZ metamaterials with light emitters is an attractive platform for realizing a low threshold subwavelength laser.« less

  18. Determination of the cosmological rate of change of G and the tidal accelerations of earth and moon from ancient and modern astronomical data

    NASA Technical Reports Server (NTRS)

    Muller, P. M.

    1976-01-01

    The theory and numerical analysis of ancient astronomical observations (1374 to 1715) are combined with modern data in a simultaneous solution for: the tidal acceleration of the lunar longitude; the observed apparent acceleration of the earth's rotation; the true nontidal geophysical part of this acceleration; and the rate of change in the gravitational constant. Provided are three independent determinations of a rate of change of G consistent with the Hubble Constant and a near zero nontidal rotational acceleration of the earth. The tidal accelerations are shown to have remained constant during the historical period within uncertainties. Ancient and modern solar system data, and extragalactic observations provided a completely consistent astronomical and cosmological scheme.

  19. ASSESSMENT OF THE MICROBIAL POTENTIAL FOR NITRATE- ENHANCED BIOREMEDIATION OF A JP-4 FUEL-CONTAMINATED AQUIFER

    EPA Science Inventory

    A site that was contaminated with JP-4 jet fuel was characterized microbiologically to assess the feasibility of nitrate-enhanced bioremediation. The results of microcosm studies indicated that the mean pseudo zero-order rate constants for alkylbenzene biodegradation and NO3...

  20. 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.

  1. The reaction of peroxy radicals with OH: rate constants and HO2 yields

    NASA Astrophysics Data System (ADS)

    Fittschen, C. M.; Assaf, E.; Schoemaecker, C.; Vereecken, L.

    2017-12-01

    Peroxy radicals, RO2, are key species in the atmosphere. They are formed from a reaction of OH radicals with hydrocarbon: RH + OH + O2 → RO2 + H2O In polluted environments, RO2 radicals react predominantly with NO, leading to formation of NO2 and eventually through photolysis of NO2 to formation of O3. At low NOx concentrations such as in the marine boundary layer or the background troposphere, the lifetime of RO2 radicals increases and other reaction pathways become competitive. Atmospheric chemistry models have considered until recently only the self- and cross reaction with other RO2 radicals or with HO2 radicals as the major fate for RO2 radicals under low NOx conditions. Recently, the rate constants for the reaction of peroxy radicals with OH radicals RO2 + OH → products has been measured for CH3O2 [1, 2] and C2H5O2 [3] and it was shown to become competitive to other sinks [4]. However, in order to evaluate the impact of this so far neglected sink for peroxy radicals on the composition of remote atmospheres, the reaction products must be known. A recently improved experimental set-up combining laser photolysis with two simultaneous cw-CRDS detections in the near IR allowing for a time resolved, absolute quantification of OH and RO2 radicals has been used for a further investigation of this class of reactions. High-repetition rate LIF is used for determining relative OH profiles. For CH3O2 radicals, HO2 has been determined as major product recently [5]. Currently, we study the next larger perxoy, C2H5O2, using different radical precursors (C2H5I, (COCl)2/C2H6, XeF2/C2H6) and also deuterated C2D5I in order to elucidate the product yield. Preliminary results show a much lower HO2 yield for C2H5O2 compared to CH3O2. The most recent results will be presented at the conference. [1] A. Bossolasco, E. Faragó, C. Schoemaecker, and C. Fittschen, CPL, 593, 7, (2014). [2] E. Assaf, B. Song, A. Tomas, C. Schoemaecker, C. Fittschen, JPC A, 120, 8923 (2016) [3] Eszter

  2. Calculation of the rate constant for state-selected recombination of H+O2(v) as a function of temperature and pressure

    NASA Astrophysics Data System (ADS)

    Teitelbaum, Heshel; Caridade, Pedro J. S. B.; Varandas, António J. C.

    2004-06-01

    Classical trajectory calculations using the MERCURY/VENUS code have been carried out on the H+O2 reactive system using the DMBE-IV potential energy surface. The vibrational quantum number and the temperature were selected over the ranges v=0 to 15, and T=300 to 10 000 K, respectively. All other variables were averaged. Rate constants were determined for the energy transfer process, H+O2(v)-->H+O2(v''), for the bimolecular exchange process, H+O2(v)-->OH(v')+O, and for the dissociative process, H+O2(v)-->H+O+O. The dissociative process appears to be a mere extension of the process of transferring large amounts of energy. State-to-state rate constants are given for the exchange reaction, and they are in reasonable agreement with previous results, while the energy transfer and dissociative rate constants have never been reported previously. The lifetime distributions of the HO2 complex, calculated as a function of v and temperature, were used as a basis for determining the relative contributions of various vibrational states of O2 to the thermal rate coefficients for recombination at various pressures. This novel approach, based on the complex's ability to survive until it collides in a secondary process with an inert gas, is used here for the first time. Complete falloff curves for the recombination of H+O2 are also calculated over a wide range of temperatures and pressures. The combination of the two separate studies results in pressure- and temperature-dependent rate constants for H+O2(v)(+Ar)⇄HO2(+Ar). It is found that, unlike the exchange reaction, vibrational and rotational-translational energy are liabilities in promoting recombination.

  3. Double-Zero-Index Structural Phononic Waveguides

    NASA Astrophysics Data System (ADS)

    Zhu, Hongfei; Semperlotti, Fabio

    2017-12-01

    We report on the theoretical and experimental realization of a double-zero-index elastic waveguide and the corresponding acoustic cloaking and supercoupling effects. The proposed waveguide uses geometric tapers in order to induce Dirac-like cones at k → =0 due to accidental degeneracy. The nature of the degeneracy is explored by a k .p perturbation method adapted to thin structural waveguides. The results confirm the linear nature of the dispersion around the degeneracy and the possibility to map the material to effective-medium properties. Effective parameters numerically extracted using boundary medium theory confirm that the phononic waveguide maps into a double-zero-index material. Numerical and experimental results confirm the expected cloaking and supercoupling effects.

  4. Absolute rate constant for the reaction of atomic chlorine with hydrogen peroxide vapor over the temperature range 265-400 K

    NASA Technical Reports Server (NTRS)

    Michael, J. V.; Whytock, D. A.; Lee, J. H.; Payne, W. A.; Stief, L. J.

    1977-01-01

    Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400 K using the flash photolysis-resonance fluorescence technique. Analytical techniques were developed to measure H2O2 under reaction conditions. Due to ambiguity in the interpretation of the analytical results, the data combine to give two equally acceptable representations of the temperature dependence. The results are compared to previous work at 298 K and are theoretically discussed in terms of the mechanism of the reaction. Additional experiments on the H + H2O2 reaction at 298 and 359 K are compared with earlier results from this laboratory and give a slightly revised bimolecular rate constant.

  5. Zero-Base Curriculum Revision: A Concept Worth Trying.

    ERIC Educational Resources Information Center

    Miller, William C.

    1981-01-01

    Argues for a "zero-base" revision of school curricula in order to weed out poorly functioning components. Outlines procedures for carrying out such a revision at both the district and building levels. (WD)

  6. Zero-range effective field theory for resonant wino dark matter. Part III. Annihilation effects

    NASA Astrophysics Data System (ADS)

    Braaten, Eric; Johnson, Evan; Zhang, Hong

    2018-05-01

    Near a critical value of the wino mass where there is a zero-energy S-wave resonance at the neutral-wino-pair threshold, low-energy winos can be described by a zero-range effective field theory (ZREFT) in which the winos interact nonperturbatively through a contact interaction and through Coulomb interactions. The effects of wino-pair annihilation into electroweak gauge bosons are taken into account through the analytic continuation of the real parameters for the contact interaction to complex values. The parameters of ZREFT can be determined by matching wino-wino scattering amplitudes calculated by solving the Schrödinger equation for winos interacting through a real potential due to the exchange of electroweak gauge bosons and an imaginary potential due to wino-pair annihilation into electroweak gauge bosons. ZREFT at leading order gives an accurate analytic description of low-energy wino-wino scattering, inclusive wino-pair annihilation, and a wino-pair bound state. ZREFT can also be applied to partial annihilation rates, such as the Sommerfeld enhancement of the annihilation rate of wino pairs into monochromatic photons.

  7. Three-body interactions and the elastic constants of hcp solid 4He

    NASA Astrophysics Data System (ADS)

    Barnes, Ashleigh L.; Hinde, Robert J.

    2017-09-01

    The effect of three-body interactions on the elastic properties of hexagonal close packed solid 4He is investigated using variational path integral (VPI) Monte Carlo simulations. The solid's nonzero elastic constants are calculated, at T = 0 K and for a range of molar volumes from 7.88 cm3/mol to 20.78 cm3/mol, from the bulk modulus and the three pure shear constants C0, C66, and C44. Three-body interactions are accounted for using our recently reported perturbative treatment based on the nonadditive three-body potential of Cencek et al. Previous studies have attempted to account for the effect of three-body interactions on the elastic properties of solid 4He; however, these calculations have treated zero point motions using either the Einstein or Debye approximations, which are insufficient in the molar volume range where solid 4He is characterized as a quantum solid. Our VPI calculations allow for a more accurate treatment of the zero point motions which include atomic correlation. From these calculations, we find that agreement with the experimental bulk modulus is significantly improved when three-body interactions are considered. In addition, three-body interactions result in non-negligible differences in the calculated pure shear constants and nonzero elastic constants, particularly at higher densities, where differences of up to 26.5% are observed when three-body interactions are included. We compare to the available experimental data and find that our results are generally in as good or better agreement with experiment as previous theoretical investigations.

  8. 20 CFR 345.303 - Computation of rate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... a percentage rate, and then round such rate to the nearest 100th of one percent. If the rate so computed is zero or less than zero, the percentage rate will be deemed zero at this point; (5) Step 5. Add...

  9. Friction falls towards zero in quartz rock as slip velocity approaches seismic rates.

    PubMed

    Di Toro, Giulio; Goldsby, David L; Tullis, Terry E

    2004-01-29

    An important unsolved problem in earthquake mechanics is to determine the resistance to slip on faults in the Earth's crust during earthquakes. Knowledge of coseismic slip resistance is critical for understanding the magnitude of shear-stress reduction and hence the near-fault acceleration that can occur during earthquakes, which affects the amount of damage that earthquakes are capable of causing. In particular, a long-unresolved problem is the apparently low strength of major faults, which may be caused by low coseismic frictional resistance. The frictional properties of rocks at slip velocities up to 3 mm s(-1) and for slip displacements characteristic of large earthquakes have been recently simulated under laboratory conditions. Here we report data on quartz rocks that indicate an extraordinary progressive decrease in frictional resistance with increasing slip velocity above 1 mm s(-1). This reduction extrapolates to zero friction at seismic slip rates of approximately 1 m s(-1), and appears to be due to the formation of a thin layer of silica gel on the fault surface: it may explain the low strength of major faults during earthquakes.

  10. Measurement of Rate Constants for Homodimer Subunit Exchange Using Double Electron-Electron Resonance and Paramagnetic Relaxation Enhancements

    PubMed Central

    Yang, Yunhuang; Ramelot, Theresa A.; Ni, Shuisong; McCarrick, Robert M.; Kennedy, Michael A.

    2013-01-01

    Here, we report novel methods to measure rate constants for homodimer subunit exchange using double electron-electron resonance (DEER) electron paramagnetic resonance spectroscopy measurements and nuclear magnetic resonance spectroscopy based paramagnetic relaxation enhancement (PRE) measurements. The techniques were demonstrated using the homodimeric protein Dsy0195 from the strictly anaerobic bacterium Desulfitobacterium hafniense Y51. At specific times following mixing site-specific MTSL-labeled Dsy0195 with uniformly 15N-labeled Dsy0195, the extent of exchange was determined either by monitoring the decrease of MTSL-labeled homodimer from the decay of the DEER modulation depth or by quantifying the increase of MTSL-labeled/15N-labeled heterodimer using PREs. Repeated measurements at several time points following mixing enabled determination of the homodimer subunit dissociation rate constant, k−1;, which was 0.037 ± 0.005 min−1 derived from DEER experiments with a corresponding half-life time of 18.7 minutes. These numbers agreed with independent measurements obtained from PRE experiments. These methods can be broadly applied to protein-protein and protein-DNA complex studies. PMID:23180051

  11. Direct rate constant measurements for the reaction of ground-state atomic oxygen with ethylene, 244-1052 K

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

    Klemm, R.B.; Nesbitt, F.L.; Skolnik, E.G.

    The rate constant for the reaction of ground-state atomic oxygen with ethylene was determined by using two techniques: flash photolysis-resonance fluorescence (FP-RF, 244-1052 K) and discharge flow-resonance fluorescence (DF-RF, 298-1017 K). Kinetic complications due to the presence of molecular oxygen in the FP-RF experiments at high temperatures (T > 800 K) were overcome by using NO as the photolytic source of the O atoms. The rate constant, k/sub 1/ (T), derived in this study exhibits extreme non-Arrhenius behavior, but it can be successfully fit to the sum of exponentials expression, 244-1052 K, k/sub 1/(T) = (1.02 +/- 0.06) x 10/supmore » -11/ exp(-753 +/- 17 K/T) + (2.75 +/- 0.26) x 10/sup -10/ exp(-4220 +/- 550 K/T), in units of cm/sup 3/ molecule/sup -1/ s/sup -1/. Additionally, a fit of the results of this work to a simple transition-state theory expression and the comparison of these results with those of other workers are discussed.« less

  12. Averaging of elastic constants for polycrystals

    DOE PAGES

    Blaschke, Daniel N.

    2017-10-13

    Many materials of interest are polycrystals, i.e., aggregates of single crystals. Randomly distributed orientations of single crystals lead to macroscopically isotropic properties. Here in this paper, we briefly review strategies of calculating effective isotropic second and third order elastic constants from the single crystal ones. Our main emphasis is on single crystals of cubic symmetry. Specifically, the averaging of third order elastic constants has not been particularly successful in the past, and discrepancies have often been attributed to texturing of polycrystals as well as to uncertainties in the measurement of elastic constants of both poly and single crystals. While thismore » may well be true, we also point out here shortcomings in the theoretical averaging framework.« less

  13. Viscoelastic optical nonlocality of doped cadmium oxide epsilon-near-zero thin films

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

    Luk, Ting S.; De Ceglia, Domenico; Scalora, Michael

    Optical nonlocalities are elusive and hardly observable in traditional plasmonic materials like noble and alkali metals. Here we experimentally observe and theoretically model viscoelastic nonlocalities in the infrared optical response of a doped, cadmium oxide epsilon-near-zero thin film. The nonlocality is clearly detectable thanks to the low damping rate of conduction electrons and the virtual absence of interband transitions at infrared wavelengths. We describe the motion of conduction electrons using a hydrodynamic model for a viscoelastic fluid, and find excellent agreement with experimental results. The electrons’ elasticity blue-shifts the infrared plasmonic resonance associated with the main epsilon-near-zero mode, and triggersmore » the onset of higher-order resonances due to the excitation of electron-pressure modes above the bulk plasma frequency. We also provide evidence of the existence of nonlocal damping, i.e., viscosity, in the motion of optically-excited conduction electrons using a combination of spectroscopic ellipsometry data and predictions based on the viscoelastic hydrodynamic model.« less

  14. Asympotics with positive cosmological constant

    NASA Astrophysics Data System (ADS)

    Bonga, Beatrice; Ashtekar, Abhay; Kesavan, Aruna

    2014-03-01

    Since observations to date imply that our universe has a positive cosmological constant, one needs an extension of the theory of isolated systems and gravitational radiation in full general relativity from the asymptotically flat to asymptotically de Sitter space-times. In current definitions, one mimics the boundary conditions used in asymptotically AdS context to conclude that the asymptotic symmetry group is the de Sitter group. However, these conditions severely restricts radiation and in fact rules out non-zero flux of energy, momentum and angular momentum carried by gravitational waves. Therefore, these formulations of asymptotically de Sitter space-times are uninteresting beyond non-radiative spacetimes. The situation is compared and contrasted with conserved charges and fluxes at null infinity in asymptotically flat space-times.

  15. The chiral quark condensate and pion decay constant in nuclear matter at next-to-leading order

    NASA Astrophysics Data System (ADS)

    Lacour, A.; Oller, J. A.; Meißner, U.-G.

    2010-12-01

    Making use of the recently developed chiral power counting for the physics of nuclear matter (Oller et al 2010 J. Phys. G: Nucl. Part. Phys. 37 015106, Lacour et al Ann. Phys. at press), we evaluate the in-medium chiral quark condensate up to next-to-leading order for both symmetric nuclear matter and neutron matter. Our calculation includes the full in-medium iteration of the leading order local and one-pion exchange nucleon-nucleon interactions. Interestingly, we find a cancellation between the contributions stemming from the quark mass dependence of the nucleon mass appearing in the in-medium nucleon-nucleon interactions. Only the contributions originating from the explicit quark mass dependence of the pion mass survive. This cancellation is the reason of previous observations concerning the dominant role of the long-range pion contributions and the suppression of short-range nucleon-nucleon interactions. We find that the linear density contribution to the in-medium chiral quark condensate is only slightly modified for pure neutron matter by the nucleon-nucleon interactions. For symmetric nuclear matter, the in-medium corrections are larger, although smaller compared to other approaches due to the full iteration of the lowest order nucleon-nucleon tree-level amplitudes. Our calculation satisfies the Hellmann-Feynman theorem to the order worked out. Also we address the problem of calculating the leading in-medium corrections to the pion decay constant. We find that there are no extra in-medium corrections that violate the Gell-Mann-Oakes-Renner relation up to next-to-leading order.

  16. Stress, temperature, heart rate, and hibernating factors in hamsters. [pathophysiological conditions resulting from exposure to zero gravity

    NASA Technical Reports Server (NTRS)

    Musacchia, X. J.

    1974-01-01

    Pathophysiological conditions resulting from prolonged exposure to zero gravity, cabin constraint, altered ambient environment, whether it be noise, vibrations, high temperatures, or combinations of such factors, are studied in laboratory animals and applied to manned space flight. Results and plans for further study are presented. Specific topics covered include: thermoregulation and its role in reflecting stress and adaptation to the gravity free environment and cabin confinement with its altered circadian forcings; renal function and its measurement in electrolyte distribution and blood flow dynamics; gastronintestinal function and an assessment of altered absorptive capacity in the intestinal mucosa; and catecholamine metabolism in terms of distribution and turnover rates in specific tissues.

  17. First-principles method for calculating the rate constants of internal-conversion and intersystem-crossing transitions.

    PubMed

    Valiev, R R; Cherepanov, V N; Baryshnikov, G V; Sundholm, D

    2018-02-28

    A method for calculating the rate constants for internal-conversion (k IC ) and intersystem-crossing (k ISC ) processes within the adiabatic and Franck-Condon (FC) approximations is proposed. The applicability of the method is demonstrated by calculation of k IC and k ISC for a set of organic and organometallic compounds with experimentally known spectroscopic properties. The studied molecules were pyrromethene-567 dye, psoralene, hetero[8]circulenes, free-base porphyrin, naphthalene, and larger polyacenes. We also studied fac-Alq 3 and fac-Ir(ppy) 3 , which are important molecules in organic light emitting diodes (OLEDs). The excitation energies were calculated at the multi-configuration quasi-degenerate second-order perturbation theory (XMC-QDPT2) level, which is found to yield excitation energies in good agreement with experimental data. Spin-orbit coupling matrix elements, non-adiabatic coupling matrix elements, Huang-Rhys factors, and vibrational energies were calculated at the time-dependent density functional theory (TDDFT) and complete active space self-consistent field (CASSCF) levels. The computed fluorescence quantum yields for the pyrromethene-567 dye, psoralene, hetero[8]circulenes, fac-Alq 3 and fac-Ir(ppy) 3 agree well with experimental data, whereas for the free-base porphyrin, naphthalene, and the polyacenes, the obtained quantum yields significantly differ from the experimental values, because the FC and adiabatic approximations are not accurate for these molecules.

  18. Sustaining 1,2-Dichloroethane Degradation in Nanoscale Zero-Valent Iron induced Fenton system by using Sequential H2O2 Addition at Natural pH

    NASA Astrophysics Data System (ADS)

    Phenrat, T.; Le, T. S. T.

    2017-12-01

    1,2-Dichloroethane (1,2-DCA) is a prevalent subsurface contaminant found in groundwater and soil around the world. Nanoscale zero-valent iron (NZVI) is a promising in situ remediation agent for chlorinated organics. Nevertheless, 1,2-DCA is recalcitrant to reductive dechlorination using NZVI. Chemical oxidation using Fenton's reaction with conventional Fe2+ is a valid option for 1,2-DCA remediation with a major technical challenge, i.e. aquifer acidification is needed to maintain Fe2+ for catalytic reaction. In this work, NZVI Fenton's process at neutral pH was applied to degrade 1,2-DCA at high concentration (2,000 mg/L) representing dissolved 1,2-DCA concentration close to non-aqueous phase liquid source zone. Instead of using acidification to maintain dissolved Fe2+ concentration, NZVI Fenton's process is self-catalytic based on oxidative dissolution of NZVI in the present of H2O2. Interfacial H+ is produced at NZVI surface to provide appropriate local pH which continuously releases Fe2+ for Fenton's reaction. Approximately, 87% of 1,2-DCA was degraded at neutral pH with the pseudo first-order rate constant of 0.98 hour-1 using 10 g/L of NZVI and 200 mM of H2O2. However, the reaction was prohibited quickly within 3 hours presumably due to the rapid depletion of H2O2. The application of sequential H2O2 addition provided a better approach to prevent rapid inhibition via controlling the H2O2 concentration in the system to be sufficient but not excess, thus resulting in the higher degradation efficiency (the pseudo first-order rate constant of 0.49 hour-1 and 99 % degradation in 8 hours). Using NZVI with sequential H2O2 addition was also successful in degrading 1,2-DCA sorbed on to soil, yielding 99% removal of 1,2-DCA within 16 hours at the rate constant of 0.23 hour-1, around two times slower than in the system without soil presumably due to rate-limited 1,2-DCA desorption from soil. Mechanistic understanding of how sequential addition of H2O2, in comparison to

  19. A computational study of photo-induced electron transfer rate constants in subphthalocyanine/C60 organic photovoltaic materials via Fermi's golden rule

    NASA Astrophysics Data System (ADS)

    Lee, Myeong H.; Dunietz, Barry D.; Geva, Eitan

    2014-03-01

    We present a methodology to obtain the photo-induced electron transfer rate constant in organic photovoltaic (OPV) materials within the framework of Fermi's golden rule, using inputs obtained from first-principles electronic structure calculation. Within this approach, the nuclear vibrational modes are treated quantum-mechanically and a short-time approximation is avoided in contrast to the classical Marcus theory where these modes are treated classically within the high-temperature and short-time limits. We demonstrate our methodology on boron-subphthalocyanine-chloride/C60 OPV system to determine the rate constants of electron transfer and electron recombination processes upon photo-excitation. We consider two representative donor/acceptor interface configurations to investigate the effect of interface configuration on the charge transfer characteristics of OPV materials. In addition, we determine the time scale of excited states population by employing a master equation after obtaining the rate constants for all accessible electronic transitions. This work is pursued as part of the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US Department of Energy Office of Science, Office of Basic Energy Sciences under 390 Award No. DE-SC0000957.

  20. 75 FR 57912 - Boulder Canyon Project-Rate Order No. WAPA-150

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-09-23

    ...-setting Formula and Approval of FY 2011 Base Charge and Rates. SUMMARY: The Deputy Secretary of Energy... existing Boulder Canyon Project (BCP) rate-setting formula and approving the base charge and rates for FY... financial and load data. The existing rate-setting formula is being extended under Rate Order No. WAPA-150...

  1. Rate of antioxidant degradation and color variations in dehydrated apples as related to water activity.

    PubMed

    Lavelli, Vera; Vantaggi, Claudia

    2009-06-10

    Dehydrated apples were studied to evaluate the effects of water activity on the stability of their antioxidants and color. Apples were freeze-dried, ground, then equilibrated, and stored at eight water activity levels, ranging from 0.058 to 0.747, at 40 degrees C. Their contents of hydroxycinnamic acids, dihydrochalcones, catechin, epicatechin, polymeric flavan-3-ols, and hydroxymethylfurfural, their antioxidant activity values, and their Hunter colorimetric parameters were analyzed at different storage times. Antioxidant degradation followed pseudo-first-order kinetics and was accelerated by increasing the water activity. The order of antioxidant stability in the products at water activity levels below 0.316 was catechin, epicatechin, and ascorbic acid < total procyanidins < dihydrochalcones and p-coumaric acid < chlorogenic acid; however, in the products at water activity levels above 0.316, the degradation of all antioxidants was very fast. The hydroxymethylfurfural formation rate increased exponentially during storage, especially at high water activity levels. The antioxidant activity of the dehydrated apples decreased during storage, consistent with antioxidant loss. The variations of the colorimetric parameters, namely, lightness (L*), redness (a*), and yellowness (b*), followed pseudo-zero-order kinetics and were accelerated by increasing water activity. All analytical indices indicated that the dehydrated apples were stable at water activity levels below 0.316, with the degradation rate accelerating upon exposure to higher relative humidities. Above 0.316, a small increase in water activity of the product would sharply increase the degradation rate constants for both antioxidant and color variations.

  2. Asymptotically zero power charge-recycling bus architecture for battery-operated ultrahigh data rate ULSI's

    NASA Astrophysics Data System (ADS)

    Yamauchi, Hiroyuki; Akamatsu, Hironori; Fujita, Tsutomu

    1995-04-01

    An asymptotically zero power charge recycling bus (CRB) architecture, featuring virtual stacking of the individual bus-capacitance into a series configuration between supply voltage and ground, has been proposed. This CRB architecture makes it possible to reduce not only each bus-swing but also a total equivalent bus-capacitance of the ultramultibit buses running in parallel. The voltage swing of each bus is given by the recycled charge-supplying from the upper adjacent bus capacitance, instead of the power line. The dramatical power reduction was verified by the simulated and measured data. According to these data, the ultrahigh data rate of 25.6 Gb/s can be achieved while maintaining the power dissipation to be less than 100 mW, which corresponds to less than 10% that of the previously reported 0.9 V suppressed bus-swing scheme, at V(sub cc) = 3.6 V for the bus width of 512 b with the bus-capacitance of 14 pF per bit operating at 50 MHz.

  3. Digitizing Sound: How Can Sound Waves Be Turned into Ones and Zeros?

    ERIC Educational Resources Information Center

    Vick, Matthew

    2010-01-01

    From MP3 players to cell phones to computer games, we're surrounded by a constant stream of ones and zeros. Do we really need to know how this technology works? While nobody can understand everything, digital technology is increasingly making our lives a collection of "black boxes" that we can use but have no idea how they work. Pursuing…

  4. From Zero Energy Buildings to Zero Energy Districts

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

    Polly, Ben; Kutscher, Chuck; Macumber, Dan

    Some U.S. cities are planning advanced districts that have goals for zero energy, water, waste, and/or greenhouse gas emissions. From an energy perspective, zero energy districts present unique opportunities to cost-effectively achieve high levels of energy efficiency and renewable energy penetration across a collection of buildings that may be infeasible at the individual building scale. These high levels of performance are accomplished through district energy systems that harness renewable and wasted energy at large scales and flexible building loads that coordinate with variable renewable energy supply. Unfortunately, stakeholders face a lack of documented processes, tools, and best practices to assistmore » them in achieving zero energy districts. The National Renewable Energy Laboratory (NREL) is partnering on two new district projects in Denver: the National Western Center and the Sun Valley Neighborhood. We are working closely with project stakeholders in their zero energy master planning efforts to develop the resources needed to resolve barriers and create replicable processes to support future zero energy district efforts across the United States. Initial results of these efforts include the identification and description of key zero energy district design principles (maximizing building efficiency, solar potential, renewable thermal energy, and load control), economic drivers, and master planning principles. The work has also resulted in NREL making initial enhancements to the U.S. Department of Energy's open source building energy modeling platform (OpenStudio and EnergyPlus) with the long-term goal of supporting the design and optimization of energy districts.« less

  5. 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

  6. Zero-stress states of human pulmonary arteries and veins.

    PubMed

    Huang, W; Yen, R T

    1998-09-01

    The zero-stress states of the pulmonary arteries and veins from order 3 to order 9 were determined in six normal human lungs within 15 h postmortem. The zero-stress state of each vessel was obtained by cutting the vessel transversely into a series of short rings, then cutting each ring radially, which caused the ring to spring open into a sector. Each sector was characterized by its opening angle. The mean opening angle varied between 92 and 163 degrees in the arterial tree and between 89 and 128 degrees in the venous tree. There was a tendency for opening angles to increase as the sizes of the arteries and veins increased. We computed the residual strains based on the experimental measurements and estimated the residual stresses according to Hooke's law. We found that the inner wall of a vessel at the state in which the internal pressure, external pressure, and longitudinal stress are all zero was under compression and the outer wall was in tension, and that the magnitude of compressive stress was greater than the magnitude of tensile stress.

  7. An Analysis of Descriptors of Volatile Organic Compounds and Their Impact on Rate Constant for Reaction with Hydroxyl Radicals

    DTIC Science & Technology

    2018-05-01

    the descriptors were correlated to experimental rate constants. The five descriptors fell into one of two categories: whole molecule descriptors or...model based on these correlations . Although that goal was not achieved in full, considerable progress has been made, and there is potential for a...readme.txt) and compiled. We then searched for correlations between the calculated properties from theory and the experimental measurements of reaction rate

  8. Pulsed EPR measurements on reaction rate constants for addition of photo-generated radicals to double bonds of diethyl fumarate and diethyl maleate

    NASA Astrophysics Data System (ADS)

    Takahashi, Hirona; Hagiwara, Kenta; Kawai, Akio

    2016-11-01

    Addition reaction of photo-generated radicals to double bonds of diethyl fumarate (deF) and diethyl maleate (deM), which are geometrical isomers, was studied by means of time-resolved- (TR-) and pulsed-electron paramagnetic resonance (EPR). Analysis of TR-EPR spectra indicates that adduct radicals from deF and deM should have the same structure. The double bonds of these monomers are converted to single ones by addition reaction, which allows hindered internal rotation to give the same structure of adduct radical. The rate constants for addition reaction of photo-generated radicals were determined by Stern-Volmer analysis of the decay time of electron spin-echo intensity of these radicals measured by the pulsed EPR method. Rate constants for deF were found to be larger than those for deM. This relation is in good consistent with efficiency of polymerisation of deF and deM. Experimentally determined rate constants were evaluated by introducing the addition reaction model on the basis of two important factors enthalpy and polar effects.

  9. PLZT capacitor and method to increase the dielectric constant

    DOEpatents

    Taylor, Ralph S.; Fairchild, Manuel Ray; Balachjandran, Uthamalingam; Lee, Tae H.

    2017-12-12

    A ceramic-capacitor includes a first electrically-conductive-layer, a second electrically-conductive-layer arranged proximate to the first electrically-conductive-layer, and a dielectric-layer interposed between the first electrically-conductive-layer and the second electrically-conductive-layer. The dielectric-layer is formed of a lead-lanthanum-zirconium-titanate material (PLZT), wherein the PLZT is characterized by a dielectric-constant greater than 125, when measured at 25 degrees Celsius and zero Volts bias, and an excitation frequency of ten-thousand Hertz (10 kHz). A method for increasing a dielectric constant of the lead-lanthanum-zirconium-titanate material (PLZT) includes the steps of depositing PLZT to form a dielectric-layer of a ceramic-capacitor, and heating the ceramic-capacitor to a temperature not greater than 300.degree. C.

  10. Do semiclassical zero temperature black holes exist?

    PubMed

    Anderson, P R; Hiscock, W A; Taylor, B E

    2000-09-18

    The semiclassical Einstein equations are solved to first order in epsilon = Planck's over 2pi/M2 for the case of a Reissner-Nordström black hole perturbed by the vacuum stress energy of quantized free fields. Massless and massive fields of spin 0, 1/2, and 1 are considered. We show that in all physically realistic cases, macroscopic zero temperature black hole solutions do not exist. Any static zero temperature semiclassical black hole solutions must then be microscopic and isolated in the space of solutions; they do not join smoothly onto the classical extreme Reissner-Nordström solution as epsilon-->0.

  11. [Zero citation of Russian institute publications on the psychiatry and addiction].

    PubMed

    Nemtsov, A V; Kuznetsova-Moreva, E A

    To evaluate the zero-citation sizes. Based on the data of the Russian Science Citation Index the publication activity of four leading institutes in the field of Psychiatry and Addiction is analyzed. The same indices in the field of Neurology were used as a control. Number and percentage of publications with ≥1 citations and zero-citation were analyzed. It has been shown that in psychiatric science zero citation rate is quite high (from 32.8% to 47.2%, an average of 42.9%). It is higher compared to the control. Zero-citation indicator is essential to evaluate the effectiveness of scientific institutions.

  12. The Effects of Response Option Order and Question Order on Self-Rated Health

    PubMed Central

    Garbarski, Dana; Schaeffer, Nora Cate; Dykema, Jennifer

    2014-01-01

    Objectives This study aims to assess the impact of response option order and question order on the distribution of responses to the self-rated health (SRH) question and the relationship between SRH and other health-related measures. Methods In an online panel survey, we implement a 2-by-2 between-subjects factorial experiment, manipulating the following levels of each factor: 1) order of response options (“excellent” to “poor” versus “poor” to “excellent”); and 2) order of SRH item (either preceding or following the administration of domain-specific health items). We use chi-square difference tests, polychoric correlations, and differences in means and proportions to evaluate the effect of the experimental treatments on SRH responses and the relationship between SRH and other health measures. Results Mean SRH is higher (better health) and proportion in “fair” or “poor” health lower when response options are ordered from “excellent” to “poor” and SRH is presented first compared to other experimental treatments. Presenting SRH after domain-specific health items increases its correlation with these items, particularly when response options are ordered “excellent” to “poor.” Among participants with the highest level of current health risks, SRH is worse when it is presented last versus first. Conclusion While more research on the presentation of SRH is needed across a range of surveys, we suggest that ordering response options from “poor” to “excellent” might reduce positive clustering. Given the question order effects found here, we suggest presenting SRH before domain-specific health items in order to increase inter-survey comparability, as domain-specific health items will vary across surveys. PMID:25409654

  13. Optical factors determined by the T-matrix method in turbidity measurement of absolute coagulation rate constants.

    PubMed

    Xu, Shenghua; Liu, Jie; Sun, Zhiwei

    2006-12-01

    Turbidity measurement for the absolute coagulation rate constants of suspensions has been extensively adopted because of its simplicity and easy implementation. A key factor in deriving the rate constant from experimental data is how to theoretically evaluate the so-called optical factor involved in calculating the extinction cross section of doublets formed during aggregation. In a previous paper, we have shown that compared with other theoretical approaches, the T-matrix method provides a robust solution to this problem and is effective in extending the applicability range of the turbidity methodology, as well as increasing measurement accuracy. This paper will provide a more comprehensive discussion of the physical insight for using the T-matrix method in turbidity measurement and associated technical details. In particular, the importance of ensuring the correct value for the refractive indices for colloidal particles and the surrounding medium used in the calculation is addressed, because the indices generally vary with the wavelength of the incident light. The comparison of calculated results with experiments shows that the T-matrix method can correctly calculate optical factors even for large particles, whereas other existing theories cannot. In addition, the data of the optical factor calculated by the T-matrix method for a range of particle radii and incident light wavelengths are listed.

  14. Ordered Rate Constitutive Theories: Development of Rate Constitutive Equations for Solids, Liquids, and Gases

    DTIC Science & Technology

    2010-08-18

    the author(s) and should not contrued as an official Department of the Army position, policy or decision, unless so designated by other documentation...Daniel S. Nunez 0.50 Yong-Ting Ma 0.50 Tristan Moody 0.50 1.50FTE Equivalent: 3Total Number: Names of Post Doctorates PERCENT_SUPPORTEDNAME FTE...demonstrated that the constitutive theory for ordered thermofluids of all orders is indeed rate constitutive theory. The reseach work presented in this chapter

  15. 20 CFR 345.302 - Definition of terms and phrases used in experience-rating.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... raised in order to bring that rate to the minimum rate of zero is multiplied by the employer's 1-year...-year compensation base of each employer whose experience-based contribution rate, computed at Step 6 of.... Effective January 1, 1991, and on the first of each subsequent calendar year, the Board will reduce each...

  16. 20 CFR 345.302 - Definition of terms and phrases used in experience-rating.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... raised in order to bring that rate to the minimum rate of zero is multiplied by the employer's 1-year...-year compensation base of each employer whose experience-based contribution rate, computed at Step 6 of.... Effective January 1, 1991, and on the first of each subsequent calendar year, the Board will reduce each...

  17. 20 CFR 345.302 - Definition of terms and phrases used in experience-rating.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... raised in order to bring that rate to the minimum rate of zero is multiplied by the employer's 1-year...-year compensation base of each employer whose experience-based contribution rate, computed at Step 6 of.... Effective January 1, 1991, and on the first of each subsequent calendar year, the Board will reduce each...

  18. Comment on ‘The paradoxical zero reflection at zero energy’

    NASA Astrophysics Data System (ADS)

    van Dijk, W.; Nogami, Y.

    2017-05-01

    We point out that the anomalous threshold effect in one dimension occurs when the reflection probability at zero energy R(0) has some other value than unity, rather than R(0)=0 or R(0)\\ll 1 as implied by Ahmed et al in their paper entitled ‘The paradoxical zero reflection at zero energy’ (2017 Eur. J. Phys. 38 025401).

  19. Neutrino Masses, Cosmological Bound and Four Zero Yukawa Textures

    NASA Astrophysics Data System (ADS)

    Adhikary, Biswajit; Ghosal, Ambar; Roy, Probir

    Four zero neutrino Yukawa textures in a specified weak basis, combined with μτ symmetry and type-I seesaw, yield a highly constrained and predictive scheme. Two alternately viable 3×3 light neutrino Majorana mass matrices mνA/mνB result with inverted/normal mass ordering. Neutrino masses, Majorana in character and predicted within definite ranges with laboratory and cosmological inputs, will have their sum probed cosmologically. The rate for 0νββ decay, though generally below the reach of planned experiments, could approach it in some parameter region. Departure from μτ symmetry due to RG evolution from a high scale and consequent CP violation, with a Jarlskog invariant whose magnitude could almost reach 6×10-3, are explored.

  20. Thermodynamic Analysis of Chemically Reacting Mixtures-Comparison of First and Second Order Models.

    PubMed

    Pekař, Miloslav

    2018-01-01

    Recently, a method based on non-equilibrium continuum thermodynamics which derives thermodynamically consistent reaction rate models together with thermodynamic constraints on their parameters was analyzed using a triangular reaction scheme. The scheme was kinetically of the first order. Here, the analysis is further developed for several first and second order schemes to gain a deeper insight into the thermodynamic consistency of rate equations and relationships between chemical thermodynamic and kinetics. It is shown that the thermodynamic constraints on the so-called proper rate coefficient are usually simple sign restrictions consistent with the supposed reaction directions. Constraints on the so-called coupling rate coefficients are more complex and weaker. This means more freedom in kinetic coupling between reaction steps in a scheme, i.e., in the kinetic effects of other reactions on the rate of some reaction in a reacting system. When compared with traditional mass-action rate equations, the method allows a reduction in the number of traditional rate constants to be evaluated from data, i.e., a reduction in the dimensionality of the parameter estimation problem. This is due to identifying relationships between mass-action rate constants (relationships which also include thermodynamic equilibrium constants) which have so far been unknown.