A Decreasing Failure Rate, Mixed Exponential Model Applied to Reliability.

DTIC Science & Technology

1981-06-01

Trident missile systems have been observed. The mixed exponential distribu- tion has been shown to fit the life data for the electronic equipment on...these systems . This paper discusses some of the estimation problems which occur with the decreasing failure rate mixed exponential distribution when...assumption of constant or increasing failure rate seemed to be incorrect. 2. However, the design of this electronic equipment indicated that

Theoretical and experimental study on the effects of particle size and temperature on the reaction kinetics of cubic nano-Cu2O

NASA Astrophysics Data System (ADS)

Tang, Huanfeng; Huang, Zaiyin; Xiao, Ming; Liang, Min; Chen, Liying; Tan, XueCai

2017-09-01

The activities, selectivities, and stabilities of nanoparticles in heterogeneous reactions are size-dependent. In order to investigate the influencing laws of particle size and temperature on kinetic parameters in heterogeneous reactions, cubic nano-Cu2O particles of four different sizes in the range of 40-120 nm have been controllably synthesized. In situ microcalorimetry has been used to attain thermodynamic data on the reaction of Cu2O with aqueous HNO3 and, combined with thermodynamic principles and kinetic transition-state theory, the relevant reaction kinetic parameters have been evaluated. The size dependences of the kinetic parameters are discussed in terms of the established kinetic model and the experimental results. It was found that the reaction rate constants increased with decreasing particle size. Accordingly, the apparent activation energy, pre-exponential factor, activation enthalpy, activation entropy, and activation Gibbs energy decreased with decreasing particle size. The reaction rate constants and activation Gibbs energies increased with increasing temperature. Moreover, the logarithms of the apparent activation energies, pre-exponential factors, and rate constants were found to be linearly related to the reciprocal of particle size, consistent with the kinetic models. The influence of particle size on these reaction kinetic parameters may be explained as follows: the apparent activation energy is affected by the partial molar enthalpy, the pre-exponential factor is affected by the partial molar entropy, and the reaction rate constant is affected by the partial molar Gibbs energy. [Figure not available: see fulltext.

Oxidation of octylphenol by ferrate(VI).

PubMed

Anquandah, George A K; Sharma, Virender K

2009-01-01

The rates of the oxidation of octylphenols (OP) by potassium ferrate(VI) (K(2)FeO(4)) in water were determined as a function of pH (8.0-10.9) at 25 degrees C. The rate law for the oxidation of OP by Fe(VI) was found to be first order with each reactant. The observed second-order rate constants, k(obs), for the oxidation of alkylphenols decreased with an increase in pH. The speciation of Fe(VI) (HFeO(4)(-) and FeO(4)(2 -)) and OP (OP-OH and OP-O(-)) species were used to determine individual rate constants of the reactions. Comparison of rate constants and half-lives of oxidation of OP by Fe(VI) with nonylphenol (NP) and bisphenol-A (BPA) were conducted to demonstrate that Fe(VI) efficiently oxidizes environmentally relevant alkylphenols in water.

Effect of solvent on crystallization behavior of xylitol

NASA Astrophysics Data System (ADS)

Hao, Hongxun; Hou, Baohong; Wang, Jing-Kang; Lin, Guangyu

2006-04-01

Effect of organic solvents content on crystallization behavior of xylitol was studied. Solubility and crystallization kinetics of xylitol in methanol-water system were experimentally determined. It was found that the solubility of xylitol at various methanol content all increases with increase of temperature. But it decreases when increasing methanol content at constant temperature. Based on the theory of population balance, the nucleation and growth rates of xylitol in methanol-water mixed solvents were calculated by moments method. From a series of experimental population density data of xylitol gotten from a batch-operated crystallizer, parameters of crystal nucleation and growth rate equations at different methanol content were got by the method of nonlinear least-squares. By analyzing, it was found that the content of methanol had an apparent effect on nucleation and growth rate of xylitol. At constant temperature, the nucleation and growth rate of xylitol all decrease with increase of methanol content.

Stress and Protein Turnover in Lemna minor1

PubMed Central

Cooke, Robert J.; Oliver, Jane; Davies, David D.

1979-01-01

Transfer of fronds of Lemna minor L. to adverse growth conditions or stress situations causes a lowering of the growth rate and a loss of soluble protein per frond, the extent of the loss being dependent on the nature of the stress. The loss or protein is due to two factors: (a) a decrease in the rate constant of protein synthesis (ks); (b) an increase in the rate constant of protein degradation (kd). In plants adapted to the stresses, protein synthesis increases and the initially rapid rate of proteolysis is reduced. Addition of abscisic acid both lowers ks and increases kd, whereas benzyladenine seems to alleviate the effects of stress on protein content by decreasing kd rather than by altering ks. Based on the measurement of enzyme activities, stress-induced protein degradation appears to be a general phenomenon, affecting many soluble proteins. The adaptive significance of stress-induced proteolysis is discussed. PMID:16661102

The influence of polarizability and charge transfer on specific ion effects in the dynamics of aqueous salt solutions

NASA Astrophysics Data System (ADS)

Nguyen, Mary; Rick, Steven W.

2018-06-01

The diffusion rates for water molecules in salt solutions depend on the identity of the ions, as well as their concentration. Among the alkali metal ions, cesium and potassium increase and sodium strongly decreases the diffusion constant of water. The origin of the difference can be understood by examining the simulation results using different potential models. In this work, aqueous solutions of salts are simulated with a variety of models. Commonly used non-polarizable models, which otherwise reproduce many experimental properties, do not capture the trend in the diffusion constant, while models which include polarization and/or charge transfer interactions do. For the non-polarizable models, the diffusion constant decreases too strongly with salt concentration. The changes in the water diffusion constant with increasing salt concentration match the diffusion constant of the ion. The ion diffusion constant is dependent on the residence time for water in the ion solvation shell. The non-polarizable models over-estimate the residence time, relative to the translational diffusion constant and so tend to under-estimate the ion and water diffusion constants.

Effect of surface curvature on diffusion-limited reactions on a curved surface

NASA Astrophysics Data System (ADS)

Eun, Changsun

2017-11-01

To investigate how the curvature of a reactive surface can affect reaction kinetics, we use a simple model in which a diffusion-limited bimolecular reaction occurs on a curved surface that is hollowed inward, flat, or extended outward while keeping the reactive area on the surface constant. By numerically solving the diffusion equation for this model using the finite element method, we find that the rate constant is a non-linear function of the surface curvature and that there is an optimal curvature providing the maximum value of the rate constant, which indicates that a spherical reactant whose entire surface is reactive (a uniformly reactive sphere) is not the most reactive species for a given reactive surface area. We discuss how this result arises from the interplay between two opposing effects: the exposedness of the reactive area to its partner reactants, which causes the rate constant to increase as the curvature increases, and the competition occurring on the reactive surface, which decreases the rate constant. This study helps us to understand the role of curvature in surface reactions and allows us to rationally design reactants that provide a high reaction rate.

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.

Voltage dependence of acetylcholine receptor channel gating in rat myoballs

PubMed Central

1992-01-01

Whole-cell currents from nicotinic acetylcholine receptor (AChR) channels were studied in rat myoballs using a light-activated agonist to determine the voltage dependence of the macroscopic opening and closing rate constants. Myoballs were bathed in a solution containing a low concentration of the inactive isomer of the photoisomerizable azobenzene derivative, cis-Bis-Q. A light flash was then presented to produce a known concentration jump of agonist, trans-Bis-Q, across a wide range of membrane potentials in symmetrical solutions (NaCl or CsCl on both sides) or asymmetrical solutions (NaCl in the bath and CsCl in the pipette). At the low agonist concentration used in this study, the reciprocal of the macroscopic time constants gives an unambiguous measure of the effective closing rate. It showed an exponential decrease with membrane hyperpolarization between +20 and - 100 mV, but tended to level off at more depolarized and at more hyperpolarized membrane potentials. The relative effective opening rate was derived from the steady-state conductance, the single-channel conductance, and the apparent closing rate; it decreased sharply in the depolarizing region and tended to level off and then turn up in the hyperpolarizing region. The two effective rate constants were shown to depend on the first, second, and third power of membrane potential. PMID:1460456

Chemiluminescence and reactivity of the composites based on blends of polypropylene and polyamide

NASA Astrophysics Data System (ADS)

Vorontsov, N. V.; Popov, A. A.; Margolin, A. L.

2017-12-01

The effect of the composition of blends based on isotactic polypropylene (PP) and aliphatic polyamide 6/66-4 (PA) on the rate of photo-oxidation of their mixtures in air at room temperature has been studied. The decay of photoinduced chemiluminescence was studied to determine the kinetics of peroxyl radical termination in composites and the rate constants of this process depending on the composition of the mixtures. In the presence of PA, the rate of photo-oxidation of mixtures is much higher than the rates of photo-oxidation of separately taken components, PP and PA. Thus, the kinetics of photo-oxidation of mixtures differs from the simple sum of photo-oxidation kinetics of PP and PA, which should be expected in the absence of chemical and physical interaction of the components of the mixture. A decrease in the rate constants due to PA additives indicates a decrease in the mobility of molecules in the composites and explains the observed increase in photo-oxidation of mixtures.

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

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

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].

Time- and Space-Resolved Spectroscopic Investigation on Pi-Conjugated Nanostructures

DTIC Science & Technology

2013-03-26

compared with 1 suggest that the nonradiative rates in the S1 states of 2 and 3 substantially decrease with respect to the radiative rate constants. By... nonradiative internal conversion rates. Moreover, to investigate the NLO properties of the biradical 2-OS, two-photon absorption measurements were

Instability of chlorophyll in yellow lupin seedlings grown in soil contaminated with ciprofloxacin and tetracycline.

PubMed

Rydzyński, Dariusz; Piotrowicz-Cieślak, Agnieszka I; Grajek, Hanna; Michalczyk, Dariusz J

2017-10-01

With increasing soil concentrations of ciprofloxacin and tetracycline a decrease of leaf chlorophyll content was observed. Tetracycline was more detrimental than ciprofloxacin. The chlorophyll content in plants growing for ten days on a tetracycline containing soil decreased by 68%. The decrease of chlorophyll concentration was even sharper in new leaves that formed after application of the antibiotic (up to 81% drop). The comparison of absorption spectra of commercial, reagent grade chlorophyll, alone and incubated with antibiotics, has shown that ciprofloxacin and tetracycline can react directly with chlorophyll and decrease its concentration by 47.7% and 48.5%, respectively. The changes in fluorescence spectra confirmed the formation of chlorophyll degradation product. The chlorophyll decay was a second order reaction and depended on antibiotic concentration and duration of exposure. Reaction rate constants differed with antibiotics and their soil concentrations. With increasing contents of antibiotics in soil the constant of chlorophyll degradation rate in lupin plants increased from k = 870 M -1 day -1 for 3 mg ciprofloxacin to k = 2490 M -1 day -1 for 90 mg ciprofloxacin, and in the case of tetracycline the reaction rate constant increased from k = 1330 M -1 day -1 to k = 2910 M -1 day -1 . The sensitivity of chlorophyll to ciprofloxacin and tetracycline was confirmed by determining EC and TU indices. Copyright © 2017 Elsevier Ltd. All rights reserved.

Luminescence of the (O2(a(1)Δ(g)))2 collisional complex in the temperature range of 90-315 K: Experiment and theory.

PubMed

Zagidullin, M V; Pershin, A A; Azyazov, V N; Mebel, A M

2015-12-28

Experimental and theoretical studies of collision induced emission of singlet oxygen molecules O2(a(1)Δg) in the visible range have been performed. The rate constants, half-widths, and position of peaks for the emission bands of the (O2(a(1)Δg))2 collisional complex centered around 634 nm (2) and 703 nm (3) have been measured in the temperature range of 90-315 K using a flow-tube apparatus that utilized a gas-liquid chemical singlet oxygen generator. The absolute values of the spontaneous emission rate constants k2 and k3 are found to be similar, with the k3/k2 ratio monotonically decreasing from 1.1 at 300 K to 0.96 at 90 K. k2 slowly decreases with decreasing temperature but a sharp increase in its values is measured below 100 K. The experimental results were rationalized in terms of ab initio calculations of the ground and excited potential energy and transition dipole moment surfaces of singlet electronic states of the (O2)2 dimole, which were utilized to compute rate constants k2 and k3 within a statistical model. The best theoretical results reproduced experimental rate constants with the accuracy of under 40% and correctly described the observed temperature dependence. The main contribution to emission process (2), which does not involve vibrational excitation of O2 molecules at the ground electronic level, comes from the spin- and symmetry-allowed 1(1)Ag←(1)B3u transition in the rectangular H configuration of the dimole. Alternatively, emission process (3), in which one of the monomers becomes vibrationally excited in the ground electronic state, is found to be predominantly due to the vibronically allowed 1(1)Ag←2(1)Ag transition induced by the asymmetric O-O stretch vibration in the collisional complex. The strong vibronic coupling between nearly degenerate excited singlet states of the dimole makes the intensities of vibronically and symmetry-allowed transitions comparable and hence the rate constants k2 and k3 close to one another.

Kinetics of phloretin binding to phosphatidylcholine vesicle membranes

PubMed Central

1980-01-01

The submillisecond kinetics for phloretin binding to unilamellar phosphatidylcholine (PC) vesicles was investigated using the temperature-jump technique. Spectrophotometric studies of the equilibrium binding performed at 328 nm demonstrated that phloretin binds to a single set of independent, equivalent sites on the vesicle with a dissociation constant of 8.0 microM and a lipid/site ratio of 4.0. The temperature of the phloretin-vesicle solution was jumped by 4 degrees C within 4 microseconds producing a monoexponential, concentration-dependent relaxation process with time constants in the 30--200-microseconds time range. An analysis of the concentration dependence of relaxation time constants at pH 7.30 and 24 degrees C yielded a binding rate constant of 2.7 X 10(8) M-1 s-1 and an unbinding constant of 2,900 s-1; approximately 66 percent of total binding sites are exposed at the outer vesicle surface. The value of the binding rate constant and three additional observations suggest that the binding kinetics are diffusion limited. The phloretin analogue, naringenin, which has a diffusion coefficient similar to phloretin yet a dissociation constant equal to 24 microM, bound to PC vesicle with the same rate constant as phloretin did. In addition, the phloretin-PC system was studied in buffers made one to six times more viscous than water by addition of sucrose or glycerol to the differ. The equilibrium affinity for phloretin binding to PC vesicles is independent of viscosity, yet the binding rate constant decreases with the expected dependence (kappa binding alpha 1/viscosity) for diffusion-limited processes. Thus, the binding rate constant is not altered by differences in binding affinity, yet depends upon the diffusion coefficient in buffer. Finally, studies of the pH dependence of the binding rate constant showed a dependence (kappa binding alpha [1 + 10pH-pK]) consistent with the diffusion-limited binding of a weak acid. PMID:7391812

Time trends and latitude dependence of uveal and cutaneous malignant melanoma induced by solar radiation

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

Moan, J.; Setlow, R.; Cicarma, E.

2010-01-01

In order to evaluate the role of solar radiation in uveal melanoma etiology, the time and latitude dependency of the incidence rates of this melanoma type were studied in comparison with those of cutaneous malignant melanoma (CMM). Norway and several other countries with Caucasian populations were included. There is a marked north - south gradient of the incidence rates of CMM in Norway, with three times higher rates in the south than in the north. No such gradient is found for uveal melanoma. Similar findings have been published for CMM in other Caucasian populations, with the exception of Europe asmore » a whole. In most populations the ratios of uveal melanoma incidence rates to those of CMM tend to decrease with increasing CMM rates. This is also true for Europe, in spite of the fact that in this region there is an inverse latitude gradient of CMM, with higher rates in the north than in the south. In Norway the incidence rates of CMM have increased until about 1990 but have been constant, or even decreased (for young people) after that time, indicating constant or decreasing sun exposure. The uveal melanoma rates have been increasing after 1990. In most other populations the incidence rates of CMM have been increasing until recently while those of uveal melanoma have been decreasing. These data generally support the assumption that uveal melanomas are not generated by ultraviolet (UV) radiation and that solar UV, via its role in vitamin D photosynthesis, may have a protective effect.« less

Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol.

PubMed

Smith, Jeremy D; Kinney, Haley; Anastasio, Cort

2015-04-21

Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ˙OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ˙OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ˙OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 μg mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol.

Alcohols potentiate the function of 5-HT3 receptor–channels on NCB-20 neuroblastoma cells by favouring and stabilizing the open channel state

PubMed Central

Zhou, Qing; Verdoorn, Todd A; Lovinger, David M

1998-01-01

5-HT3 receptor-mediated ion current was recorded from NCB-20 neuroblastoma cells using the whole-cell patch-clamp technique. Rapid drug superfusion was used to study the mechanism of alcohol potentiation of 5-HT3 receptor function and to analyse effects of alcohols on receptor-channel kinetics in detail.Trichloroethanol (TCEt) increased in a dose-dependent way the initial slope, 20–80 % rise time and measured desensitization rate of the current induced by low concentrations (1–2 μm) of 5-HT. Ethanol (EtOH) and butanol (ButOH) had similar effects on the 5-HT3 receptor-induced current.TCEt and ButOH decreased the measured desensitization rate of current induced by 10 μm 5-HT, a maximally effective concentration of agonist. These alcohols also increased the relative amplitude of steady state to peak current induced by 2 or 10 μm 5-HT, indicating a possible decrease in the intrinsic rate of desensitization.TCEt also decreased the deactivation rate of the current activated by 2 μm 5-HT after a short pulse of agonist application.Current sweeps generated by 1 μm 5-HT in the presence or absence of 10 mm TCEt or 100 mm EtOH were well fitted using a modified standard kinetic model derived from the nicotinic acetylcholine receptor. This analysis indicated that potentiation by alcohols could be accounted for by increases in the association rate constant coupled with decreases in the dissociation and desensitization rate constants.This study suggests that alcohols potentiate 5-HT3 receptor-mediated current by both increasing the rate of channel activation and stabilizing the open state by decreasing the rates of channel deactivation and desensitization. PMID:9518697

Hydroxynonenal-stimulated activity of the uncoupling protein in Acanthamoeba castellanii mitochondria under phosphorylating conditions.

PubMed

Woyda-Ploszczyca, Andrzej; Jarmuszkiewicz, Wieslawa

2013-05-01

The influence of 4-hydroxy-2-nonenal (HNE), a lipid peroxidation end product, on the activity of the amoeba Acanthamoeba castellanii uncoupling protein (AcUCP) in isolated phosphorylating mitochondria was studied. Under phosphorylating conditions, exogenously added HNE induced GTP-sensitive AcUCP-mediated mitochondrial uncoupling. The HNE-induced proton leak decreased the yield of oxidative phosphorylation in an HNE concentration-dependent manner. The present study describes how the contributions of ATP synthase and HNE-induced AcUCP in phosphorylating respiration vary when the rate of succinate oxidation is decreased by limiting succinate uptake or inhibiting complex III activity within the range of a constant membrane potential. In phosphorylating mitochondria, at a given HNE concentration (100 μM), the efficiency of AcUCP in mitochondrial uncoupling increased as the respiratory rate decreased because the AcUCP contribution remained constant while the ATP synthase contribution decreased with the respiratory rate. HNE-induced uncoupling can be inhibited by GTP only when ubiquinone is sufficiently oxidized, indicating that in phosphorylating A. castellanii mitochondria, the sensitivity of AcUCP activity to GTP depends on the redox state of the membranous ubiquinone.

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 is unlikely that the efficiency of (PO3-) transfer to the 6-hydroxyl group of bound Glc-1-P (thermodynamically favorable direction) is reduced by more than an order of magnitude in the Cd2+ enzyme. By contrast, the efficiency of the Li+ enzyme in the same (PO3-)-transfer step is less than 4 x 10(-8) that of the Mg2+ enzyme.(ABSTRACT TRUNCATED AT 400 WORDS)

Effect of Dunaliella tertiolecta organic exudates on the Fe(II) oxidation kinetics in seawater.

PubMed

González, A G; Santana-Casiano, J M; González-Dávila, M; Pérez-Almeida, N; Suárez de Tangil, M

2014-07-15

The role played by the natural organic ligands excreted by the green algae Dunaliella tertiolecta on the Fe(II) oxidation rate constants was studied at different stages of growth. The concentration of dissolved organic carbon increased from 2.1 to 7.1 mg L(-1) over time of culture. The oxidation kinetics of Fe(II) was studied at nanomolar levels and under different physicochemical conditions of pH (7.2-8.2), temperature (5-35 °C), salinity (10-37), and dissolved organic carbon produced by cells (2.1-7.1 mg L(-1)). The experimental rate always decreased in the presence of organic exudates with respect to that in the control seawater. The Fe(II) oxidation rate constant was also studied in the context of Marcus theory, where ΔG° was 39.31-51.48 kJ mol(-1). A kinetic modeling approach was applied for computing the equilibrium and rate constants for Fe(II) and exudates present in solution, the Fe(II) speciation, and the contribution of each Fe(II) species to the overall oxidation rate constant. The best fit model took into account two acidity equilibrium constants for the Fe(II) complexing ligands with pKa,1=9.45 and pKa,2=4.9. The Fe(II) complexing constants were KFe(II)-LH=3×10(10) and KFe(II)-L=10(7), and the corresponding computed oxidation rates were 68±2 and 36±8 M(-1) min(-1), respectively.

Mechanism of thermal electron attachment to NO/sub 2/

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

Shimamori, H.; Hotta, H.

1986-03-15

The mechanism of thermal electron attachment to NO/sub 2/ has been reexamined by observing the dependence of the attachment rates on the nature and the pressure of the environmental gases. Measurements for mixtures of NO/sub 2/ with rare gases, H/sub 2/, D/sub 2/, N/sub 2/, CO/sub 2/, and n-C/sub 4/H/sub 10/ all showed two-body pressure dependence of the attachment rates at buffer-gas pressures of about 10 to 100 Torr. They gave the same two-body rate constant of (1.13 +- 0.07) x 10/sup -10/ cm/sup 3/ molecule/sup -1/ s/sup -1/. The latter result disagrees with the data reported by Mahan andmore » Walker in 1967. The present results indicate that the collisional electron detachment process introduced previously to interpret the effect of the nature of environmental gases should be negligible. We have also observed the decrease of the two-body rate constants at pressures below about 10 Torr for all the mixtures studied. This strongly suggests that the attachment mechanism is an ordinary two-step three-body process. The three-body rate constants then obtained are mostly of the orders of 10/sup -27/ cm/sup 6/ molecule/sup -2/ s/sup -1/ and do not differ much with nature of the third bodies. An autoionization lifetime of 1 x 10/sup -8/ s has been estimated for the transient-negative ion of NO/sub 2/. It has been found that even room light could cause appreciable decrease of the rate constants, probably through decomposition of NO/sub 2/ molecules. The discrepancy between the present results and the previous ones may be due to such an effect.« less

QSAR ANALYSIS OF SORPTION-CORRECTED RATE CONSTANTS FOR REDUCTIVE BIOTRANSFORMATION OF HALOGENATED AROMATICS

EPA Science Inventory

The inherent coupling among geochemical and microbial reactions may have significant effects on the environmental fate of a containinant. For example, sorption processes may decrease the concentration of an organic compound in solution, thereby reducing the biodegradation rate of...

Investigation of operating parameters on CO2 splitting by dielectric barrier discharge plasma

NASA Astrophysics Data System (ADS)

Pan, CHEN; Jun, SHEN; Tangchun, RAN; Tao, YANG; Yongxiang, YIN

2017-12-01

Experiments of CO2 splitting by dielectric barrier discharge (DBD) plasma were carried out, and the influence of CO2 flow rate, plasma power, discharge voltage, discharge frequency on CO2 conversion and process energy efficiency were investigated. It was shown that the absolute quantity of CO2 decomposed was only proportional to the amount of conductive electrons across the discharge gap, and the electron amount was proportional to the discharge power; the energy efficiency of CO2 conversion was almost a constant at a lower level, which was limited by CO2 inherent discharge character that determined a constant gap electric field strength. This was the main reason why CO2 conversion rate decreased as the CO2 flow rate increase and process energy efficiency was decreased a little as applied frequency increased. Therefore, one can improve the CO2 conversion by less feed flow rate or larger discharge power in DBD plasma, but the energy efficiency is difficult to improve.

In VIVO tracer kinetics of plant function using positron emission technology

NASA Astrophysics Data System (ADS)

Fares, Y.; Goeschl, J. D.; Magnuson, C. E.; Mckinney, C. J.; Musser, R. L.; Strain, B. R.

1989-04-01

A 11CO 2 storage and dispensing system was developed and used successfully to deliver constant activity levels for 2 h plant tracer experiments. Using tracer kinetics of a step input function the relationships between diurnal patterns of carbon partitioning and gas exchange properties of leaves in C 3 and C 4 plants were studied. We also studied the immediate and long term effects of the abrupt changes in CO 2 concentrations on carbon partitioning of these species. Results indicate that raising the CO 2 concentration above ambient immediately increases 11C storage over export rates, while lowering the CO 2 concentration immediately decreases storage more than export rates. This long term accumulation of starch may depend as much on the biochemistry of partitioning within the leaf as on limitations in the sink capacity of plants. Although gas exchange remained constant during the photoperiod, the photosynthate storage rate increased and the export rate decreased. These changes were more pronounced in C 4 plants.

Kinetic analysis of cooperative interactions induced by Mn2+ binding to the chloroplast H(+)-ATPase.

PubMed

Hiller, R; Carmeli, C

1990-07-03

The kinetics of Mn2+ binding to three cooperatively interacting sites in chloroplast H(+)-ATPase (CF1) were measured by EPR following rapid mixing of the enzyme with MnCl2 with a time resolution of 8 ms. Mixing of the enzyme-bound Mn2+ with MgCl2 gave a measure of the rate of exchange. The data could be best fitted to a kinetic model assuming three sequential, positively cooperative binding sites. (1) In the latent CF1, the binding to all three sites had a similar on-rate constants of (1.1 +/- 0.04) X 10(4) M-1s-1. (2) Site segregation was found in the release of ions with off-rate constants of 0.69 +/- 0.04 s-1 for the first two and 0.055 +/- 0.003 s-1 for the third. (3) Addition of one ADP per CF1 caused a decrease in the off-rate constants to 0.31 +/- 0.02 and 0.033 +/- 0.008 s-1 for the first two and the third sites, respectively. (4) Heat activation of CF1 increased the on-rate constant to (4.2 +/- 0.92) X 10(4) M-1s-1 and the off-rate constants of the first two and the third site to 1.34 +/- 0.08 and 0.16 +/- 0.07 s-1, respectively. (5) The calculated thermodynamic dissociation constants were similar to those previously obtained from equilibrium binding studies. These findings were correlated to the rate constants obtained from studies of the catalysis and regulation of the H(+)-ATPase. The data support the suggestion that regulation induces sequential progress of catalysis through the three active sites of the enzyme.

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

USGS Publications Warehouse

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

1996-01-01

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

Auger-generated hot carrier current in photo-excited forward biased single quantum well blue light emitting diodes

NASA Astrophysics Data System (ADS)

Espenlaub, Andrew C.; Alhassan, Abdullah I.; Nakamura, Shuji; Weisbuch, Claude; Speck, James S.

2018-04-01

We report on measurements of the photo-modulated current-voltage and electroluminescence characteristics of forward biased single quantum well, blue InGaN/GaN light emitting diodes with and without electron blocking layers. Low intensity resonant optical excitation of the quantum well was observed to induce an additional forward current at constant forward diode bias, in contrast to the usual sense of the photocurrent in photodiodes and solar cells, as well as an increased electroluminescence intensity. The presence of an electron blocking layer only slightly decreased the magnitude of the photo-induced current at constant forward bias. Photo-modulation at constant forward diode current resulted in a reduced diode bias under optical excitation. We argue that this decrease in diode bias at constant current and the increase in forward diode current at constant applied bias can only be due to additional hot carriers being ejected from the quantum well as a result of an increased Auger recombination rate within the quantum well.

Irrigation model of bleached Kraft mill wastewater through volcanic soil as a pollutants attenuation process.

PubMed

Navia, R; Inostroza, X; Diez, M C; Lorber, K E

2006-05-01

An irrigation process through volcanic soil columns was evaluated for bleached Kraft mill effluent pollutants retention. The system was designed to remove color and phenolic compounds and a simple kinetic model for determining the global mass transfer coefficient and the adsorption rate constant was used. The results clearly indicate that the global mass transfer coefficient values (K(c)a) and the adsorption rate constants are higher for the irrigation processes onto acidified soil. This means that the pretreatment of washing the volcanic soil with an acid solution has a positive effect on the adsorption rate for both pollutant groups. The enhanced adsorption capacity is partially explained by the activation of the metal oxides present in the soil matrix during the acid washing process. Increasing the flow rate from 1.5 to 2.5 ml/min yielded higher (K(c)a) values and adsorption rate constants for both pollutant groups. For instance, regarding color adsorption onto acidified soil, there is an increment of 43% in the (K(c)a) value for the experiment with a flow rate of 2.5 ml/min. Increasing the porosity of the column from 0.55 to 0.59, yielded a decrease in the (K(c)a) values for color and phenolic compounds adsorption processes. Onto natural soil for example, these decreases reached 21% and 24%, respectively. Therefore, the (K(c)a) value is dependent on both the liquid-phase velocity (external resistance) and the soil fraction in the column (internal resistance); making forced convection and diffusion to be the main transport mechanisms involved in the adsorption process. Analyzing the adsorption rate constants (K(c)a)/m, phenolic compounds and color adsorption rates onto acidified soil of 2.25 x 10(-6) and 2.62 x 10(-6) l/mg min were achieved for experiment 1. These adsorption rates are comparable with other adsorption systems and adsorbent materials.

Effect of hypoxia on metabolic rate, core body temperature, and c-fos expression in the naked mole rat.

PubMed

Nathaniel, Thomas I; Otukonyong, Effiong; Abdellatif, Ahmed; Soyinka, Julius O

2012-10-01

Recent investigations of hypoxia physiology in the naked mole rat have opened up an interesting line of research into the basic physiological and genomic alterations that accompany hypoxia survival. The extent to which such findings connect the effect of hypoxia to metabolic rate (O₂ consumption), core body temperature (Tb), and transcripts encoding the immediate early gene product (such as c-fos) under a constant ambient temperature (Ta) is not well known. We investigated this issue in the current study. Our first sets of experiments measured Tb and metabolic rates during exposure of naked mole rats to hypoxia over a constant Ta. Hypoxia significantly decreased metabolic rates in the naked mole rat. Although core Tb also decreased during hypoxia, the effect of hypoxia in suppressing core Tb was not significant. The second series of experiments revealed that c-fos protein and mRNA expression in the hippocampus neurons (CA1) increased in naked mole rats that were repeatedly exposed to 3% O₂ for 60 min per day for 5 days when compared to normoxia. Our findings provide evidence for the up-regulation of c-fos and suppression of metabolic rate in hypoxia tolerating naked mole rats under constant ambient temperature. Metabolic suppression and c-fos upregulation constitute part of the physiological complex associated with adaptation to hypoxia. Published by Elsevier Ltd.

Kinetic studies of amino acid-based surfactant binding to DNA.

PubMed

Santhiya, Deenan; Dias, Rita S; Dutta, Sounak; Das, Prasanta Kumar; Miguel, Maria G; Lindman, Björn; Maiti, Souvik

2012-05-24

In this work, the binding kinetics of amino acid-based surfactants, presenting different linkers and head groups, with calf thymus (CT)-DNA was studied using stopped-flow fluorescence spectroscopy. The kinetic studies were carried out as a function of Na(+) concentration and surfactant-to-DNA charge ratio. The surfactant binding on DNA took place in two consecutive steps, for which the corresponding first and second relative rate constants (k(1) and k(2)) were determined. The fast step was attributed to the surfactant binding to DNA and micelle formation in its vicinity, the slower step to DNA condensation and possible rearrangement of the surfactant aggregates. In general, both relative rate constants increase with surfactant concentration and decrease with the ionic strength of the medium. The architecture of the surfactant was found to have a significant impact on the kinetics of the DNA-surfactant complexation. Surfactants with amide linkers showed larger relative rate constants than those with ester linkers. The variation of the relative rate constants with the head groups of the surfactants, alanine and proline, was found to be less obvious, being partially dependent on the surfactant concentration.

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

NASA Technical Reports Server (NTRS)

Shanabarger, M. R.

1979-01-01

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

Impact of uncertainties in inorganic chemical rate constants on tropospheric composition and ozone radiative forcing

NASA Astrophysics Data System (ADS)

Newsome, Ben; Evans, Mat

2017-12-01

Chemical rate constants determine the composition of the atmosphere and how this composition has changed over time. They are central to our understanding of climate change and air quality degradation. Atmospheric chemistry models, whether online or offline, box, regional or global, use these rate constants. Expert panels evaluate laboratory measurements, making recommendations for the rate constants that should be used. This results in very similar or identical rate constants being used by all models. The inherent uncertainties in these recommendations are, in general, therefore ignored. We explore the impact of these uncertainties on the composition of the troposphere using the GEOS-Chem chemistry transport model. Based on the Jet Propulsion Laboratory (JPL) and International Union of Pure and Applied Chemistry (IUPAC) evaluations we assess the influence of 50 mainly inorganic rate constants and 10 photolysis rates on tropospheric composition through the use of the GEOS-Chem chemistry transport model. We assess the impact on four standard metrics: annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime. Uncertainty in the rate constants for NO2 + OH →M HNO3 and O3 + NO → NO2 + O2 are the two largest sources of uncertainty in these metrics. The absolute magnitude of the change in the metrics is similar if rate constants are increased or decreased by their σ values. We investigate two methods of assessing these uncertainties, addition in quadrature and a Monte Carlo approach, and conclude they give similar outcomes. Combining the uncertainties across the 60 reactions gives overall uncertainties on the annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime of 10, 11, 16 and 16 %, respectively. These are larger than the spread between models in recent model intercomparisons. Remote regions such as the tropics, poles and upper troposphere are most uncertain. This chemical uncertainty is sufficiently large to suggest that rate constant uncertainty should be considered alongside other processes when model results disagree with measurement. Calculations for the pre-industrial simulation allow a tropospheric ozone radiative forcing to be calculated of 0.412 ± 0.062 W m-2. This uncertainty (13 %) is comparable to the inter-model spread in ozone radiative forcing found in previous model-model intercomparison studies where the rate constants used in the models are all identical or very similar. Thus, the uncertainty of tropospheric ozone radiative forcing should expanded to include this additional source of uncertainty. These rate constant uncertainties are significant and suggest that refinement of supposedly well-known chemical rate constants should be considered alongside other improvements to enhance our understanding of atmospheric processes.

Salt effects on an ion-molecule reaction--hydroxide-catalyzed hydrolysis of benzocaine.

PubMed

Al-Maaieh, Ahmad; Flanagan, Douglas R

2006-03-01

This work investigates the effect of various salts on the rate of a reaction involving a neutral species (benzocaine alkaline hydrolysis). Benzocaine hydrolysis kinetics in NaOH solutions in the presence of different salts were studied at 25 degrees C. Benzocaine solubility in salt solutions was also determined. Solubility data were used to estimate salt effects on benzocaine activity coefficients, and pH was used to estimate salt effects on hydroxide activity coefficients. Salts either increased or decreased benzocaine solubility. For example, solubility increased with 1.0 M tetraethylammonium chloride (TEAC) approximately 3-fold, whereas solubility decreased approximately 35% with 0.33 M Na2SO4. Salt effects on hydrolysis rates were more complex and depended on the relative magnitudes of the salt effects on the activity coefficients of benzocaine, hydroxide ion, and the transition state. As a result, some salts increased the hydrolysis rate constant, whereas others decreased it. For example, the pseudo-first-order rate constant decreased approximately 45% (to 0.0584 h(-1)) with 1 M TEAC, whereas it increased approximately 8% (to 0.116 h(-1)) with 0.33 M Na2SO4. Different salt effects on degradation kinetics can be demonstrated for a neutral compound reacting with an ion. These salt effects depend on varying effects on activity coefficients of reacting and intermediate species.

The impact of desorption kinetics from albumin on hepatic extraction efficiency and hepatic clearance: a model study.

PubMed

Krause, Sophia; Goss, Kai-Uwe

2018-05-23

Until now, the question whether slow desorption of compounds from transport proteins like the plasma protein albumin can affect hepatic uptake and thereby hepatic metabolism of these compounds has not yet been answered conclusively. This work now combines recently published experimental desorption rate constants with a liver model to address this question. For doing so, the used liver model differentiates the bound compound in blood, the unbound compound in blood and the compound within the hepatocytes as three well-stirred compartments. Our calculations show that slow desorption kinetics from albumin can indeed limit hepatic metabolism of a compound by decreasing hepatic extraction efficiency and hepatic clearance. The extent of this decrease, however, depends not only on the value of the desorption rate constant but also on how much of the compound is bound to albumin in blood and how fast intrinsic metabolism of the compound in the hepatocytes is. For strongly sorbing and sufficiently fast metabolized compounds, our calculations revealed a twentyfold lower hepatic extraction efficiency and hepatic clearance for the slowest known desorption rate constant compared to the case when instantaneous equilibrium between bound and unbound compound is assumed. The same desorption rate constant, however, has nearly no effect on hepatic extraction efficiency and hepatic clearance of weakly sorbing and slowly metabolized compounds. This work examines the relevance of desorption kinetics in various example scenarios and provides the general approach needed to quantify the effect of flow limitation, membrane permeability and desorption kinetics on hepatic metabolism at the same time.

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)

Effect of emplaced nZVI mass and groundwater velocity on PCE dechlorination and hydrogen evolution in water-saturated sand.

PubMed

Kim, Hye-Jin; Leitch, Megan; Naknakorn, Bhanuphong; Tilton, Robert D; Lowry, Gregory V

2017-01-15

The effect of nZVI mass loading and groundwater velocity on the tetrachloroethylene (PCE) dechlorination rate and the hydrogen evolution rate for poly(maleic acid-co-olefin) (MW=12K) coated nZVI was examined. In batch reactors, the PCE reaction rate constant (3.7×10 -4 Lhr -1 m -2 ) and hydrogen evolution rate constant (1.4 nanomolLhr -1 m -2 ) were independent of nZVI concentration above 10g/L, but the PCE dechlorination rate decreased and the hydrogen evolution rate increased for nZVI concentration below 10g/L. The nonlinearity between nZVI mass loading and PCE dechlorination and H 2 evolution was explained by differences in pH and E h at each nZVI mass loading; PCE reactivity increased when solution E h decreased, and the H 2 evolution rate increased with decreasing pH. Thus, nZVI mass loading of <5g/L yields lower reactivity with PCE and lower efficiency of Fe° utilization than for higher nZVI mass loading. The PCE dechlorination rate increased with increasing pore-water velocity, suggesting that mass transfer limits the reaction at low porewater velocity. Overall, this work suggests that design of nZVI-based reactive barriers for groundwater treatment should consider the non-linear effects of both mass loading and flow velocity on performance and expected reactive lifetime. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of the Effects of Medium Composition on the Monochloramine Disinfection Kinetics of Nitrosomonas europaea by the Propidium Monoazide Quantitative PCR and Live/Dead BacLight Methods ▿

PubMed Central

Wahman, David G.; Schrantz, Karen A.; Pressman, Jonathan G.

2010-01-01

Various medium compositions (phosphate, 1 to 50 mM; ionic strength, 2.8 to 150 meq/liter) significantly affected Nitrosomonas europaea monochloramine disinfection kinetics, as determined by the Live/Dead BacLight (LD) and propidium monoazide quantitative PCR (PMA-qPCR) methods (lag coefficient, 37 to 490 [LD] and 91 to 490 [PMA-qPCR] mg·min/liter; Chick-Watson rate constant, 4.0 × 10−3 to 9.3 × 10−3 [LD] and 1.6 × 10−3 to 9.6 × 10−3 [PMA-qPCR] liter/mg·min). Two competing effects may account for the variation in disinfection kinetic parameters: (i) increasing kinetics (disinfection rate constant [k] increased, lag coefficient [b] decreased) with increasing phosphate concentration and (ii) decreasing kinetics (k decreased, b increased) with increasing ionic strength. The results support development of a standard medium for evaluating disinfection kinetics in drinking water. PMID:20952645

Luminescence of the (O{sub 2}(a{sup 1}Δ{sub g})){sub 2} collisional complex in the temperature range of 90-315 K: Experiment and theory

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

Zagidullin, M. V., E-mail: marsel@fian.smr.ru; Pershin, A. A., E-mail: anchizh93@gmail.com; Azyazov, V. N., E-mail: azyazov@ssau.ru

Experimental and theoretical studies of collision induced emission of singlet oxygen molecules O{sub 2}(a{sup 1}Δ{sub g}) in the visible range have been performed. The rate constants, half-widths, and position of peaks for the emission bands of the (O{sub 2}(a{sup 1}Δ{sub g})){sub 2} collisional complex centered around 634 nm (2) and 703 nm (3) have been measured in the temperature range of 90–315 K using a flow-tube apparatus that utilized a gas-liquid chemical singlet oxygen generator. The absolute values of the spontaneous emission rate constants k{sub 2} and k{sub 3} are found to be similar, with the k{sub 3}/k{sub 2} ratiomore » monotonically decreasing from 1.1 at 300 K to 0.96 at 90 K. k{sub 2} slowly decreases with decreasing temperature but a sharp increase in its values is measured below 100 K. The experimental results were rationalized in terms of ab initio calculations of the ground and excited potential energy and transition dipole moment surfaces of singlet electronic states of the (O{sub 2}){sub 2} dimole, which were utilized to compute rate constants k{sub 2} and k{sub 3} within a statistical model. The best theoretical results reproduced experimental rate constants with the accuracy of under 40% and correctly described the observed temperature dependence. The main contribution to emission process (2), which does not involve vibrational excitation of O{sub 2} molecules at the ground electronic level, comes from the spin- and symmetry-allowed 1{sup 1}A{sub g}←{sup 1}B{sub 3u} transition in the rectangular H configuration of the dimole. Alternatively, emission process (3), in which one of the monomers becomes vibrationally excited in the ground electronic state, is found to be predominantly due to the vibronically allowed 1{sup 1}A{sub g}←2{sup 1}A{sub g} transition induced by the asymmetric O–O stretch vibration in the collisional complex. The strong vibronic coupling between nearly degenerate excited singlet states of the dimole makes the intensities of vibronically and symmetry-allowed transitions comparable and hence the rate constants k{sub 2} and k{sub 3} close to one another.« less

Start current of dielectric-loaded grating in Smith-Purcell radiation

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

Liu, Wenxin, E-mail: lwenxin@mail.ie.ac.cn; Wang, Yong, E-mail: wangyong3845@sina.com; Cao, Miaomiao, E-mail: mona486@yeah.net

In this paper, a three-dimensional dielectric loaded grating (DLG) is proposed for the Smith-Purcell (SP) device. Taking into the considerations of thickness and width of electron beam, the dispersion equation is derived by using field matches method. The complex frequency is obtained by the numerical solution of dispersion equation, in which the imaginary part represents linear growth rate. The impacts of the electron beam filling factor (EBFF) on growth rate are discussed under the condition that the beam current and beam current density are kept as constants, respectively. In addition, the start current for SP oscillator is obtained by usingmore » the dispersion relation combined with boundary conditions. The relationship between the start current and other parameters is discussed and compared with the conventional metal grating. The results show that with the increasing of EBFF, the peak growth rate increases rapidly firstly and then decreases slowly, in which the current and current density are kept as constants, respectively. For the SP oscillator, the start current is increased with the shifting up beam voltage, but it is decreased with the improved EBFF, and only it has a slightly increasing trend when EBFF is close to 1. In addition, the start current is decreased with the increasing of relative dielectric constant, which indicates that by introducing DLG, the start current can be effectively reduced. Theoretical results are in good agreement with that of the simulations.« less

An experimental study of opposed flow diffusion flame extinction over a thin fuel in microgravity. M.S. Thesis. Final Report

NASA Technical Reports Server (NTRS)

Ferkul, Paul V.

1989-01-01

The flame spread and flame extinction characteristics of a thin fuel burning in a low-speed forced convective environment in microgravity were examined. The flame spread rate was observed to decrease both with decreasing ambient oxygen concentration as well as decreasing free stream velocity. A new mode of flame extinction was observed, caused by either of two means: keeping the free stream velocity constant and decreasing the oxygen concentration, or keeping the oxygen concentration constant and decreasing the free stream velocity. This extinction is called quenching extinction. By combining this data together with a previous microgravity quiescent flame study and normal-gravity blowoff extinction data, a flammability map was constructed with molar percentage oxygen and characteristic relative velocity as coordinates. The Damkohler number is not sufficient to predict flame spread and extinction in the near quench limit region.

How the growth and freeboard of continents may relate to geometric and kinematic parameters of mid-ocean spreading ridges

USGS Publications Warehouse

Howell, D.G.

1989-01-01

If the volume of continents has been growing since 4 Ga then the area of the ocean basins must have been shrinking. Therefore, by inferring a constant continental freeboard, in addition to constant continental crustal thicknesses and seawater volume, it is possible to calculate the necessary combinations of increased ridge lengths and spreading rates required to displace the seawater in the larger oceans of the past in order to maintain the constant freeboard. A reasonable choice from the various possibilities is that at 4 Ga ago, the ridge length and spreading rates were ca. 2.5 times greater than the averages of these parameters during the past 200 Ma. By 2.5 Ga ago the ridge length and spreading rate decreased to about 1.8 times the recent average and by 1 Ga ago these features became reduced to approximately 1.4 times recent averages. ?? 1989.

Effects of particle composition and environmental parameters on catalytic hydrodechlorination of trichloroethylene by nanoscale bimetallic Ni-Fe.

PubMed

Wei, Jianjun; Qian, Yajing; Liu, Wenjuan; Wang, Lutao; Ge, Yijie; Zhang, Jianghao; Yu, Jiang; Ma, Xingmao

2014-05-01

Catalytic nickel was successfully incorporated into nanoscale iron to enhance its dechlorination efficiency for trichloroethylene (TCE), one of the most commonly detected chlorinated organic compounds in groundwater. Ethane was the predominant product. The greatest dechlorination efficiency was achieved at 22 molar percent of nickel. This nanoscale Ni-Fe is poorly ordered and inhomogeneous; iron dissolution occurred whereas nickel was relatively stable during the 24-hr reaction. The morphological characterization provided significant new insights on the mechanism of catalytic hydrodechlorination by bimetallic nanoparticles. TCE degradation and ethane production rates were greatly affected by environmental parameters such as solution pH, temperature and common groundwater ions. Both rate constants decreased and then increased over the pH range of 6.5 to 8.0, with the minimum value occurring at pH 7.5. TCE degradation rate constant showed an increasing trend over the temperature range of 10 to 25°C. However, ethane production rate constant increased and then decreased over the range, with the maximum value occurring at 20°C. Most salts in the solution appeared to enhance the reaction in the first half hour but overall they displayed an inhibitory effect. Combined ions showed a similar effect as individual salts. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Exact analytical thermodynamic expressions for a Brownian heat engine

NASA Astrophysics Data System (ADS)

Taye, Mesfin Asfaw

2015-09-01

The nonequilibrium thermodynamics feature of a Brownian motor operating between two different heat baths is explored as a function of time t . Using the Gibbs entropy and Schnakenberg microscopic stochastic approach, we find exact closed form expressions for the free energy, the rate of entropy production, and the rate of entropy flow from the system to the outside. We show that when the system is out of equilibrium, it constantly produces entropy and at the same time extracts entropy out of the system. Its entropy production and extraction rates decrease in time and saturate to a constant value. In the long time limit, the rate of entropy production balances the rate of entropy extraction, and at equilibrium both entropy production and extraction rates become zero. Furthermore, via the present model, many thermodynamic theories can be checked.

Exact analytical thermodynamic expressions for a Brownian heat engine.

PubMed

Taye, Mesfin Asfaw

2015-09-01

The nonequilibrium thermodynamics feature of a Brownian motor operating between two different heat baths is explored as a function of time t. Using the Gibbs entropy and Schnakenberg microscopic stochastic approach, we find exact closed form expressions for the free energy, the rate of entropy production, and the rate of entropy flow from the system to the outside. We show that when the system is out of equilibrium, it constantly produces entropy and at the same time extracts entropy out of the system. Its entropy production and extraction rates decrease in time and saturate to a constant value. In the long time limit, the rate of entropy production balances the rate of entropy extraction, and at equilibrium both entropy production and extraction rates become zero. Furthermore, via the present model, many thermodynamic theories can be checked.

High-rate operant behavior in two mouse strains: a response-bout analysis.

PubMed

Johnson, Joshua E; Pesek, Erin F; Newland, M Christopher

2009-06-01

Operant behavior sometimes occurs in bouts characterized by an initiation rate, within-bout response rate, and bout length. The generality of this structure was tested using high-rate nose-poking in mice. Reinforcement of short interresponse times produced high response rates while a random-interval schedule held reinforcement rates constant. BALB/c mice produced bouts that were more frequent, longer, and contained a higher within-bout rate of responding (nine nose-pokes/s) than did the C57BL/6 mice (five nose-pokes/s). Adding a running wheel decreased total nose-pokes and bout length, and increased bout-initiation rate. Free-feeding reduced nose-poking by decreasing bout-initiation rate. Photoperiod reversal decreased bout-initiation rate but not total nose-poke rate. Despite strain differences in bout structure, both strains responded similarly to the interventions. The three bout measures were correlated with overall rate but not with each other. Log-survival analyses provided independent descriptors of the structure of high-rate responding in these two strains.

Stabilizing effect of citrate buffer on the photolysis of riboflavin in aqueous solution

PubMed Central

Ahmad, Iqbal; Sheraz, Muhammad Ali; Ahmed, Sofia; Kazi, Sadia Hafeez; Mirza, Tania; Aminuddin, Mohammad

2011-01-01

In the present investigation the photolysis of riboflavin (RF) in the presence of citrate species at pH 4.0–7.0 has been studied. A specific multicomponent spectrophotometric method has been used to assay RF in the presence of photoproducts during the reactions. The overall first-order rate constants (kobs) for the photolysis of RF range from 0.42 to 1.08×10–2 min−1 in the region. The values of kobs have been found to decrease with an increase in citrate concentration indicating an inhibitory effect of these species on the rate of reaction. The second-order rate constants for the interaction of RF with total citrate species causing inhibition range from 1.79 to 5.65×10–3 M−1 min−1 at pH 4.0–7.0. The log k–pH profiles for the reactions at 0.2–1.0 M citrate concentration show a gradual decrease in kobs and the value at 1.0 M is more than half compared to that of k0, i.e., in the absence of buffer, at pH 5.0. Divalent citrate ions cause a decrease in RF fluorescence due to the quenching of the excited singlet state resulting in a decrease in the rate of reaction and consequently leading to the stabilization of RF solutions. The greater quenching of fluorescence at pH 4.0 compared to that of 7.0 is in accordance with the greater concentration of divalent citrate ions (99.6%) at that pH. The trivalent citrate ions exert a greater inhibitory effect on the rate of RF photolysis compared to that of the divalent citrate ions probably as a result of excited triplet state quenching. The values of second-order rate constants for the interaction of divalent and trivalent citrate ions are 0.44×10–2 and 1.06×10–3 M–1 min–1, respectively, indicating that the trivalent ions exert a greater stabilizing effect, compared to the divalent ions, on RF solutions. PMID:25755977

Dynamics of Soil Water Evaporation during Soil Drying: Laboratory Experiment and Numerical Analysis

PubMed Central

Han, Jiangbo; Zhou, Zhifang

2013-01-01

Laboratory and numerical experiments were conducted to investigate the evolution of soil water evaporation during a continuous drying event. Simulated soil water contents and temperatures by the calibrated model well reproduced measured values at different depths. Results show that the evaporative drying process could be divided into three stages, beginning with a relatively high evaporation rate during stage 1, followed by a lower rate during transient stage and stage 2, and finally maintaining a very low and constant rate during stage 3. The condensation zone was located immediately below the evaporation zone in the profile. Both peaks of evaporation and condensation rate increased rapidly during stage 1 and transition stage, decreased during stage 2, and maintained constant during stage 3. The width of evaporation zone kept a continuous increase during stages 1 and 2 and maintained a nearly constant value of 0.68 cm during stage 3. When the evaporation zone totally moved into the subsurface, a dry surface layer (DSL) formed above the evaporation zone at the end of stage 2. The width of DSL also presented a continuous increase during stage 2 and kept a constant value of 0.71 cm during stage 3. PMID:24489492

Dynamics of soil water evaporation during soil drying: laboratory experiment and numerical analysis.

PubMed

Han, Jiangbo; Zhou, Zhifang

2013-01-01

Laboratory and numerical experiments were conducted to investigate the evolution of soil water evaporation during a continuous drying event. Simulated soil water contents and temperatures by the calibrated model well reproduced measured values at different depths. Results show that the evaporative drying process could be divided into three stages, beginning with a relatively high evaporation rate during stage 1, followed by a lower rate during transient stage and stage 2, and finally maintaining a very low and constant rate during stage 3. The condensation zone was located immediately below the evaporation zone in the profile. Both peaks of evaporation and condensation rate increased rapidly during stage 1 and transition stage, decreased during stage 2, and maintained constant during stage 3. The width of evaporation zone kept a continuous increase during stages 1 and 2 and maintained a nearly constant value of 0.68 cm during stage 3. When the evaporation zone totally moved into the subsurface, a dry surface layer (DSL) formed above the evaporation zone at the end of stage 2. The width of DSL also presented a continuous increase during stage 2 and kept a constant value of 0.71 cm during stage 3.

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.

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

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

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

1988-12-01

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

Characterization of Active Site Residues of Nitroalkane Oxidase†

PubMed Central

Valley, Michael P.; Fenny, Nana S.; Ali, Shah R.; Fitzpatrick, Paul F.

2010-01-01

The flavoenzyme nitroalkane oxidase catalyzes the oxidation of primary and secondary nitrolkanes to the corresponding aldehydes and ketones plus nitrite. The structure of the enzyme shows that Serl71 forms a hydrogen bond to the flavin N5, suggesting that it plays a role in catalysis. Cys397 and Tyr398 were previously identified by chemical modification as potential active site residues. To more directly probe the roles of these residues, the S171A, S171V, S171T, C397S, and Y398F enzymes have been characterized with nitroethane as substrate. The C397S and Y398 enzymes were less stable than the wild-type enzyme, and the C397S enzyme routinely contained a substoichiometric amount of FAD. Analysis of the steady-state kinetic parameters for the mutant enzymes, including deuterium isotope effects, establishes that all of the mutations result in decreases in the rate constants for removal of the substrate proton by ~5-fold and decreases in the rate constant for product release of ~2-fold. Only the S171V and S171T mutations alter the rate constant for flavin oxidation. These results establish that these residues are not involved in catalysis, but rather are required for maintaining the protein structure. PMID:20056514

Characterization of active site residues of nitroalkane oxidase.

PubMed

Valley, Michael P; Fenny, Nana S; Ali, Shah R; Fitzpatrick, Paul F

2010-06-01

The flavoenzyme nitroalkane oxidase catalyzes the oxidation of primary and secondary nitroalkanes to the corresponding aldehydes and ketones plus nitrite. The structure of the enzyme shows that Ser171 forms a hydrogen bond to the flavin N5, suggesting that it plays a role in catalysis. Cys397 and Tyr398 were previously identified by chemical modification as potential active site residues. To more directly probe the roles of these residues, the S171A, S171V, S171T, C397S, and Y398F enzymes have been characterized with nitroethane as substrate. The C397S and Y398 enzymes were less stable than the wild-type enzyme, and the C397S enzyme routinely contained a substoichiometric amount of FAD. Analysis of the steady-state kinetic parameters for the mutant enzymes, including deuterium isotope effects, establishes that all of the mutations result in decreases in the rate constants for removal of the substrate proton by approximately 5-fold and decreases in the rate constant for product release of approximately 2-fold. Only the S171V and S171T mutations alter the rate constant for flavin oxidation. These results establish that these residues are not involved in catalysis, but rather are required for maintaining the protein structure. 2009 Elsevier Inc. All rights reserved.

Volcanic gas composition changes during the gradual decrease of the gigantic degassing activity of Miyakejima volcano, Japan, 2000-2015

NASA Astrophysics Data System (ADS)

Shinohara, Hiroshi; Geshi, Nobuo; Matsushima, Nobuo; Saito, Genji; Kazahaya, Ryunosuke

2017-02-01

The composition of volcanic gases discharged from Miyakejima volcano has been monitored during the intensive degassing activity that began after the eruption in 2000. During the 15 years from 2000 to 2015, Miyakejima volcano discharged 25.5 Mt of SO2, which required degassing of 3 km3 of basaltic magma. The SO2 emission rate peaked at 50 kt/day at the end of 2000 and quickly decreased to 5 kt/day by 2003. During the early degassing period, the volcanic gas composition was constant with the CO2/SO2 = 0.8 (mol ratio), H2O/SO2 = 35, HCl/SO2 = 0.08, and SO2/H2S = 15. The SO2 emission rate decreased gradually to 0.5 kt/day by 2012, and the gas composition also changed gradually to CO2/SO2 = 1.5, H2O/SO2 = 150, HCl/SO2 = 0.15, and SO2/H2S = 6. The compositional changes are not likely caused by changes in degassing pressure or volatile heterogeneity of a magma chamber but are likely attributed to an increase of hydrothermal scrubbing caused by large decrease of the volcanic gas emission rate, suggesting a supply of gases with constant composition during the 15 years. The intensive degassing was modeled based on degassing of a convecting magma conduit. The gradual SO2 emission rate that decrease without changes in volcanic gas composition is attributed to a reduction of diameter of the convecting magma conduit.

Amino acid residues in Anabaena ferredoxin crucial to interaction with ferredoxin-NADP+ reductase: site-directed mutagenesis and laser flash photolysis.

PubMed

Hurley, J K; Salamon, Z; Meyer, T E; Fitch, J C; Cusanovich, M A; Markley, J L; Cheng, H; Xia, B; Chae, Y K; Medina, M

1993-09-14

Ferredoxin (Fd) functions in photosynthesis to transfer electrons from photosystem I to ferredoxin-NADP+ reductase (FNR). We have made several site-directed mutants of Anabaena 7120 Fd and have used laser flash photolysis to investigate the effects of these mutations on the kinetics of reduction of oxidized Fd by deazariboflavin semiquinone (dRfH.) and the reduction of oxidized Anabaena FNR by reduced Fd. None of the mutations influenced the second-order rate constant for dRfH. reduction by more than a factor of 2, suggesting that the ability of the [2Fe-2S] cluster to participate in electron transfer was not seriously affected. In contrast, a surface charge reversal mutation, E94K, resulted in a 20,000-fold decrease in the second-order rate constant for electron transfer from Fd to FNR, whereas a similar mutation at an adjacent site, E95K, produced little or no change in reaction rate constant compared to wild-type Fd. Such a dramatic difference between contiguous surface mutations suggests a very precise surface complementarity at the protein-protein interface. Mutations introduced at F65 (F65I and F65A) also decreased the rate constant for the Fd/FNR electron transfer reaction by more than 3 orders of magnitude. Spectroscopic and thermodynamic measurements with both the E94 and F65 mutants indicated that the kinetic differences cannot be ascribed to changes in gross conformation, redox potential, or FNR binding constant but rather reflect the protein-protein interactions that control electron transfer. Several mutations at other sites in the vicinity of E94 and F65 (R42, T48, D68, and D69) resulted in little or no perturbation of the Fd/FNR interaction.(ABSTRACT TRUNCATED AT 250 WORDS)

Scale-Dependent Rates of Uranyl Surface Complexation Reaction in Sediments

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

Liu, Chongxuan; Shang, Jianying; Kerisit, Sebastien N.

Scale-dependency of uranyl[U(VI)] surface complexation rates was investigated in stirred flow-cell and column systems using a U(VI)-contaminated sediment from the US Department of Energy, Hanford site, WA. The experimental results were used to estimate the apparent rate of U(VI) surface complexation at the grain-scale and in porous media. Numerical simulations using molecular, pore-scale, and continuum models were performed to provide insights into and to estimate the rate constants of U(VI) surface complexation at the different scales. The results showed that the grain-scale rate constant of U(VI) surface complexation was over 3 to 10 orders of magnitude smaller, dependent on themore » temporal scale, than the rate constant calculated using the molecular simulations. The grain-scale rate was faster initially and slower with time, showing the temporal scale-dependency. The largest rate constant at the grain-scale decreased additional 2 orders of magnitude when the rate was scaled to the porous media in the column. The scaling effect from the grain-scale to the porous media became less important for the slower sorption sites. Pore-scale simulations revealed the importance of coupled mass transport and reactions in both intragranular and inter-granular domains, which caused both spatial and temporal dependence of U(VI) surface complexation rates in the sediment. Pore-scale simulations also revealed a new rate-limiting mechanism in the intragranular porous domains that the rate of coupled diffusion and surface complexation reaction was slower than either process alone. The results provided important implications for developing models to scale geochemical/biogeochemical reactions.« less

Removal of emerging pollutants by Ru/TiO2-catalyzed permanganate oxidation.

PubMed

Zhang, Jing; Sun, Bo; Xiong, Xinmei; Gao, Naiyun; Song, Weihua; Du, Erdeng; Guan, Xiaohong; Zhou, Gongming

2014-10-15

TiO2 supported ruthenium nanoparticles, Ru/TiO2 (0.94‰ as Ru), was synthesized to catalyze permanganate oxidation for degrading emerging pollutants (EPs) with diverse organic moieties. The presence of 1.0 g L(-1) Ru/TiO2 increased the second order reaction rate constants of bisphenol A, diclofenac, acetaminophen, sulfamethoxazole, benzotriazole, carbamazepine, butylparaben, diclofenac, ciprofloxacin and aniline at mg L(-1) level (5.0 μM) by permanganate oxidation at pH 7.0 by 0.3-119 times. The second order reaction rate constants of EPs with permanganate or Ru/TiO2-catalyzed permanganate oxidation obtained at EPs concentration of mg L(-1) level (5.0 μM) underestimated those obtained at EPs concentration of μg L(-1) level (0.050 μM). Ru/TiO2-catalyzed permanganate could decompose a mixture of nine EPs at μg L(-1) level efficiently and the second order rate constant for each EP was not decreased due to the competition of other EPs. The toxicity tests revealed that Ru/TiO2-catalyzed permanganate oxidation was effective not only for elimination of EPs but also for detoxification. The removal rates of sulfamethoxazole by Ru/TiO2-catalyzed permanganate oxidation in ten successive cycles remained almost constant in ultrapure water and slightly decreased in Songhua river water since the sixth run, indicating the satisfactory stability of Ru/TiO2. Ru/TiO2-catalyzed permanganate oxidation was selective and could remove selected EPs spiked in real waters more efficiently than chlorination. Therefore, Ru/TiO2-catalyzed permanganate oxidation is promising for removing EPs with electron-rich moieties. Copyright © 2014 Elsevier Ltd. All rights reserved.

Dissolution of nontronite in chloride brines and implications for the aqueous history of Mars

NASA Astrophysics Data System (ADS)

Steiner, M. H.; Hausrath, E. M.; Elwood Madden, M. E.; Tschauner, O.; Ehlmann, B. L.; Olsen, A. A.; Gainey, S. R.; Smith, J. S.

2016-12-01

Increasing evidence suggests the presence of recent liquid water, including brines, on Mars. Brines have therefore likely impacted clay minerals such as the Fe-rich mineral nontronite found in martian ancient terrains. To interpret these interactions, we conducted batch experiments to measure the apparent dissolution rate constant of nontronite at 25.0 °C at activities of water (aH2O) of 1.00 (0.01 M CaCl2 or NaCl), 0.75 (saturated NaCl or 3.00 mol kg-1 CaCl2), and 0.50 (5.00 mol kg-1 CaCl2). Experiments at aH2O = 1.00 (0.01 M CaCl2) were also conducted at 4.0 °C, 25.0 °C, and 45.0 °C to measure an apparent activation energy for the dissolution of nontronite. Apparent dissolution rate constants at 25.0 °C in CaCl2-containing solutions decrease with decreasing activity of water as follows: 1.18 × 10-12 ± 9 × 10-14 mol mineral m-2 s-1 (aH2O = 1.00) > 2.36 × 10-13 ± 3.1 × 10-14 mol mineral m-2 s-1 (aH2O = 0.75) > 2.05 × 10-14 ± 2.9 × 10-15 mol mineral m-2 s-1 (aH2O = 0.50). Similar results were observed at 25.0 °C in NaCl-containing solutions: 1.89 × 10-12 ± 1 × 10-13 mol mineral m-2 s-1 (aH2O = 1.00) > 1.98 × 10-13 ± 2.3 × 10-14 mol mineral m-2 s-1 (aH2O = 0.75). This decrease in apparent dissolution rate constants with decreasing activity of water follows a relationship of the form: log kdiss = 3.70 ± 0.20 × aH2O - 15.49, where kdiss is the apparent dissolution rate constant, and aH2O is the activity of water. The slope of this relationship (3.70 ± 0.20) is within uncertainty of that of other minerals where the relationship between dissolution rates and activity of water has been tested, including forsteritic olivine (log R = 3.27 ± 0.91 × aH2O - 11.00) (Olsen et al., 2015) and jarosite (log R = 3.85 ± 0.43 × aH2O - 12.84) (Dixon et al., 2015), where R is the mineral dissolution rate. This result allows prediction of mineral dissolution as a function of activity of water and suggests that with decreasing activity of water, mineral dissolution will decrease due to the role of water as a ligand in the reaction. Apparent dissolution rate constants in the dilute NaCl solution (1.89 × 10-12 ± 1 × 10-13 mol mineral m-2 s-1) are slightly greater than those in the dilute CaCl2 solutions (1.18 × 10-12 ± 9 × 10-14 mol mineral m-2 s-1). We attribute this effect to the exchange of Na with Ca in the nontronite interlayer. An apparent activation energy of 54.6 ± 1.0 kJ/mol was calculated from apparent dissolution rate constants in dilute CaCl2-containing solutions at temperatures of 4.0 °C, 25.0 °C, and 45.0 °C: 2.33 × 10-13 ± 1.3 × 10-14 mol mineral m-2 s-1 (4.0 °C), 1.18 × 10-12 ± 9 × 10-14 mol mineral m-2 s-1 (25.0 °C), and 4.98 × 10-12 ± 3.8 × 10-13 mol mineral m-2 s-1 (45.0 °C). The greatly decreased dissolution of nontronite in brines and at low temperatures suggests that any martian nontronite found to be perceptibly weathered may have experienced very long periods of water-rock interaction with brines at the low temperatures prevalent on Mars, with important implications for the paleoclimate and long-term potential habitability of Mars.

Effect of moisture on disintegration kinetics during anaerobic digestion of complex organic substrates.

PubMed

Liotta, Flavia; d'Antonio, Giuseppe; Esposito, Giovanni; Fabbricino, Massimiliano; Frunzo, Luigi; van Hullebusch, Eric D; Lens, Piet N L; Pirozzi, Francesco

2014-01-01

The role of the moisture content and particle size (PS) on the disintegration of complex organic matter during the wet anaerobic digestion (AD) process was investigated. A range of total solids (TS) from 5% to 11.3% and PS from 0.25 to 15 mm was evaluated using carrot waste as model complex organic matter. The experimental results showed that the methane production rate decreased with higher TS and PS. A modified version of the AD model no.1 for complex organic substrates was used to model the experimental data. The simulations showed a decrease of the disintegration rate constants with increasing TS and PS. The results of the biomethanation tests were used to calibrate and validate the applied model. In particular, the values of the disintegration constant for various TS and PS were determined. The simulations showed good agreement between the numerical and observed data.

Decarboxylation of 6-nitrobenzisoxazole-3-carboxylate in mixed micelles of zwitterionic and positively charged surfactants.

PubMed

Maximiano, Flavio A; Chaimovich, Hernan; Cuccovia, Iolanda M

2006-09-12

The rate of decarboxylation of 6-nitrobenzisoxazole-3-carboxylate, NBOC, was determined in micelles of N-hexadecyl-N,N,N-trimethylammonium bromide or chloride (CTAB or CTAC), N-hexadecyl-N,N-dimethyl-3-ammonium-1-propanesulfonate (HPS), N-dodecyl-N,N-dimethyl-3-ammonium-1-propanesulfonate (DPS), N-dodecyl-N,N,N-trimethylammonium bromide (DTAB), hexadecylphosphocholine (HPC), and their mixtures. Quantitative analysis of the effect on micelles on the velocity of NBOC decarboxylation allowed the estimation of the rate constants in the micellar pseudophase, k(m), for the pure surfactants and their mixtures. The extent of micellar catalysis for NBOC decarboxylation, expressed as the ratio k(m)/k(w), where k(w) is the rate constant in water, varied from 240 for HPS to 62 for HPC. With HPS or DPS, k(m) decreased linearly with CTAB(C) mole fraction, suggesting ideal mixing. With HPC, k(m) increased to a maximum at a CTAB(C) mole fraction of ca. 0.5 and then decreased at higher CTAB(C). Addition of CTAB(C) to HPC, where the negative charge of the surfactant is close to the hydrophobic core, produces tight ion pairs at the interface and, consequently, decreases interfacial water contents. Interfacial dehydration at the surface in equimolar HPC/CTAB(C) mixtures, and interfacial solubilization site of the substrate, can explain the observed catalytic synergy, since the rate of NBOC decarboxylation increases markedly with the decrease in hydrogen bonding to the carboxylate group.

Modelling Pre-eruptive Progressive Damage in Basaltic Volcanoes: Consequences for the Pre-eruptive Process

NASA Astrophysics Data System (ADS)

Got, J. L.; Amitrano, D.; Carrier, A.; Marsan, D.; Jouanne, F.; Vogfjord, K. S.

2017-12-01

At Grimsvötn volcano, high-quality earthquake and continuous GPS data were recorded by the Icelandic Meteorological Office during its 2004-2011 inter-eruptive period and exhibited remarkable patterns : acceleration of the cumulated earthquake number, and a 2-year exponential decrease in displacement rate followed by a 4-year constant inflation rate. We proposed a model with one magma reservoir in a non-linear elastic damaging edifice, with incompressible magma and a constant pressure at the base of the magma conduit. We first modelled seismicity rate and damage as a function of time, and show that Kachanov's elastic brittle damage law may be used to express the decrease of the effective shear modulus with time. We then derived simple analytical expressions for the magma reservoir overpressure and the surface displacement as a function of time. We got a very good fit of the seismicity and surface displacement data by adjusting only three phenomenological parameters and computed magma reservoir overpressure, magma flow and strain power as a function of time. Overpressure decrease is controlled by damage and shear modulus decrease. Displacement increases, although overpressure is decreasing, because shear modulus decreases more than overpressure. Normalized strain power reaches a maximum 0.25 value. This maximum is a physical limit, after which the elasticity laws are no longer valid, earthquakes cluster, cumulative number of earthquakes departs from the model. State variable extrema provide four reference times that may be used to assess the mechanical state and dynamics of the volcanic edifice. We also performed the spatial modelling of the progressive damage and strain localization around a pressurized magma reservoir. We used Kachanov's damage law and finite element modelling of an initially elastic volcanic edifice pressurized by a spherical magma reservoir, with a constant pressure in the reservoir and various external boundary conditions. At each node of the model, Young's modulus is decreased if deviatoric stress locally reaches the Mohr-Coulomb plastic threshold. For a compressive horizontal stress, the result shows a complex strain localization pattern, showing reverse and normal faulting very similar to what is obtained from analog modelling and observed at volcanic resurgent domes.

Quantification of biodegradation for o-xylene and naphthalene using first order decay models, Michaelis-Menten kinetics and stable carbon isotopes.

PubMed

Blum, Philipp; Hunkeler, Daniel; Weede, Matthias; Beyer, Christof; Grathwohl, Peter; Morasch, Barbara

2009-04-01

At a former wood preservation plant severely contaminated with coal tar oil, in situ bulk attenuation and biodegradation rate constants for several monoaromatic (BTEX) and polyaromatic hydrocarbons (PAH) were determined using (1) classical first order decay models, (2) Michaelis-Menten degradation kinetics (MM), and (3) stable carbon isotopes, for o-xylene and naphthalene. The first order bulk attenuation rate constant for o-xylene was calculated to be 0.0025 d(-1) and a novel stable isotope-based first order model, which also accounted for the respective redox conditions, resulted in a slightly smaller biodegradation rate constant of 0.0019 d(-1). Based on MM-kinetics, the o-xylene concentration decreased with a maximum rate of k(max)=0.1 microg/L/d. The bulk attenuation rate constant of naphthalene retrieved from the classical first order decay model was 0.0038 d(-1). The stable isotope-based biodegradation rate constant of 0.0027 d(-1) was smaller in the reduced zone, while residual naphthalene in the oxic part of the plume further downgradient was degraded at a higher rate of 0.0038 d(-1). With MM-kinetics a maximum degradation rate of k(max)=12 microg/L/d was determined. Although best fits were obtained by MM-kinetics, we consider the carbon stable isotope-based approach more appropriate as it is specific for biodegradation (not overall attenuation) and at the same time accounts for the dominant electron-accepting process. For o-xylene a field based isotope enrichment factor epsilon(field) of -1.4 could be determined using the Rayleigh model, which closely matched values from laboratory studies of o-xylene degradation under sulfate-reducing conditions.

Influencing factors and kinetic studies of imidacloprid degradation by ozonation.

PubMed

Chen, Shi; Deng, Jing; Deng, Yang; Gao, Naiyun

2018-03-02

Batch kinetic tests in ozonation of imidacloprid from water were performed in this study. The pseudo-first-order rate constant of imidacloprid degradation was increased from 0.079 to 0.326 min -1 with the increasing pH from 6.02 to 8.64 at an average ozone dose of 1.149 mg L -1 . When the alkalinity was increased from 0 to 250 mg L -1 NaHCO 3 , the pseudo-first-order rate constants decreased from 0.121 to 0.034 min -1 . These results suggested that the predominant oxidant gradually switched from ozone to hydroxyl radicals ([Formula: see text]) with the increase in solution pH. The secondary rate constant [Formula: see text] (10.92 ± 0.12 M -1 s -1 ) for the reaction of imidacloprid and molecular ozone was determined at pH 2.0 and in the presence of 50 mM ter-butyl alcohol (p-chlorobenzoic acid, pCBA), respectively. An indirect competition method was used to determine the secondary rate constant for [Formula: see text] oxidation of imidacloprid in the presence of pCBA as the reference compound. The rate constants [Formula: see text] were estimated to range 2.65-3.79 M -1 s -1 at pH 6.02-8.64. Results obtained from this study demonstrate that ozonation appears to be an effective method to remove imidacloprid from water.

Single genome retrieval of context-dependent variability in mutation rates for human germline.

PubMed

Sahakyan, Aleksandr B; Balasubramanian, Shankar

2017-01-13

Accurate knowledge of the core components of substitution rates is of vital importance to understand genome evolution and dynamics. By performing a single-genome and direct analysis of 39,894 retrotransposon remnants, we reveal sequence context-dependent germline nucleotide substitution rates for the human genome. The rates are characterised through rate constants in a time-domain, and are made available through a dedicated program (Trek) and a stand-alone database. Due to the nature of the method design and the imposed stringency criteria, we expect our rate constants to be good estimates for the rates of spontaneous mutations. Benefiting from such data, we study the short-range nucleotide (up to 7-mer) organisation and the germline basal substitution propensity (BSP) profile of the human genome; characterise novel, CpG-independent, substitution prone and resistant motifs; confirm a decreased tendency of moieties with low BSP to undergo somatic mutations in a number of cancer types; and, produce a Trek-based estimate of the overall mutation rate in human. The extended set of rate constants we report may enrich our resources and help advance our understanding of genome dynamics and evolution, with possible implications for the role of spontaneous mutations in the emergence of pathological genotypes and neutral evolution of proteomes.

THE EFFECT OF ADVANCE IN LACTATION AND GESTATION ON MAMMARY ACTIVITY.

PubMed

Gaines, W L; Davidson, F A

1926-01-20

The rate of milk secretion in farrow cows may be expressed as See PDF for Equation, in which y = yield and t = time from calving. Pregnancy causes a decrease in yield which may be expressed as See PDF for Equation, in which i = inhibition or decrease in yield and p = time from conception. The constant K appears to be the same for various groups but b is roughly proportional to a. The decrease in yield associated with pregnancy is interpreted as due to a hormone. The hormone hypothesis also affords an interpretation of the increasing rate of milk secretion which occurs for a short time following parturition.

The relative abundance of ethane to acetylene in the Jovian stratosphere

NASA Technical Reports Server (NTRS)

Allen, Mark; Yung, Yuk L.; Gladstone, G. R.

1992-01-01

The inclusion of the results of laboratory kinetics studies on the reaction of C2H3 and H2 to yield C2H4, which is suggestive of an efficient chemical mechanism for the hydrogenation of C2H2 to C2H6, can be included in a comprehensive model of the Jupiter atmosphere hydrocarbon photochemistry to explain the observed altitude variation of the C2H6/C2H2 ratio. The sensitivity of these results to uncertainties in key low-temperature rate constants is demonstrated. These key reaction-rate constants decrease with falling temperature.

Influence of Ar addition on ozone generation in a non-thermal plasma—a numerical investigation

NASA Astrophysics Data System (ADS)

Chen, Hsin Liang; Lee, How Ming; Chen, Shiaw Huei; Wei, Ta Chin; Been Chang, Moo

2010-10-01

A numerical model based on a dielectric barrier discharge is developed in this study to investigate the influence of Ar addition on ozone generation. The simulation results show good agreement with the experimental data, confirming the validity of the numerical model. The mechanisms regarding how the Ar addition affects ozone generation are investigated with the assistance of a numerical simulation by probing into the following two questions, (1) why the ozone concentration just slightly decreases in the low specific input energy (SIE, the ratio of discharge power to gas flow rate) region even if the inlet O2 concentration is substantially decreased and (2) why the variation of the increased rate of ozone concentration with SIE (i.e. the variation in the slope of ozone concentration versus SIE) is more significant for an O2/Ar mixture plasma. As SIE is relatively low, ozone decomposition through electron-impact and radical attack reactions is less significant because of low ozone concentration and gas temperature. Therefore, the ozone concentration depends mainly on the amount of oxygen atoms generated. The simulation results indicate that the amount of oxygen atoms generated per electronvolt for Ar concentrations of 0%, 10%, 30%, 50% and 80% are 0.178, 0.174, 0.169, 0.165 and 0.166, respectively, explaining why the ozone concentration does not decrease linearly with the inlet O2 concentration in the low SIE region. On the other hand, the simulation results show that increasing Ar concentration would lead to a lower reduced field and a higher gas temperature. The former would lead to an increase in the rate constant of e + O3 → e + O + O2 while the latter would result in a decrease in the rate constant of O + O2 + M → O3 + M and an increase in that of O3 + O → 2O2. The changes in the rate constants of these reactions would have a negative effect on ozone generation, which is the rationale for the second question.

Evolution of permeability and Biot coefficient at high mean stresses in high porosity sandstone

DOE PAGES

Ingraham, Mathew D.; Bauer, Stephen J.; Issen, Kathleen A.; ...

2017-05-01

A series of constant mean stress (CMS) and constant shear stress (CSS) tests were performed to investigate the evolution of permeability and Biot coefficient at high mean stresses in a high porosity reservoir analog (Castlegate sandstone). Permeability decreases as expected with increasing mean stress, from about 20 Darcy at the beginning of the tests to between 1.5 and 0.3 Darcy at the end of the tests (mean stresses up to 275 MPa). The application of shear stress causes permeability to drop below that of a hydrostatic test at the same mean stress. Results show a nearly constant rate decrease inmore » the Biot coefficient as the mean stress increases during hydrostatic loading, and as the shear stress increases during CMS loading. In conclusion, CSS tests show a stabilization of the Biot coefficient after the application of shear stress.« less

Evolution of permeability and Biot coefficient at high mean stresses in high porosity sandstone

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

Ingraham, Mathew D.; Bauer, Stephen J.; Issen, Kathleen A.

A series of constant mean stress (CMS) and constant shear stress (CSS) tests were performed to investigate the evolution of permeability and Biot coefficient at high mean stresses in a high porosity reservoir analog (Castlegate sandstone). Permeability decreases as expected with increasing mean stress, from about 20 Darcy at the beginning of the tests to between 1.5 and 0.3 Darcy at the end of the tests (mean stresses up to 275 MPa). The application of shear stress causes permeability to drop below that of a hydrostatic test at the same mean stress. Results show a nearly constant rate decrease inmore » the Biot coefficient as the mean stress increases during hydrostatic loading, and as the shear stress increases during CMS loading. In conclusion, CSS tests show a stabilization of the Biot coefficient after the application of shear stress.« less

Gating kinetics of batrachotoxin-modified Na+ channels in the squid giant axon. Voltage and temperature effects.

PubMed Central

Correa, A M; Bezanilla, F; Latorre, R

1992-01-01

The gating kinetics of batrachotoxin-modified Na+ channels were studied in outside-out patches of axolemma from the squid giant axon by means of the cut-open axon technique. Single channel kinetics were characterized at different membrane voltages and temperatures. The probability of channel opening (Po) as a function of voltage was well described by a Boltzmann distribution with an equivalent number of gating particles of 3.58. The voltage at which the channel was open 50% of the time was a function of [Na+] and temperature. A decrease in the internal [Na+] induced a shift to the right of the Po vs. V curve, suggesting the presence of an integral negative fixed charge near the activation gate. An increase in temperature decreased Po, indicating a stabilization of the closed configuration of the channel and also a decrease in entropy upon channel opening. Probability density analysis of dwell times in the closed and open states of the channel at 0 degrees C revealed the presence of three closed and three open states. The slowest open kinetic component constituted only a small fraction of the total number of transitions and became negligible at voltages greater than -65 mV. Adjacent interval analysis showed that there is no correlation in the duration of successive open and closed events. Consistent with this analysis, maximum likelihood estimation of the rate constants for nine different single-channel models produced a preferred model (model 1) having a linear sequence of closed states and two open states emerging from the last closed state. The effect of temperature on the rate constants of model 1 was studied. An increase in temperature increased all rate constants; the shift in Po would be the result of an increase in the closing rates predominant over the change in the opening rates. The temperature study also provided the basis for building an energy diagram for the transitions between channel states. PMID:1318096

Effect of inlet-air humidity on the formation of oxides of nitrogen in a gas-turbine combustor

NASA Technical Reports Server (NTRS)

Marchionna, N. R.

1973-01-01

Tests were conducted to determine the effect of inlet-air humidity on the formation of oxides of nitrogen from a gas-turbine combustor. Combustor inlet-air temperature ranged from 450 F to 1050 F. The tests were run at a constant pressure of 6 atmospheres and reference Mach number of 0.065. The NO sub x emission index was found to decrease with increasing inlet-air humidity at a constant exponential rate of 19 percent per mass percent water vapor in the air. This decrease of NO sub x emission index with increasing humidity was found to be independent of inlet-air temperature.

Continuous quantum error correction for non-Markovian decoherence

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

Oreshkov, Ognyan; Brun, Todd A.; Communication Sciences Institute, University of Southern California, Los Angeles, California 90089

2007-08-15

We study the effect of continuous quantum error correction in the case where each qubit in a codeword is subject to a general Hamiltonian interaction with an independent bath. We first consider the scheme in the case of a trivial single-qubit code, which provides useful insights into the workings of continuous error correction and the difference between Markovian and non-Markovian decoherence. We then study the model of a bit-flip code with each qubit coupled to an independent bath qubit and subject to continuous correction, and find its solution. We show that for sufficiently large error-correction rates, the encoded state approximatelymore » follows an evolution of the type of a single decohering qubit, but with an effectively decreased coupling constant. The factor by which the coupling constant is decreased scales quadratically with the error-correction rate. This is compared to the case of Markovian noise, where the decoherence rate is effectively decreased by a factor which scales only linearly with the rate of error correction. The quadratic enhancement depends on the existence of a Zeno regime in the Hamiltonian evolution which is absent in purely Markovian dynamics. We analyze the range of validity of this result and identify two relevant time scales. Finally, we extend the result to more general codes and argue that the performance of continuous error correction will exhibit the same qualitative characteristics.« less

An Unusual Salt Effect in an Interfacial Nucleophilic Substitution Reaction.

PubMed

Li, Shuheng; Mrksich, Milan

2018-06-12

This paper reports a kinetic characterization of the interfacial reaction of N-methylpyrrolidine with a self-assembled monolayer presenting an iodoalkyl group. SAMDI (self-assembled monolayers for matrix-assisted laser desorption/ionization) mass spectrometry was used to determine the extent of reaction for monolayers that were treated with a range of concentrations of the nucleophile for a range of times. These data revealed a second-order rate constant for the reaction that was approximately 100-fold greater than that for the analogous solution-phase reaction. However, addition of sodium iodide to the reaction mixture resulted in a 7-fold decrease in the reaction rate. Addition of bromide and chloride salts also gave slower rate constants for the reaction, but only at 100- and 1000-fold higher concentrations than was observed with iodide, respectively. The corresponding solution-phase reactions, by contrast, had rate constants that were unaffected by the concentration of halide salts. This work provides a well-characterized example illustrating the extent to which the kinetics and properties of an interfacial reaction can depart substantially from their better-understood solution-phase counterparts.

[Influence of pH on Kinetics of Anilines Oxidation by Permanganate].

PubMed

Wang, Hui; Sun, Bo; Guan, Xiao-hong

2016-02-15

To investigate the effect of pH on the oxidation of anilines by potassium permanganate, aniline and p-Chloroaniline were taken as the target contaminants, and the experiments were conducted under the condition with potassium permanganate in excess over a wide pH range. The reaction displayed remarkable autocatalysis, which was presumably ascribed to the formation of complexes by the in situ generated MnOx and the target contaminants on its surface, and thereby improved the oxidation rate of the target contaminants by permanganate. The reaction kinetics was fitted with the pseudo-first-order kinetics at different pH to obtain the pseudo-first-order reaction constants (k(obs)). The second-order rate constants calculated from permanganate concentration and k,b, increased with the increase of pH and reached the maximum near their respective pKa, after which they decreased gradually. This tendency is called parabola-like shaped pH-rate profile. The second-order rate constants between permanganate and anilines were well fitted by the proton transfer model proposed by us in previous work.

History dependent crystallization of Zr41Ti14Cu12Ni10Be23 melts

NASA Astrophysics Data System (ADS)

Schroers, Jan; Johnson, William L.

2000-07-01

The crystallization of Zr41Ti14Cu12Ni10Be23 (Vit 1) melts during constant heating is investigated. (Vit 1) melts are cooled with different rates into the amorphous state and the crystallization temperature upon subsequent heating is studied. In addition, Vit 1 melts are cooled using a constant rate to different temperatures and subsequently heated from this temperature with a constant rate. We investigate the influence of the temperature to which the melt was cooled on the crystallization temperature measured upon heating. In both cases the onset temperature of crystallization shows strong history dependence. This can be explained by an accumulating process during cooling and heating. An attempt is made to consider this process in a simple model by steady state nucleation and subsequent growth of the nuclei which results in different crystallization kinetics during cooling or heating. Calculations show qualitative agreement with the experimental results. However, calculated and experimental results differ quantitatively. This difference can be explained by a decomposition process leading to a nonsteady nucleation rate which continuously increases with decreasing temperature.

Evaluation of the rate constants of sugar transport through maltoporin (LamB) of Escherichia coli from the sugar-induced current noise

PubMed Central

1995-01-01

LamB (maltoporin) of Escherichia coli outer membrane was reconstituted into artificial lipid bilayer membranes. The channel contains a binding site for sugars and is blocked for ions when the site is occupied by a sugar. The on and off reactions of sugar binding cause an increase of the noise of the current through the channel. The sugar-induced current noise of maltoporin was used for the evaluation of the sugar-binding kinetics for different sugars of the maltooligosaccharide series and for sucrose. The on rate constant for sugar binding was between 10(6) and 10(7) M-1.s-1 for the maltooligosaccharides and corresponds to the movement of the sugars from the aqueous phase to the central binding site. The off rate (corresponding to the release of the sugars from the channel) decreased with increasing number of glucose residues in the maltooligosaccharides from approximately 2,000 s-1 for maltotriose to 180 s-1 for maltoheptaose. The kinetics for sucrose movement was considerably slower. The activation energies of the stability constant and of the rate constants for sugar binding were evaluated from noise experiments at different temperatures. The role of LamB in the transport of maltooligosaccharides across the outer membrane is discussed. PMID:7539481

Changing Epidemiology of Upper Gastrointestinal Hemorrhage in the Last Decade: A Nationwide Analysis.

PubMed

Wuerth, Brandon A; Rockey, Don C

2018-05-01

Upper gastrointestinal hemorrhage (UGIH) is common and carries substantial mortality requiring frequent hospitalizations. To investigate trends in etiology and outcome of UGIH in hospitalized patients in the USA. Retrospective, observational cohort study of the Nationwide Inpatient Sample from 2002 to 2012 was carried out. UGIH was identified in hospitalizations with a principle ICD-9-CM diagnosis of UGIH or secondary diagnosis of UGIH with a principal diagnosis of hematemesis, blood in stool, or gastrointestinal bleeding. Age 18 years or older was required for inclusion, and elective admissions and transferred patients were excluded. The hospitalization rate of UGIH in the USA decreased by 21% from 2002 to 2012, from 81 to 67 cases per 100,000 population (p < 0.01). The greatest declines occurred for gastritis and PUD, which decreased by 55 and 30%, respectively (p < 0.01). There were increases in neoplasm, Dieulafoy lesions, angiodysplasia, and esophagitis, which increased by 50, 33, 32 and 20%, respectively (p < 0.01). The all-cause inpatient mortality rate of UGIH decreased 28% from 2.6 per 100 cases in 2002 to 1.9 in 2012 (p < 0.01). The greatest decline occurred for esophagitis, Mallory-Weiss tear, and neoplasm, which decreased by 39% (p < 0.01), 36% (p = 0.02), and 36% (p < 0.01), respectively. The rate of hospitalization for bleeding caused by esophageal varices remained constant and low (approximately 2%) throughout the study period; the mortality for esophageal varices also remained constant at 6-7%. The epidemiology of UGIH hemorrhage appears to be shifting, with a decline in PUD and gastritis; an increase in hospitalization rate for neoplasm, Dieulafoy lesions, angiodysplasia, and esophagitis; and a reduction in overall mortality. The decreasing hospitalization rate and mortality rate of UGIH suggest population trends in use of treatments for PUD, improved hemostatic techniques, and overall care.

Underage College Students' Drinking Behavior, Access to Alcohol, and the Influence of Deterrence Policies: Findings from the Harvard School of Public Health College Alcohol Study.

ERIC Educational Resources Information Center

Wechsler, Henry; Lee, Jae Eun; Nelson, Toben F.; Kuo, Meichun

2002-01-01

Used data from college alcohol surveys conducted between 1993-01 to compare underage students' and older students' drinking behaviors, access to alcohol, and exposure to prevention. While underage drinking rates decreased, binge drinking rates remained constant. Underage students' frequent binge drinking and related problems increased. College…

Gamma-radiolytic stability of new methylated TODGA derivatives for minor actinide recycling

DOE PAGES

Galan, Hitos; Zarzana, Christopher A.; Wilden, Andreas; ...

2015-09-15

The stability against gamma radiation of MeTODGA (methyl tetraoctyldiglycolamide) and Me2TODGA (dimethyl tetraoctyldiglycolamide), derivatives from the well-known extractant TODGA (N,N,N',N';-tetraoctyldiglycolamide), were studied and compared. Solutions of MeTODGA and Me2TODGA in alkane diluents were subjected to 60Co γ-irradiation in the presence and absence of nitric acid and analyzed using LC-MS to determine their rates of radiolytic concentration decrease, as well as to identify radiolysis products. The results of product identification from three different laboratories are compared and found to be in good agreement. The diglycolamide (DGA) concentrations decreased exponentially with increasing absorbed dose. The MeTODGA degradation rate constants (dose constants) weremore » uninfluenced by the presence of nitric acid, but the acid increased the rate of degradation for Me2TODGA. The degradation products formed by irradiation are also initially produced in greater amounts in acid-contacted solution, but products may also be degraded by continued radiolysis. As a result, the identified radiolysis products suggest that the weakest bonds are those in the diglycolamide center of these molecules.« less

Effects of constant pH and unsteady pH at different free ammonia concentrations on shortcut nitrification for landfill leachate treatment.

PubMed

Zhang, Chaosheng; Zhang, Shaoqing; Zhang, Liqiu; Rong, Hongwei; Zhang, Kefang

2015-04-01

On the basis of achieving shortcut nitrification in a lab-scale SBR, the effects of constant pH and unsteady pH at different free ammonia concentrations on shortcut nitrification for landfill leachate treatment was investigated. The results indicate that under the condition of DO of 0.5 ± 0.2 mg/L and temperature of 30 ± 2 °C, the absolute value of nitrite accumulation increased significantly with the increase in free ammonia (FA) concentration from 5.30 to 48.67 mg/L; however, the nitrite accumulation rate remained almost constant at a constant pH of 8.0 ± 0.1. Ammonia oxidation and the nitrite accumulation become slow with the pH decreased from 8.0 ± 0.1 to 7.5 ± 0.2, and the activities of ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB) were severely inhibited when the pH further decreased to 6.5. More importantly, this study confirmed that the pH decrease from 8.0 to 6.5 within a short time exhibited significant negative effect on the ammonia oxidation rather than the FA concentration.

Rate and Equilibrium Constants for an Enzyme Conformational Change during Catalysis by Orotidine 5'-Monophosphate Decarboxylase.

PubMed

Goryanova, Bogdana; Goldman, Lawrence M; Ming, Shonoi; Amyes, Tina L; Gerlt, John A; Richard, John P

2015-07-28

The caged complex between orotidine 5'-monophosphate decarboxylase (ScOMPDC) and 5-fluoroorotidine 5'-monophosphate (FOMP) undergoes decarboxylation ∼300 times faster than the caged complex between ScOMPDC and the physiological substrate, orotidine 5'-monophosphate (OMP). Consequently, the enzyme conformational changes required to lock FOMP at a protein cage and release product 5-fluorouridine 5'-monophosphate (FUMP) are kinetically significant steps. The caged form of ScOMPDC is stabilized by interactions between the side chains from Gln215, Tyr217, and Arg235 and the substrate phosphodianion. The control of these interactions over the barrier to the binding of FOMP and the release of FUMP was probed by determining the effect of all combinations of single, double, and triple Q215A, Y217F, and R235A mutations on kcat/Km and kcat for turnover of FOMP by wild-type ScOMPDC; its values are limited by the rates of substrate binding and product release, respectively. The Q215A and Y217F mutations each result in an increase in kcat and a decrease in kcat/Km, due to a weakening of the protein-phosphodianion interactions that favor fast product release and slow substrate binding. The Q215A/R235A mutation causes a large decrease in the kinetic parameters for ScOMPDC-catalyzed decarboxylation of OMP, which are limited by the rate of the decarboxylation step, but much smaller decreases in the kinetic parameters for ScOMPDC-catalyzed decarboxylation of FOMP, which are limited by the rate of enzyme conformational changes. By contrast, the Y217A mutation results in large decreases in kcat/Km for ScOMPDC-catalyzed decarboxylation of both OMP and FOMP, because of the comparable effects of this mutation on rate-determining decarboxylation of enzyme-bound OMP and on the rate-determining enzyme conformational change for decarboxylation of FOMP. We propose that kcat = 8.2 s(-1) for decarboxylation of FOMP by the Y217A mutant is equal to the rate constant for cage formation from the complex between FOMP and the open enzyme, that the tyrosyl phenol group stabilizes the closed form of ScOMPDC by hydrogen bonding to the substrate phosphodianion, and that the phenyl group of Y217 and F217 facilitates formation of the transition state for the rate-limiting conformational change. An analysis of kinetic data for mutant enzyme-catalyzed decarboxylation of OMP and FOMP provides estimates for the rate and equilibrium constants for the conformational change that traps FOMP at the enzyme active site.

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

Olsen, Todd Andrew; Brandt, Craig C.; Brooks, Scott C.

Mercury (Hg) methylation and methylmercury (MMHg) demethylation activity of periphyton biofilms from East Fork Poplar Creek, Tennessee, USA (EFPC) were measured during 2014-2015 using stable Hg isotopic rate assays. 201Hg II and MM 202Hg were added to intact periphyton samples and the formation of MM 201Hg and loss of MM 202Hg were monitored over time and used to calculate first-order rate constants for methylation and demethylation, respectively. The influence of location, temperature/season, light exposure and biofilm structure on methylation and demethylation were examined. Between-site differences in net methylation for samples collected from an upstream versus downstream location were driven bymore » differences in the demethylation rate constant (k d). In contrast, the within-site seasonal difference in net methylation was driven by changes in the methylation rate constant (k m). Samples incubated in the dark had lower net methylation due to km values that were 60% less than those incubated in the light. Disrupting the biofilm structure decreased km by 50% and resulted in net demethylating conditions. Overall, the measured rates resulted in a net excess of MMHg generated which could account for 27-85% of the MMHg flux in EFPC and suggests intact, actively photosynthesizing periphyton biofilms harbor zones of MMHg production.« less

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.

The Casualty Network System Capstone Project

DTIC Science & Technology

2012-12-01

capable of recording and transmitting a variety of vital signs such as: pulse rate, respiratory rate, SpO2 , and skin temperature. The IBD transmits...monitor biometric data of each individual on the team. When the MM is combined with CBRN sensor detection, the device will alert in the network to...obvious. By constantly monitoring vital signs of the team involved early clues of exposure (such as decreased SpO2 , increased respiratory rate and

Sedimentation survey of Lago Caonillas, Utuado, Puerto Rico, September–November 2012

USGS Publications Warehouse

Soler-Lopez, Luis R.

2016-11-09

During September–November 2012, the U.S. Geological Survey, in cooperation with the Puerto Rico Aqueduct and Sewer Authority, conducted a sedimentation survey of Lago Caonillas to estimate current (2012) reservoir storage capacity and the recent (2000–2012) reservoir sedimentation rate by comparing the 2012 bathymetric survey data with the February 2000 data. The Lago Caonillas storage capacity, which was 42.27 million cubic meters in February 2000, decreased to 39.55 million cubic meters by September–November 2012. The intersurvey (2000–2012) storage capacity loss was about 6 percent, corresponding to a decrease of about 0.5 percent per year; this loss represents a reservoir sedimentation rate of about 226,670 cubic meters per year between 2000 and 2012. On a long-term basis, however, the sedimentation rate has remained nearly constant, decreasing from about 257,500 to 251,720 cubic meters per year during 1948–2000 and 1948–2012, respectively. Most of the sediment accumulation and associated storage capacity loss of Lago Caonillas has occurred within the eastern and Río Caonillas branches of the reservoir. In the vicinity of the Caonillas Dam, minor sediment deposition and scour have occurred. The Lago Caonillas drainage area sediment yield has decreased by about 2 percent since the previous survey, from 1,266 cubic meters per square kilometer per year in 2000 to 1,237 cubic meters per square kilometer per year in 2012. If the long-term sedimentation rate of 251,720 cubic meters per year remains constant, the useful life of Lago Caonillas may end in about 2169.

Magma supply dynamics at Westdahl volcano, Alaska, modeled from satellite radar interferometry

USGS Publications Warehouse

Lu, Z.; Masterlark, Timothy; Dzurisin, D.; Rykhus, Russ; Wicks, C.

2003-01-01

A group of satellite radar interferograms that span the time period from 1991 to 2000 shows that Westdahl volcano, Alaska, deflated during its 1991-1992 eruption and is reinflating at a rate that could produce another eruption within the next several years. The rates of inflation and deflation are approximated by exponential decay functions having time constants of about 6 years and a few days, respectively. This behavior is consistent with a deep, constant-pressure magma source connected to a shallow reservoir by a magma-filled conduit. An elastic deformation model indicates that the reservoir is located about 6 km below sea level and beneath Westdahl Peak. We propose that the magma flow rate through the conduit is governed by the pressure gradient between the deep source and the reservoir. The pressure gradient, and hence the flow rate, are greatest immediately after eruptions. Pressurization of the reservoir decreases both the pressure gradient and the flow rate, but eventually the reservoir ruptures and an eruption or intrusion ensues. The eruption rate is controlled partly by the pressure gradient between the reservoir and surface, and therefore it, too, decreases with time. When the supply of eruptible magma is exhausted, the eruption stops, the reservoir begins to repressurize at a high rate, and the cycle repeats. This model might also be appropriate for other frequently active volcanoes with stable magma sources and relatively simple magma storage systems.

Magnetic and structural studies of trivalent Co-substituted Cd-Mn ferrites

NASA Astrophysics Data System (ADS)

Amer, M. A.; Meaz, T. M.; El-Kestawy, M.; Ghoneim, A. I.

2016-05-01

Series of polycrystalline Cd0.4Mn0.6CoxFe2-xO4 ferrites, 0≤x≤1, were prepared by solid state reaction method. The samples were characterized by inductive coupling plasma, X-ray diffraction, scanning electron microscopy, Fourier-transform infrared spectra and vibrating sample magnetometry. This study proved that all samples have single-phase cubic spinel structure. The true lattice constant, saturation magnetization, magnetic moment and trend of grain size and IR band νA showed decrease against x, whereas the trend of crystallite size, threshold frequency, Debye temperature, IR bands ν1 and ν2 and force constants F1 and F2, coercivity, anisotropy constant and residual magnetization showed increase. The IR analysis proved existence of Fe2+, Co2+, Fe4+, Co4+ and/or Mn4+ ions amongst the crystal sublattices. The characteristic bands ν1 and ν2 and force constants F1 and F2 showed decrease versus the tetrahedral- and octahedral-site bond length, respectively. The strain, specific surface area, refractive index, velocity, jump rate and remnant magnetization proved dependence on Co3+ ion content x.

Estimation of dissolution rate from in vivo studies of synthetic vitreous fibers.

PubMed

Eastes, W; Potter, R M; Hadley, J G

2000-11-01

Although the dissolution rate of a fiber was originally defined by a measurement of dissolution in simulated lung fluid in vitro, it is feasible to determine it from animal studies as well. The dissolution rate constant for a fiber may be extracted from the decrease in long fiber diameter observed in certain intratracheal instillation experiments or from the observed long fiber retention in short-term biopersistence studies. These in vivo dissolution rates agree well with those measured in vitro for the same fibers. For those special types of fibers, the high-alumina rock wool fibers that could not be measured in vitro, the method provides a way of obtaining a chemical dissolution rate constant from an animal study. The inverse of the in vivo dissolution rate, the fiber dissolution time, correlates well with the weighted half life of long fibers in a biopersistence study, and the in vivo dissolution rate may be estimated accurately from this weighted half-life.

Effect of drug lipophilicity on in vitro release rate from oil vehicles using nicotinic acid esters as model prodrug derivatives.

PubMed

Weng Larsen, S; Engelbrecht Thomsen, A E; Rinvar, E; Friis, G J; Larsen, C

2001-03-23

The rate constants for transfer of a homologous series of nicotinic acid esters from oil vehicles to aqueous buffer phases were determined using a rotating dialysis cell. The chemical stability of butyl nicotinate has been investigated at 60 degrees C over pH range 0.5--10. Maximum stability occurs at pH 4--5 and an inflection point was seen around the pK(a). For the nicotinic acid esters, a linear correlation was established between the first-order rate constant related to attainment of equilibrium, k(obs) and the apparent partition coefficient, P(app): log k(obs)=-0.83log P(app)+0.26 (k(obs) in h(-1), n=9). For hexyl nicotinate with a true partition coefficient of 4 it was possible to determine k(obs) by decreasing pH in the aqueous release medium to 2.05. Thus, under the latter experimental conditions estimation of the relative release rates for the esters were performed. The ratio between the specific rate constant k(ow), related to the transport from oil vehicle to aqueous phase, for ethyl and hexyl nicotinate was 139. The hydrophobic substituent constant for a methylene group, pi(CH(2)), was determined for nicotinic acid esters in different oil/buffer partitioning systems to 0.54--0.58. Addition of hydroxypropyl-beta-cyclodextrin to the aqueous release medium did not enhance the transport rate of the esters from the oil phase.

A method to quantify at late imaging a release rate of 18F-FDG in tissues.

PubMed

Laffon, Eric; Allard, Michèle; Marthan, Roger; Ducassou, Dominique

2005-08-01

This theoretical work shows that the rate constant for the (18)F-FDG release in tissues can be assessed without needing any arterial blood sampling. The method requires that the clearance of (18)F-FDG from plasma has occurred, whereas (18)F-FDG is still present in the tissue. This condition can be met dating from 3 h after (18)F-FDG injection, when hydration and/or phlorizin injection are applied after the routine static acquisition. The release rate constant can be obtained from a graphical analysis performed at the later decreasing phase of the tissue tracer activity. A two-compartment and a three-compartment model are developed, both in accordance with one another. To cite this article: E. Laffon et al., C. R. Biologies 328 (2005).

Effects of the Acute and Chronic Ethanol Intoxication on Acetate Metabolism and Kinetics in the Rat Brain.

PubMed

Hsieh, Ya-Ju; Wu, Liang-Chih; Ke, Chien-Chih; Chang, Chi-Wei; Kuo, Jung-Wen; Huang, Wen-Sheng; Chen, Fu-Du; Yang, Bang-Hung; Tai, Hsiao-Ting; Chen, Sharon Chia-Ju; Liu, Ren-Shyan

2018-02-01

Ethanol (EtOH) intoxication inhibits glucose transport and decreases overall brain glucose metabolism; however, humans with long-term EtOH consumption were found to have a significant increase in [1- 11 C]-acetate uptake in the brain. The relationship between the cause and effect of [1- 11 C]-acetate kinetics and acute/chronic EtOH intoxication, however, is still unclear. [1- 11 C]-acetate positron emission tomography (PET) with dynamic measurement of K 1 and k 2 rate constants was used to investigate the changes in acetate metabolism in different brain regions of rats with acute or chronic EtOH intoxication. PET imaging demonstrated decreased [1- 11 C]-acetate uptake in rat brain with acute EtOH intoxication, but this increased with chronic EtOH intoxication. Tracer uptake rate constant K 1 and clearance rate constant k 2 were decreased in acutely intoxicated rats. No significant change was noted in K 1 and k 2 in chronic EtOH intoxication, although 6 of 7 brain regions showed slightly higher k 2 than baseline. These results indicate that acute EtOH intoxication accelerated acetate transport and metabolism in the rat brain, whereas chronic EtOH intoxication status showed no significant effect. In vivo PET study confirmed the modulatory role of EtOH, administered acutely or chronically, in [1- 11 C]-acetate kinetics and metabolism in the rat brain. Acute EtOH intoxication may inhibit the transport and metabolism of acetate in the brain, whereas chronic EtOH exposure may lead to the adaptation of the rat brain to EtOH in acetate utilization. [1- 11 C]-acetate PET imaging is a feasible approach to study the effect of EtOH on acetate metabolism in rat brain. Copyright © 2017 by the Research Society on Alcoholism.

Photosynthesis and Transpiration of Monterey Pine Seedlings as a Function of Soil Water Suction and Soil Temperature

PubMed Central

Babalola, O.; Boersma, L.; Youngberg, C. T.

1968-01-01

Rates of photosynthesis, respiration, and transpiration of Monterey pine (Pinus radiata D. Don) were measured under controlled conditions of soil water suction and soil temperature. Air temperature, relative humidity, light intensity, and air movement were maintained constant. Rates of net photosynthesis, respiration, and transpiration decreased with increasing soil water suction. The decrease in the rates of net photosynthesis and transpiration as a function of the soil temperature at low soil water suctions may be attributed to changes in the viscosity of water. At soil water suctions larger than 0.70 bars rates of transpiration and net photosynthesis may be affected in the same proportion by changes in stomatal apertures. Images PMID:16656800

Disease management programs for patients with COPD in Germany: a longitudinal evaluation of routinely collected patient records.

PubMed

Mehring, Michael; Donnachie, Ewan; Fexer, Johannes; Hofmann, Frank; Schneider, Antonius

2014-07-01

The primary aim of the disease management program (DMP) for patients with COPD is to improve health outcomes and thereby to reduce overall costs. Six years after its introduction in Germany, no consensus has yet been reached as to whether the DMP has been effective in reaching these goals. The objective of the study was an evaluation of the DMP for COPD in Bavaria using routinely collected subject medical records. A longitudinal population-based study, comparing the total DMP population of up to 86,560 patients with a stable cohort of 17,549 subjects over a period of 5 years. The effect of subject dropout in the cohort is further estimated by means of inverse probability weighting. The proportion of subjects in the total population who were prescribed and received treatment with oral corticosteroids declined at a constant rate of 1.0% per year (P < .001). The proportion of subjects who were given a prescription for theophylline decreased at a constant rate of 2.0% per year (P < .001). By 2012, 15.6% of the total population and 26% of the cohort had undergone self-management education. While the proportion of smokers in the total population remained constant because of the effect of newly enrolled subjects, the proportion of smokers decreased significantly even after dropout adjustment, from 29% to 21%. The occurrence of exacerbations decreased steadily at a rate of 0.9% (total population) or 0.7% (cohort) per year. While the occurrence of emergency hospital admissions decreased in the total population, an increase was observed within the cohort. Summarizing all results leads to the suggestion that the German DMP for COPD has been effective in enhancing the quality of care in regard to an improved adherence to guidelines, pharmacotherapy, exacerbations, and self-management education. However, the DMP was not able to prevent an increase in emergency hospital admissions for the stable population in the cohort. Copyright © 2014 by Daedalus Enterprises.

Packaging of single DNA molecules by the yeast mitochondrial protein Abf2p: reinterpretation of recent single molecule experiments.

PubMed

Stigter, Dirk

2004-07-01

Brewer et al. (Biophys. J. 85 (2003) 2519-2524) have studied the compaction of dsDNA in a double flow cell by observing the extension of stained DNA tethered in buffer solutions with or without Abf2p. They use a Langmuir adsorption model in which one Abf2p molecule adsorbs on one site on the DNA, and the binding constant, K, is given as the ratio of the experimental rates of adsorption and desorption. This paper presents an improved interpretation. Instead of Langmuir adsorption we use the more appropriate McGhee-von Hippel (J. Mol. Biol. 86 (1974) 469-489) theory for the adsorption of large ligands to a one-dimensional lattice. We assume that each adsorbed molecule shortens the effective contour length of DNA by the foot print of Abf2p of 27 base pairs. When Abf2p adsorbs to DNA stretched in the flowing buffer solution, we account for a tension effect that decreases the adsorption rate and the binding constant by a factor of 2 to 4. The data suggest that the accessibility to Abf2p decreases significantly with increasing compaction of DNA, resulting in a lower adsorption rate and a lower binding constant. The kinetics reported by Brewer et al. (Biophys. J. 85 (2003) 2519-2524) lead to a binding constant K=3.6 x 10(6) M(-1) at the beginning, and to K=5 x 10(5) M(-1) near the end of a compaction run, more than an order of magnitude lower than the value K=2.57 x 10(7) M(-1) calculated by Brewer et al. (Biophys. J. 85 (2003) 2519-2524).

Biogeochemical factors influencing net mercury methylation in contaminated freshwater sediments from the St. Lawrence River in Cornwall, Ontario, Canada.

PubMed

Avramescu, Mary-Luyza; Yumvihoze, Emmanuel; Hintelmann, Holger; Ridal, Jeff; Fortin, Danielle; Lean, David R S

2011-02-01

The activity of various anaerobic microbes, including sulfate reducers (SRB), iron reducers (FeRP) and methanogens (MPA) has been linked to mercury methylation in aquatic systems, although the relative importance of each microbial group in the overall process is poorly understood in natural sediments. The present study focused on the biogeochemical factors (i.e. the relative importance of various groups of anaerobic microbes (FeRP, SRB, and MPA) that affect net monomethylmercury (MMHg) formation in contaminated sediments of the St. Lawrence River (SRL) near Cornwall (Zone 1), Ontario, Canada. Methylation and demethylation potentials were measured separately by using isotope-enriched mercury species ((200)Hg(2+) and MM(199)Hg(+)) in sediment microcosms treated with specific microbial inhibitors. Sediments were sampled and incubated in the dark at room temperature in an anaerobic chamber for 96h. The potential methylation rate constants (K(m)) and demethylation rates (K(d)) were found to differ significantly between microcosms. The MPA-inhibited microcosm had the highest potential methylation rate constant (0.016d(-1)), whereas the two SRB-inhibited microcosms had comparable potential methylation rate constants (0.003d(-1) and 0.002d(-1), respectively). The inhibition of methanogens stimulated net methylation by inhibiting demethylationand by stimulating methylation along with SRB activity. The inhibition of both methanogens and SRB was found to enhance the iron reduction rates but did not completely stop MMHg production. The strong positive correlation between K(m) and Sulfate Reduction Rates (SRR) and between K(d) and Methane Production Rates (MPR) supports the involvement of SRB in Hg methylation and MPA in MMHg demethylation in the sediments. In contrast, the strong negative correlation between K(d) and Iron Reduction Rates (FeRR) shows that the increase in FeRR corresponds to a decrease in demethylation, indicating that iron reduction may influence net methylation in the SLR sediments by decreasing demethylation rather than favouring methylation. Copyright © 2010 Elsevier B.V. All rights reserved.

Effects of alteration product precipitation on glass dissolution

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

Strachan, Denis M.; Neeway, James J.

2014-06-01

Understanding the mechanisms that control the durability of nuclear waste glass is paramount if reliable models are to be constructed so that the glass dissolution rate in a given geological repository can be calculated. Presently, it is agreed that (boro)silicate glasses dissolve in water at a rate dependent on the solution concentration of orthosilicic acid (H 4SiO 4) with higher [H 4SiO 4] leading to lower dissolution rates. Once the reaction has slowed as a result of the buildup of H 4SiO 4, another increase in the rate has been observed that corresponds to the precipitation of certain silica-bearing alterationmore » products. However, it has also been observed that the concentration of silica-bearing solution species does not significantly decrease, indicating saturation, while other glass tracer elements concentrations continue to increase, indicating that the glass is still dissolving. In this study, we have used the Geochemist’s Workbench code to investigate the relationship between glass dissolution rates and the precipitation rate of a representative zeolitic silica-bearing alteration product, analcime [Na(AlSi 2O 6)∙H 2O]. To simplify the calculations, we suppressed all alteration products except analcime, gibbsite (Al(OH) 3), and amorphous silica. The pseudo-equilibrium-constant matrix for amorphous silica was substituted for the glass pseudo-equilibrium-constant matrix because it has been shown that silicate glasses act as a silica-only solid with respect to kinetic considerations. In this article, we present the results of our calculations of the glass dissolution rate at different values for the analcime precipitation rate constant and the effects of varying the glass dissolution rate constant at a constant analcime precipitation rate constant. From the simulations we conclude, firstly, that the rate of glass dissolution is dependent on the kinetics of formation of the zeolitic phase. Therefore, the kinetics of secondary phase formation is an important parameter that should be taken into account in future glass dissolution modeling efforts. Secondly, the results indicate that, in the absence of a gel layer, the glass dissolution rate controls the rate of analcime precipitation in the long term. Finally, the meaning of these results pertinent to long-term glass durability is discussed.« less

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.

Na(+) transport, and the E(1)P-E(2)P conformational transition of the Na(+)/K(+)-ATPase.

PubMed Central

Babes, A; Fendler, K

2000-01-01

We have used admittance analysis together with the black lipid membrane technique to analyze electrogenic reactions within the Na(+) branch of the reaction cycle of the Na(+)/K(+)-ATPase. ATP release by flash photolysis of caged ATP induced changes in the admittance of the compound membrane system that are associated with partial reactions of the Na(+)/K(+)-ATPase. Frequency spectra and the Na(+) dependence of the capacitive signal are consistent with an electrogenic or electroneutral E(1)P <--> E(2)P conformational transition which is rate limiting for a faster electrogenic Na(+) dissociation reaction. We determine the relaxation rate of the rate-limiting reaction and the equilibrium constants for both reactions at pH 6.2-8.5. The relaxation rate has a maximum value at pH 7.4 (approximately 320 s(-1)), which drops to acidic (approximately 190 s(-1)) and basic (approximately 110 s(-1)) pH. The E(1)P <--> E(2)P equilibrium is approximately at a midpoint position at pH 6.2 (equilibrium constant approximately 0.8) but moves more to the E(1)P side at basic pH 8.5 (equilibrium constant approximately 0.4). The Na(+) affinity at the extracellular binding site decreases from approximately 900 mM at pH 6.2 to approximately 200 mM at pH 8.5. The results suggest that during Na(+) transport the free energy supplied by the hydrolysis of ATP is mainly used for the generation of a low-affinity extracellular Na(+) discharge site. Ionic strength and lyotropic anions both decrease the relaxation rate. However, while ionic strength does not change the position of the conformational equilibrium E(1)P <--> E(2)P, lyotropic anions shift it to E(1)P. PMID:11053130

Root elongation against a constant force: experiment with a computerized feedback-controlled device

NASA Technical Reports Server (NTRS)

Kuzeja, P. S.; Lintilhac, P. M.; Wei, C.

2001-01-01

Axial force was applied to the root tip of corn (Zea mays L. cv. Merit) seedlings using a computerized, feedback-controlled mechanical device. The system's feedback capability allowed continuous control of a constant tip load, and the attached displacement transducer provided the time course of root elongation. Loads up to 7.5 g decreased the root elongation rate by 0.13 mm h-1 g-1, but loads 7.5 to 17.5 g decreased the growth rate by only 0.04 mm h-1 g-1. Loads higher than 18 g stopped root elongation completely. Measurement of the cross-sectional areas of the root tips indicated that the 18 g load had applied about 0.98 MPa of axial pressure to the root, thereby exceeding the root's ability to respond with increased turgor pressure. Recorded time-lapse images of loaded roots showed that radial thickening (swelling) occurred behind the root cap, whose cross-sectional area increased with tip load.

RXTE/PCA and Swift/XRT observations of GRO J1655-40 during decay

NASA Astrophysics Data System (ADS)

Homan, Jeroen; Kong, Albert; Tomsick, John; Miller, Jon; Campana, Sergio; Wijnands, Rudy; Belloni, Tomaso; Lewin, Walter

2005-10-01

Following its transition to the hard state (ATels #607,#612), we have continued our daily RXTE/PCA observations of the black hole X-ray transient GRO J1655-40 (see http://tahti.mit.edu/opensource/1655). Between September 23, when the source reached the hard state, and October 10, the RXTE/ PCA count rate decreased exponentially, with an e-folding time of ~7 days. After October 10 the decrease started to slow down and data from the last few days suggest that the count rate may have reached a constant level.

Kinetics of thorium and particle cycling along the U.S. GEOTRACES North Atlantic Transect

NASA Astrophysics Data System (ADS)

Lerner, Paul; Marchal, Olivier; Lam, Phoebe J.; Buesseler, Ken; Charette, Matthew

2017-07-01

The high particle reactivity of thorium has resulted in its widespread use in tracing processes impacting marine particles and their chemical constituents. The use of thorium isotopes as tracers of particle dynamics, however, largely relies on our understanding of how the element scavenges onto particles. Here, we estimate apparent rate constants of Th adsorption (k1), Th desorption (k-1), bulk particle degradation (β-1), and bulk particle sinking speed (w) along the water column at 11 open-ocean stations occupied during the GEOTRACES North Atlantic Section (GA03). First, we provide evidence that the budgets of Th isotopes and particles at these stations appear to be generally dominated by radioactive production and decay sorption reactions, particle degradation, and particle sinking. Rate parameters are then estimated by fitting a Th and particle cycling model to data of dissolved and particulate 228,230,234Th, 228Ra, particle concentrations, and 234,238U estimates based on salinity, using a nonlinear programming technique. We find that the adsorption rate constant (k1) generally decreases with depth across the section: broadly, the time scale 1 /k1 averages 1.0 yr in the upper 1000 m and (1.4-1.5) yr below. A positive relationship between k1 and particle concentration (P) is found, i.e., k1 ∝Pb , where b ≥ 1 , consistent with the notion that k1 increases with the number of surface sites available for adsorption. The rate constant ratio, K =k1 / (k-1 +β-1) , which measures the collective influence of rate parameters on Th scavenging, averages 0.2 for most stations and most depths. We clarify the conditions under which K / P is equivalent to the distribution coefficient, KD, test that the conditions are met at the stations, and find that K / P decreases with P, in line with a particle concentration effect (dKD / dP < 0). In contrast to the influence of colloids as envisioned by the Brownian pumping hypothesis, we provide evidence that the particle concentration effect arises from the joint effect of P on the rate constants for thorium attachment to, and detachment from, particles.

Exercise science: research to sustain and enhance performance

NASA Astrophysics Data System (ADS)

Wingo, Jonathan E.

2013-05-01

Cardiovascular adjustments accompanying exercise in high ambient temperatures are likely responsible for diminished aerobic capacity and performance in such conditions. These adjustments include a phenomenon known as cardiovascular drift in which heart rate rises and stroke volume declines progressively over time during constant-rate exercise. A variety of factors modulate the magnitude of cardiovascular drift, e.g., elevated core and skin temperatures, dehydration, and exercise intensity. Regardless of the mode of manipulation, decreases in stroke volume associated with cardiovascular drift result in directionally and proportionally similar decreases in maximal aerobic capacity. Maximal aerobic capacity is determined by maximal heart rate, maximal tissue oxygen extraction, and maximal stroke volume. Because maximal heart rate and maximal tissue oxygen extraction are unaffected during exercise in the heat, decreased stroke volume associated with cardiovascular drift likely persists during maximal efforts and explains the decrease in maximal aerobic capacity. Decreased maximal aerobic capacity results in a greater perceptual and physiological strain accompanying any given level of work. Therefore, sustaining and enhancing performance involves sophisticated monitoring of physiological strain combined with development of countermeasures that mitigate the magnitude of deleterious phenomena like cardiovascular drift.

Low-Temperature Friction-Stir Welding of 2024 Aluminum

NASA Technical Reports Server (NTRS)

Benavides, S.; Li, Y.; Murr, L. E.; Brown, D.; McClure, J. C.

1998-01-01

Solid state friction-stir welding (FSW) has been demonstrated to involve dynamic recrystallization producing ultra-fine, equiaxed grain structures to facilitate superplastic deformation as the welding or joining mechanism. However, the average residual, equiaxed, grain size in the weld zone has ranged from roughly 0.5 micron to slightly more than 10 micron, and the larger weld zone grain sizes have been characterized as residual or static grain growth as a consequence of the temperatures in the weld zone (where center-line temperatures in the FSW of 6061 Al have been shown to be as high as 480C or -0.8 T(sub M) where T(sub M) is the absolute melting temperature)). In addition, the average residual weld zone grain size has been observed to increase near the top of the weld, and to decrease with distance on either side of the weld-zone centerline, an d this corresponds roughly to temperature variations within the weld zone. The residual grain size also generally decreases with decreasing FSW tool rotation speed. These observations are consistent with the general rules for recrystallization where the recrystallized grain size decreases with increasing strain (or deformation) at constant strain rate, or with increasing strain-rate, or with increasing strain rate at constant strain; especially at lower ambient temperatures, (or annealing temperatures). Since the recrystallization temperature also decreases with increasing strain rate, the FSW process is somewhat complicated because the ambient temperature, the frictional heating fraction, and the adiabatic heating fraction )proportional to the product of strain and strain-rate) will all influence both the recrystallization and growth within the FSW zone. Significantly reducing the ambient temperature of the base metal or work pieces to be welded would be expected to reduce the residual weld-zone grain size. The practical consequences of this temperature reduction would be the achievement of low temperature welding. This study compares the residual grain sizes and microstructures in 2024 Al friction-stir welded at room temperature (about 30C and low temperature (-30C).

Bubble formation dynamics in a planar co-flow configuration: Influence of geometric and operating characteristics

NASA Astrophysics Data System (ADS)

Gutiérrez-Montes, Cándido; Bolaños-Jiménez, Rocío; Martínez-Bazán, Carlos; Sevilla, Alejandro

2014-11-01

An experimental and numerical study has been performed to explore the influence of different geometric features and operating conditions on the dynamics of a water-air-water planar co-flow. Specifically, regarding the nozzle used, the inner-to-outer thickness ratio of the air injector, β = Hi/Ho, the water-to-air thickness ratio, h = Hw/Ho, and the shape of the injector tip, have been described. As for the operating conditions, the water exit velocity profile under constant flow rate and constant air feeding pressure has been assessed. The results show that the jetting-bubbling transition is promoted for increasing values of β, decreasing values of h, rounded injector tip, and for uniform water exit velocity profiles. As for the bubble formation frequency, it increases with increasing values of β, decreasing values of h, rounded injector and parabolic-shaped water exit profiles. Furthermore, the bubble formation frequency has been shown to be lower under constant air feeding pressure conditions than at constant gas flow rate conditions. Finally, the effectiveness of a time-variable air feeding stream has been numerically studied, determining the forcing receptivity space in the amplitude-frequency plane. Experimental results corroborate the effectiveness of this control technique. Work supported by Spanish MINECO, Junta de Andalucía, European Funds and UJA under Projects DPI2011-28356-C03-02, DPI2011-28356-C03-03, P11-TEP7495 and UJA2013/08/05.

Feasibility study of volumetric modulated arc therapy with constant dose rate for endometrial cancer

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

Yang, Ruijie; Wang, Junjie, E-mail: junjiewang47@yahoo.com; Xu, Feng

2013-10-01

To investigate the feasibility, efficiency, and delivery accuracy of volumetric modulated arc therapy with constant dose rate (VMAT-CDR) for whole-pelvic radiotherapy (WPRT) of endometrial cancer. The nine-field intensity-modulated radiotherapy (IMRT), VMAT with variable dose-rate (VMAT-VDR), and VMAT-CDR plans were created for 9 patients with endometrial cancer undergoing WPRT. The dose distribution of planning target volume (PTV), organs at risk (OARs), and normal tissue (NT) were compared. The monitor units (MUs) and treatment delivery time were also evaluated. For each VMAT-CDR plan, a dry run was performed to assess the dosimetric accuracy with MatriXX from IBA. Compared with IMRT, the VMAT-CDRmore » plans delivered a slightly greater V{sub 20} of the bowel, bladder, pelvis bone, and NT, but significantly decreased the dose to the high-dose region of the rectum and pelvis bone. The MUs decreased from 1105 with IMRT to 628 with VMAT-CDR. The delivery time also decreased from 9.5 to 3.2 minutes. The average gamma pass rate was 95.6% at the 3%/3 mm criteria with MatriXX pretreatment verification for 9 patients. VMAT-CDR can achieve comparable plan quality with significant shorter delivery time and smaller number of MUs compared with IMRT for patients with endometrial cancer undergoing WPRT. It can be accurately delivered and be an alternative to IMRT on the linear accelerator without VDR capability.« less

Liquid-phase hydrogenation of citral over Pt/SiO{sub 2} catalysts. 2. Hydrogenation of reaction intermediate compounds

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

Singh, U.K.; Sysak, M.N.; Vannice, M.A.

2000-04-01

Liquid-phase hydrogenation of the four principal reaction intermediates formed during citral hydrogenation, i.e., nerol, geraniol, citronellal, and citronellol, was studied at 298 and 373 K under 20 atm H{sub 2} at concentrations of 0.5 to 1.0 M in hexane. A decrease in the initial reaction rate as temperature increased from 298 to 373 K was exhibited during the hydrogenation of all four compounds, just as reported earlier for citral; however, the decrease in rate at 373 K was only one-half for citronellal whereas it was orders of magnitude greater for nerol and geraniol. Furthermore, simultaneous hydrogenation of citronellal and geraniolmore » at 298 K resulted in a continuous decrease in the rate of citronellal disappearance in contrast to the nearly constant rate of disappearance observed during hydrogenation of citronellal alone. Competitive hydrogenation of citral with either geraniol or citronellal showed that geraniol hydrogenation to citronellol is kinetically insignificant during citral hydrogenation at 373 K. The initial activity for hydrogenation of the intermediates at 298 K follows the following trend: geraniol > nerol < citronellol < E-citral, citronellal > Z-citral. Based on the relative hydrogenation rates of the intermediate alone versus its hydrogenation in the presence of other reactants, the relative size of the adsorption equilibrium constants for the various organic compounds appears to be as follows: citral > citronellal > geraniol, nerol > citronellol > 3,7-dimethyloctanol. This study indicates that activation of the C{double_bond}O bond should be performed at higher reaction temperatures to maximize selectivity to the unsaturated alcohols.« less

G-Jitter Induced Magnetohydrodynamics Flow of Nanofluid with Constant Convective Thermal and Solutal Boundary Conditions

PubMed Central

Uddin, Mohammed J.; Khan, Waqar A.; Ismail, Ahmad Izani Md.

2015-01-01

Taking into account the effect of constant convective thermal and mass boundary conditions, we present numerical solution of the 2-D laminar g-jitter mixed convective boundary layer flow of water-based nanofluids. The governing transport equations are converted into non-similar equations using suitable transformations, before being solved numerically by an implicit finite difference method with quasi-linearization technique. The skin friction decreases with time, buoyancy ratio, and thermophoresis parameters while it increases with frequency, mixed convection and Brownian motion parameters. Heat transfer rate decreases with time, Brownian motion, thermophoresis and diffusion-convection parameters while it increases with the Reynolds number, frequency, mixed convection, buoyancy ratio and conduction-convection parameters. Mass transfer rate decreases with time, frequency, thermophoresis, conduction-convection parameters while it increases with mixed convection, buoyancy ratio, diffusion-convection and Brownian motion parameters. To the best of our knowledge, this is the first paper on this topic and hence the results are new. We believe that the results will be useful in designing and operating thermal fluids systems for space materials processing. Special cases of the results have been compared with published results and an excellent agreement is found. PMID:25933066

Decision time, slow inhibition, and theta rhythm.

PubMed

Smerieri, Anteo; Rolls, Edmund T; Feng, Jianfeng

2010-10-20

In this paper, we examine decision making in a spiking neuronal network and show that longer time constants for the inhibitory neurons can decrease the reaction times and produce theta rhythm. We analyze the mechanism and find that the spontaneous firing rate before the decision cues are applied can drift, and thereby influence the speed of the reaction time when the decision cues are applied. The drift of the firing rate in the population that will win the competition is larger if the time constant of the inhibitory interneurons is increased from 10 to 33 ms, and even larger if there are two populations of inhibitory neurons with time constants of 10 and 100 ms. Of considerable interest is that the decision that will be made can be influenced by the noise-influenced drift of the spontaneous firing rate over many seconds before the decision cues are applied. The theta rhythm associated with the longer time constant networks mirrors the greater integration in the firing rate drift produced by the recurrent connections over long time periods in the networks with slow inhibition. The mechanism for the effect of slow waves in the theta and delta range on decision times is suggested to be increased neuronal spiking produced by depolarization of the membrane potential on the positive part of the slow waves when the neuron's membrane potential is close to the firing threshold.

[In-vitro evaluation of cinnarizine as a competing agent to beta-cyclodextrin inclusion complexes: effect of cinnarizine on the membrane permeation rate of progesterone from its beta-cyclodextrin inclusion complex].

PubMed

Muraoka, Atsushi; Tokumura, Tadakazu; Machida, Yoshiharu

2008-01-01

The use of competing agents is considered a powerful tool for the development of a drug-delivery system with drug/cyclodextrin inclusion complexes. However, there are very few studies examining this issue. To explain this phenomenon, it was thought that a competing agent with a sufficiently high stability constant had not yet been reported. In this study, cinnarizine (CN), which has a high stability constant with beta-cyclodextrin (beta-CD) and unique solubility characteristics, was selected, and its ability as a competing agent was examined in a membrane permeability study. The permeability study showed that the permeation rates of the drugs flurbiprofen, progesterone, and spironolactone decreased with their stability constants with the addition of beta-CD. In one of the drugs, progesterone (Pro), the decrease was restored by the addition of CN. The amount of CN added was a 1:1 molar ratio to the amount of Pro. However, no similar action was induced with the addition of DL-phenylalanine (Phe) in the permeation study at the 1:5 (Pro:Phe) molar ratio. These finding indicate that CN acts as a competing agent, and its action is much stronger than that of Phe.

Impacts of Activated Carbon Amendment on Hg Methylation, Demethylation and Microbial Activity in Marsh Soils

NASA Astrophysics Data System (ADS)

Gilmour, C. C.; Ghosh, U.; Santillan, E. F. U.; Soren, A.; Bell, J. T.; Butera, D.; McBurney, A. W.; Brown, S.; Henry, E.; Vlassopoulos, D.

2015-12-01

In-situ sorbent amendments are a low-impact approach for remediation of contaminants in sediments, particular in habitats like wetlands that provide important ecosystem services. Laboratory microcosm trials (Gilmour et al. 2013) and early field trials show that activated carbon (AC) can effectively increase partitioning of both inorganic Hg and methylmercury to the solid phase. Sediment-water partitioning can serve as a proxy for Hg and MeHg bioavailability in soils. One consideration in using AC in remediation is its potential impact on organisms. For mercury, a critical consideration is the potential impact on net MeHg accumulation and bioavailability. In this study, we specifically evaluated the impact of AC on rates of methylmercury production and degradation, and on overall microbial activity, in 4 different Hg-contaminated salt marsh soils. The study was done over 28 days in anaerobic, sulfate-reducing slurries. A double label of enriched mercury isotopes (Me199Hg and inorganic 201Hg) was used to separately follow de novo Me201Hg production and Me199Hg degradation. AC amendments decreased both methylation and demethylation rate constants relative to un-amended controls, but the impact on demethylation was stronger. The addition of 5% (dry weight) regenerated AC to soil slurries drove demethylation rate constants to nearly zero; i.e. MeHg sorption to AC almost totally blocked its degradation. The net impact was increased solid phase MeHg concentrations in some of the soil slurries with the highest methylation rate constants. However, the net impact of AC amendments was to increase MeHg (and inorganic Hg) partitioning to the soil phase and decrease concentrations in the aqueous phase. AC significantly decreased aqueous phase inorganic Hg and MeHg concentrations after 28 days. Overall, the efficacy of AC in reducing aqueous MeHg was highest in the soils with the highest MeHg concentrations. The AC addition did not significantly impact microbial activity, as assessed by CO2 production and sulfate depletion, in two of the four soils, but resulted in a up to a 40% decrease in two other soils. AC amendment has little effect on slurry pH, but decreased aqueous Fe, sulfide and DOC concentrations.

BACTERIAL METHYLMERCURY DEGRADATION IN FLORIDA EVERGLADES PEAT SEDIMENT

EPA Science Inventory

Methylmercury (MeHg) degradation was investigated along an eutrophication gradient in the Florida Everglades by quantifying 14CH4 and 14CO2 production after incubation of anaerobic sediments with [14C]MeHg. Degradation rate constants (k) were consistently <=0.1 d-1 and decreased ...

Impairment of Lymph Drainage in Subfascial Compartment of Forearm in Breast Cancer-Related Lymphedema

PubMed Central

MELLOR, R.H.; COOK, G.J.; SVENSSON, W.E.; PETERS, A.M.; LEVICK, J.R.; MORTIMER, P.S.

2005-01-01

Background: In arm lymphedema secondary to axillary surgery and radiotherapy (breast cancer-related lymphedema), the swelling is largely epifascial and lymph flow per unit epifascial volume is impaired. The subfascial muscle compartment is not measurably swollen despite the iatrogenic damage to its axillary drainage pathway, but this could be due to its low compliance. Our aim was to test the hypothesis that subfascial lymph drainage too is impaired. Methods and Results: Quantitative lymphoscintigraphy was used to measure the removal rate constant (local lymph flow per unit distribution volume) for technetium-99m-human immunoglobulin G injected intramuscularly in the forearms of nine women with unilateral lymphedema. The removal rate constant was on average 31% lower in the ipsilateral swollen forearm than in the contralateral forearm (swollen arm: −0.096 ± 0.041% min−1, contralateralarm: −0.138 ± 0.037% min−1; mean ± SD, p = 0.037). The decrease in subfascial rate constant correlated strongly with increase in arm volume (r 0.88, p = 0.002), even though the swelling is mainly epifascial. There was no convincing evidence of dermal backflow. Conclusions: Lymph flow in the subfascial muscle compartment is decreased in breast cancer-related lymphedema. The correlation between impairment of subfascial drainage and epifascial arm swelling could be because both depend on the severity of axillary damage, or because loss of function in subfascial lymphatics impairs drainage from the epifascial to the subfascial system. PMID:15624420

Effect of contact time and force on monocyte adhesion to vascular endothelium.

PubMed Central

Rinker, K D; Prabhakar, V; Truskey, G A

2001-01-01

In this study we examined whether monocytic cell attachment to vascular endothelium was affected by elevating shear stress at a constant shear rate. Contact time, which is inversely related to the shear rate, was fixed and viscosity elevated with dextran to increase the shear stress (and hence the net force on the cell) independently of shear rate. At a fixed contact time, tethering frequencies increased, rolling velocities decreased, and median arrest durations increased with increasing shear stress. Rolling and short arrests (< 0.2 s) were well fit by a single exponential consistent with adhesion via the formation of a single additional bond. The cell dissociation constant, k(off), increased when the shear stress was elevated at constant shear rate. Firmly adherent cells arresting for at least 0.2 s were well fit by a stochastic model involving dissociation from multiple bonds. Therefore, at a fixed contact time and increasing shear stress, bonds formed more frequently for rolling cells resulting in more short arrests, and more bonds formed for firmly arresting cells resulting in longer arrest durations. Possible mechanisms for this increased adhesion include greater monocyte deformation and/or more frequent penetration of microvilli through steric and charge barriers. PMID:11259286

History dependent crystallization of Zr{sub 41}Ti{sub 14}Cu{sub 12}Ni{sub 10}Be{sub 23} melts

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

Schroers, Jan; Johnson, William L.

The crystallization of Zr{sub 41}Ti{sub 14}Cu{sub 12}Ni{sub 10}Be{sub 23} (Vit 1) melts during constant heating is investigated. (Vit 1) melts are cooled with different rates into the amorphous state and the crystallization temperature upon subsequent heating is studied. In addition, Vit 1 melts are cooled using a constant rate to different temperatures and subsequently heated from this temperature with a constant rate. We investigate the influence of the temperature to which the melt was cooled on the crystallization temperature measured upon heating. In both cases the onset temperature of crystallization shows strong history dependence. This can be explained by anmore » accumulating process during cooling and heating. An attempt is made to consider this process in a simple model by steady state nucleation and subsequent growth of the nuclei which results in different crystallization kinetics during cooling or heating. Calculations show qualitative agreement with the experimental results. However, calculated and experimental results differ quantitatively. This difference can be explained by a decomposition process leading to a nonsteady nucleation rate which continuously increases with decreasing temperature. (c) 2000 American Institute of Physics.« less

Amino acid geochemistry of fossil bones from the Rancho La Brea asphalt deposit, California

USGS Publications Warehouse

McMenamin, M.A.S.; Blunt, D.J.; Kvenvolden, K.A.; Miller, S.E.; Marcus, L.F.; Pardi, R.R.

1982-01-01

Low aspartic acid d:l ratios and modern collagenlike concentration values indicate that amino acids in bones from the Rancho La Brea asphalt deposit, Los Angeles, California are better preserved than amino acids in bones of equivalent age that have not been preserved in asphalt. Amino acids were recovered from 10 Rancho La Brea bone samples which range in age from less than 200 to greater than 36,000 yr. The calibrated rates of aspartic acid racemization range from 2.1 to 5.0 ?? 10-6yr-1. Although this wide range of rate constants decreases the level of confidence for age estimates, use of the larger rate constant of 5.0 ?? 10-6yr-1 provides minimum age estimates which fit the known stratigraphic and chronologic records of the Rancho La Brea deposits. ?? 1982.

Detonation in TATB Hemispheres

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

Druce, B; Souers, P C; Chow, C

2004-03-17

Streak camera breakout and Fabry-Perot interferometer data have been taken on the outer surface of 1.80 g/cm{sup 3} TATB hemispherical boosters initiated by slapper detonators at three temperatures. The slapper causes breakout to occur at 54{sup o} at ambient temperatures and 42{sup o} at -54 C, where the axis of rotation is 0{sup o}. The Fabry velocities may be associated with pressures, and these decrease for large timing delays in breakout seen at the colder temperatures. At room temperature, the Fabry pressures appear constant at all angles. Both fresh and decade-old explosive are tested and no difference is seen. Themore » problem has been modeled with reactive flow. Adjustment of the JWL for temperature makes little difference, but cooling to -54 C decreases the rate constant by 1/6th. The problem was run both at constant density and with density differences using two different codes. The ambient code results show that a density difference is probably there but it cannot be quantified.« less

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

Effect of Sodium Chloride on α-Dicarbonyl Compound and 5-Hydroxymethyl-2-furfural Formations from Glucose under Caramelization Conditions: A Multiresponse Kinetic Modeling Approach.

PubMed

Kocadağlı, Tolgahan; Gökmen, Vural

2016-08-17

This study aimed to investigate the kinetics of α-dicarbonyl compound formation in glucose and glucose-sodium chloride mixture during heating under caramelization conditions. Changes in the concentrations of glucose, fructose, glucosone, 1-deoxyglucosone, 3-deoxyglucosone, 3,4-dideoxyglucosone, 5-hydroxymethyl-2-furfural (HMF), glyoxal, methylglyoxal, and diacetyl were determined. A comprehensive reaction network was built, and the multiresponse model was compared to the experimentally observed data. Interconversion between glucose and fructose became 2.5 times faster in the presence of NaCl at 180 and 200 °C. The effect of NaCl on the rate constants of α-dicarbonyl compound formation varied across the precursor and the compound itself and temperature. A decrease in rate constants of 3-deoxyglucosone and 1-deoxyglucosone formations by the presence of NaCl was observed. HMF formation was revealed to be mainly via isomerization to fructose and dehydration over cyclic intermediates, and the rate constants increase 4-fold in the presence of NaCl.

Enhanced sonochemical degradation of azure B dye by the electroFenton process.

PubMed

Martínez, Susana Silva; Uribe, Edgar Velasco

2012-01-01

The degradation of azure B dye (C15H16ClN3S; AB) has been studied by Fenton, sonolysis and sono-electroFenton processes employing ultrasound at 23 kHz and the electrogeneration of H2O2 at the reticulated vitreous carbon electrode. It was found that the dye degradation followed apparent first-order kinetics in all the degradation processes tested. The rate constant was affected by both the pH of the solution and initial concentration of Fe2+, with the highest degradation obtained at pH between 2.6 and 3. The first-order rate constant decreased in the following order: sono-electroFenton>Fenton>sonolysis. The rate constant for AB degradation by sono-electroFenton is ∼10-fold that of sonolysis and ∼2-fold the one obtained by Fenton under silent conditions. The chemical oxygen demand was abated ∼68% and ∼85% by Fenton and sono-electroFenton respectively, achieving AB concentration removal over 90% with both processes. Copyright © 2011 Elsevier B.V. All rights reserved.

Investigation and kinetic evaluation of the reactions of hydroxymethylfurfural with amino and thiol groups of amino acids.

PubMed

Hamzalıoğlu, Aytül; Gökmen, Vural

2018-02-01

In this study, reactions of hydroxymethylfurfural (HMF) with selected amino acids (arginine, cysteine and lysine) were investigated in HMF-amino acid (high moisture) and Coffee-amino acid (low moisture) model systems at 5, 25 and 50°C. The results revealed that HMF reacted efficiently and effectively with amino acids in both high and low moisture model systems. High-resolution mass spectrometry (HRMS) analyses of the reaction mixtures confirmed the formations of Michael adduct and Schiff base of HMF with amino acids. Calculated pseudo-first order reaction rate constants were in the following order; k Cysteine >k Arginine >k Lysine for high moisture model systems. Comparing to these rate constants, the k Cysteine decreased whereas, k Arginine and k Lysine increased under the low moisture conditions of Coffee-amino acid model systems. The temperature dependence of the rate constants was found to obey the Arrhenius law in a temperature range of 5-50°C under both low and high moisture conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

The rate of sulfide oxidation by δMnO 2 in seawater

NASA Astrophysics Data System (ADS)

Yao, Wensheng; Millero, Frank J.

1993-07-01

The rate of oxidation of hydrogen sulfide by manganese dioxide in seawater was determined as a function of pH (2.0-9.0), temperature (5-45°C), and ionic strength (0-4 M). The overall rate constant, k, in seawater at pH = 8.17 was found to be first order with respect to both sulfide and manganese dioxide: - d[H 2S] T/dt = k[H 2S] τ[MnO 2] . The rate constant, k, for seawater (S = 35.8, pH = 8.17) at 25°C was found to be 436 M -1 min -1, or 0.0244 m -2 1 min -1 when [MnO 2] is expressed in surface area (m 2/L). The energies of activation were found to be 14 ± 1 KJ mol -1 and 10 ± 1 KJ mol -1, respectively, for pH = 8.2 and pH = 5.0 in seawater (S = 35). The rate increased from pH 2.0 to a maximum at a pH of about 5.0 and decreased at higher pH. This pH dependence was attributed to formation of a surface complex between >MnO - and H 2S. As the concentration of HS - increases above pH = 5 the rate of the reaction decreases. The rate of sulfide oxidation by MnO 2 is not strongly dependent on ionic strength. The rates in 0.57 M NaCl were found to be slightly higher than the rates in seawater. Measurements made in solutions of the major sea salts indicated that Ca 2+ and Mg 2+ caused the rates to decrease, apparently by absorbing on the surface of manganese dioxide. Measurements made in artificial seawater (Na +, Mg 2+, Ca 2+, Cl -, and SO 2-4) were found to be in good agreement with the measurements in actual seawater. Phosphate was found to inhibit the reaction significantly.

Behaviour of aqueous sulfamethizole solution and temperature effects in cold plasma oxidation treatment.

PubMed

Sokolov, Alexander; Louhi-Kultanen, Marjatta

2018-06-07

The increase in volume and variety of pharmaceuticals found in natural water bodies has become an increasingly serious environmental problem. The implementation of cold plasma technology, specifically gas-phase pulsed corona discharge (PCD), for sulfamethizole abatement was studied in the present work. It was observed that sulfamethizole is easily oxidized by PCD. The flow rate and pH of the solution have no significant effect on the oxidation. Treatment at low pulse repetition frequency is preferable from the energy efficiency point of view but is more time-consuming. The maximum energy efficiency was around 120 g/kWh at half-life and around 50 g/kWh at the end of the treatment. Increasing the solution temperature from room temperature to 50 °C led to a significant reaction retardation of the process and decrease in energy efficiency. The pseudo-first order reaction rate constant (k 1 ) grows with increase in pulse repetition frequency and does not depend on pH. By contrast, decreasing frequency leads to a reduction of the second order reaction rate constant (k 2 ). At elevated temperature of 50 °C, the k 1 , k 2 values decrease 2 and 2.9 times at 50 pps and 500 pps respectively. Lower temperature of 10 °C had no effect on oxidation efficiency compared with room temperature.

Dynamics of chest wall volume regulation during constant work rate exercise in patients with chronic obstructive pulmonary disease

PubMed Central

Takara, L.S.; Cunha, T.M.; Barbosa, P.; Rodrigues, M.K.; Oliveira, M.F.; Nery, L.E.; Neder, J.A.

2012-01-01

This study evaluated the dynamic behavior of total and compartmental chest wall volumes [(VCW) = rib cage (VRC) + abdomen (VAB)] as measured breath-by-breath by optoelectronic plethysmography during constant-load exercise in patients with stable chronic obstructive pulmonary disease. Thirty males (GOLD stages II-III) underwent a cardiopulmonary exercise test to the limit of tolerance (Tlim) at 75% of peak work rate on an electronically braked cycle ergometer. Exercise-induced dynamic hyperinflation was considered to be present when end-expiratory (EE) VCW increased in relation to resting values. There was a noticeable heterogeneity in the patterns of VCW regulation as EEVCW increased non-linearly in 17/30 “hyperinflators” and decreased in 13/30 “non-hyperinflators” (P < 0.05). EEVAB decreased slightly in 8 of the “hyperinflators”, thereby reducing and slowing the rate of increase in end-inspiratory (EI) VCW (P < 0.05). In contrast, decreases in EEVCW in the “non-hyperinflators” were due to the combination of stable EEVRC with marked reductions in EEVAB. These patients showed lower EIVCW and end-exercise dyspnea scores but longer Tlim than their counterparts (P < 0.05). Dyspnea increased and Tlim decreased non-linearly with a faster rate of increase in EIVCW regardless of the presence or absence of dynamic hyperinflation (P < 0.001). However, no significant between-group differences were observed in metabolic, pulmonary gas exchange and cardiovascular responses to exercise. Chest wall volumes are continuously regulated during exercise in order to postpone (or even avoid) their migration to higher operating volumes in patients with COPD, a dynamic process that is strongly dependent on the behavior of the abdominal compartment. PMID:23250012

Pheromone lures to monitor sparse populations of spruce budworm, Choristoneura fumiferana (Lepidoptera: Tortricidae)

Treesearch

David G. Grimble

1988-01-01

Four types of spruce budworm pheromone lures were field-tested in sparse spruce budworm populations in Maine. BioLures® with constant pheromone emission rates less than 1.0, ca. 1.0-1.5, and ca. 15.0 micrograms of pheromone per day were compared to polyvinyl chloride (PVC) lures with rapidly decreasing pheromone emission rates. Mean trap catch was roughly proportional...

Decline in stroke mortality in North Carolina. Description, predictions, and a possible underlying cause.

PubMed

Howard, G

1993-09-01

Data from the National Center for Health Statistics were used to describe the decline in age-adjusted stroke mortality rates from 1962 to 1987 for North Carolina and for six regions of the state. For the state as a whole, stroke mortality decreased from 0.0050 to 0.0018 (64% decrease) for white males, 0.0039 to 0.0016 (59% decrease) for white females, 0.0072 to 0.0030 (58% decrease) for black males, and 0.0064 to 0.0025 (61% decrease) for black females. Under the hypothesis that the rate of decline in stroke mortality will slow and approach a "floor," a four-parameter logistic model was fit to the data. This model suggests that most of the decline in North Carolina stroke rates had occurred by 1987 and that the rates are now approaching the floor. For example, the estimated 1987 white male stroke mortality rate was 0.00190 and the floor 0.00176, suggesting only a 7% decline in the future. Similar percentage differences between 1987 levels and the floor were estimated for the three other race-gender groups. This analysis also suggested that while the absolute disparity by sex and race decreased between 1962 and 1987, the ratio of black to white mortality rates and the ratio of male to female mortality rates remained relatively constant. Estimates of 1-year case-fatality rates from two surveys of hospitalized stroke patients in a high-mortality five-county region of North Carolina decreased from 51% in 1970 to 38% in 1980. This decrease in stroke fatality rate is sufficient to account for 64% of the decrease in mortality estimated for this region over the same period.

[Effects of different drying methods on processing performance and quality in bulbus of Tulipa edulis].

PubMed

Yang, Xiao-hua; Guo, Qiao-sheng; Zhu, Zai-biao; Chen, Jun; Miao, Yuan-yuan; Yang, Ying; Sun, Yuan

2015-10-01

Effects of different drying methods including sun drying, steamed, boiled, constant temperature drying (at 40, 50, 60 °C) on appearance, hardness, rehydration ratio, dry rate, moisture, total ash, extractive and polysaccharides contents were studied to provide the basis of standard processing method for Tulipa edulis bulbus. The results showed that the treatments of sun drying and 40 °C drying showed higher rehydration ratios, but lower dry rate, higher hardness, worse color, longer time and obvious distortion and shrinkage in comparison with other drying methods. The treatments of 60 °C constant temperature drying resulted in shorter drying time, lower water and higher polysaccharides content. Drying time is shorter and appearance quality is better in the treatment of steaming and boiling compared with other treatments, but the content of extractive and polysaccharides decreased significantly. The treatments of 50 °C constant temperature drying led to similar appearance quality of bulb to commercial bulb, and it resulted in lowest hardness and highest dry rate as well as higher rehydration ratio, extractive and polysaccharides content, moderate moisture and total ash contents among these treatments. Based on the results obtained, 50 °C constant temperature drying is the better way for the processing of T. edulis bulbus.

The Viscoelastic Properties of Nematic Monodomains Containing Liquid Crystal Polymers.

NASA Astrophysics Data System (ADS)

Gu, Dongfeng

The work presented here investigates the viscoelastic properties of nematic materials containing liquid crystal polymers (LCP). We focus on how the elastic constants and the viscosity coefficients of the mixture systems are influenced by polymer architectures. In dynamic light scattering studies of the relaxation of the director orientation fluctuations for the splay, twist, and bend deformation modes, decrease of the relaxation rates was observed when LCPs were dissolved into low molar mass nematics (LMMN). For the side-chain LCPs, the slowing down in the bend mode is comparable to or larger than those of the splay and twist modes. For main-chain LCPs, the relative changes in the relaxation rates for the twist and splay modes are about one order of magnitude larger than that for the bend mode. The results of light scattering under an electric field show that the decrease in the twist relaxation rate is due to a large increase in the twist viscosity and a minor decrease in the twist elastic constant. These changes were found to increase with decrease of the spacer length, with increase of molecular weight, and with decrease of the backbone flexibility. In Freedericksz transition measurements, the splay and bend elastic constants and the dielectric anisotropies of the nematic mixtures were determined and the values are 5~15% lower than those of the pure solvent. From the analysis of the results of Freedericksz transition and light scattering experiments, a complete set of the elastic constants and viscosity coefficients corresponding to the three director deformation modes were obtained for the LCP mixtures. The changes in the viscosity coefficients due to addition of LCPs were analysed to estimate the anisotropic shapes of the polymer backbone via a hydrodynamic model. The results suggest that an oblate backbone configuration is maintained by the side-chain LCPs and a prolate chain configuration appears for the main-chain LCPs. The rheological behavior of a side-chain and a main-chain LCP nematic solutions were investigated. The addition of the side-chain LCP into a flow-aligning LMMN (5CB) induces director tumbling in the mixture, and, the dissolution of the main-chain LCP into a director tumbling LMMN (8CB) makes the solution become a flow-aligning nematic. Based on the hydrodynamic theory, these observations are further confirmation of the chain anisotropies of the LCPs investigated. Ericksen's transversely isotropic fluid model was used to extract the various viscosity coefficients with good accuracy. In addition, we believe that this is the first time the bulk rheological consequences of director tumbling in LMMNs has been observed.

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 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 SPMBs was also similar. The rates of uptake generally increased or decreased with increasing KOW, depending on the assumption of presence or absence of TOC.

Use of an Impedance Threshold Device in Spontaneously Breathing Patients with Hypotension Secondary to Trauma: An Observational Cohort Feasibility Study

DTIC Science & Technology

2014-09-09

hypotensive patient. Crystalloid infusion is not necessarily benign.1,2 Difficult vascular access, hemodilution, acidosis , decreased oxygen delivery, and...blood pressure, heart rate (HR), respiratory rate, and arterial oxygen saturation (SpO2) were recorded im- mediately before application of the ITD...per minute (p = 0.007). The respiratory rate was constant: 19 (7) breaths before to 18 (4) breaths (p = 0.31) per minute after ITD use. Oxygen

Reliability Growth in Space Life Support Systems

NASA Technical Reports Server (NTRS)

Jones, Harry W.

2014-01-01

A hardware system's failure rate often increases over time due to wear and aging, but not always. Some systems instead show reliability growth, a decreasing failure rate with time, due to effective failure analysis and remedial hardware upgrades. Reliability grows when failure causes are removed by improved design. A mathematical reliability growth model allows the reliability growth rate to be computed from the failure data. The space shuttle was extensively maintained, refurbished, and upgraded after each flight and it experienced significant reliability growth during its operational life. In contrast, the International Space Station (ISS) is much more difficult to maintain and upgrade and its failure rate has been constant over time. The ISS Carbon Dioxide Removal Assembly (CDRA) reliability has slightly decreased. Failures on ISS and with the ISS CDRA continue to be a challenge.

Capture of shrinking targets with realistic shrink patterns.

PubMed

Hoffmann, Errol R; Chan, Alan H S; Dizmen, Coskun

2013-01-01

Previous research [Hoffmann, E. R. 2011. "Capture of Shrinking Targets." Ergonomics 54 (6): 519-530] reported experiments for capture of shrinking targets where the target decreased in size at a uniform rate. This work extended this research for targets having a shrink-size versus time pattern that of an aircraft receding from an observer. In Experiment 1, the time to capture the target in this case was well correlated in terms of Fitts' index of difficulty, measured at the time of capture of the target, a result that is in agreement with the 'balanced' model of Johnson and Hart [Johnson, W. W., and Hart, S. G. 1987. "Step Tracking Shrinking Targets." Proceedings of the human factors society 31st annual meeting, New York City, October 1987, 248-252]. Experiment 2 measured the probability of target capture for varying initial target sizes and target shrink rates constant, defined as the time for the target to shrink to half its initial size. Data of shrink time constant for 50% probability of capture were related to initial target size but did not greatly affect target capture as the rate of target shrinking decreased rapidly with time.

Periphyton biofilms influence net methylmercury production in an industrially contaminated system

DOE PAGES

Olsen, Todd Andrew; Brandt, Craig C.; Brooks, Scott C.

2016-09-12

Mercury (Hg) methylation and methylmercury (MMHg) demethylation activity of periphyton biofilms from East Fork Poplar Creek, Tennessee, USA (EFPC) were measured during 2014-2015 using stable Hg isotopic rate assays. 201Hg II and MM 202Hg were added to intact periphyton samples and the formation of MM 201Hg and loss of MM 202Hg were monitored over time and used to calculate first-order rate constants for methylation and demethylation, respectively. The influence of location, temperature/season, light exposure and biofilm structure on methylation and demethylation were examined. Between-site differences in net methylation for samples collected from an upstream versus downstream location were driven bymore » differences in the demethylation rate constant (k d). In contrast, the within-site seasonal difference in net methylation was driven by changes in the methylation rate constant (k m). Samples incubated in the dark had lower net methylation due to km values that were 60% less than those incubated in the light. Disrupting the biofilm structure decreased km by 50% and resulted in net demethylating conditions. Overall, the measured rates resulted in a net excess of MMHg generated which could account for 27-85% of the MMHg flux in EFPC and suggests intact, actively photosynthesizing periphyton biofilms harbor zones of MMHg production.« less

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

NASA Astrophysics Data System (ADS)

Millero, Frank J.

1985-02-01

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

The Cancer Pattern in Africans at Bargwanath Hospital, Johannesburg†

PubMed Central

Robertson, M. A.; Harington, J. S.; Bradshaw, Evelyn

1971-01-01

Material on African cancer cases admitted to Baragwanath Hospital, Johannesburg, over the years 1948-64 has been analysed, and it has been possible to obtain a useful incidence rate, a ratio study and a tribal analysis for purposes of comparison. The incidence rate, when compared to an earlier Johannesburg survey, showed a rise in oesophageal cancers for males and females. Both lung and prostate cancers showed rising rates in the men, while the female breast and cervix cancer rates remained relatively constant. Liver cancers had decreased in both sexes. PMID:5144511

Influence of excitons interaction with charge carriers on photovoltaic parameters in organic solar cells

NASA Astrophysics Data System (ADS)

Głowienka, Damian; Szmytkowski, Jędrzej

2018-03-01

We report on theoretical analysis of excitons annihilation on charge carriers in organic solar cells. Numerical calculations based on transient one-dimensional drift-diffusion model have been carried out. An impact of three quantities (an annihilation rate constant, an exciton mobility and a recombination reduction factor) on current density and concentrations of charge carriers and excitons is investigated. Finally, we discuss the influence of excitons interaction with electrons and holes on four photovoltaic parameters (a short-circuit current, an open-circuit voltage, a fill factor and a power conversion efficiency). The conclusion is that the annihilation process visibly decreases the efficiency of organic photocells, if the annihilation rate constant is greater than 10-15m3s-1 .

Influence of fluids on the abrasion of silicon by diamond

NASA Technical Reports Server (NTRS)

Danyluk, S.

1982-01-01

Silicon wafers ((100)-p-type) were abraded at room temperature in acetone, absolute ethanol and water by a pyramid diamond and the resulting groove depth was measured as a function of normal force on the diamond and the absorbed fluids, while all other experimental conditions were held constant. The groove depth rates are in the ratio of 1:2:3 for water, absolute ethanol, and acetone, respectively, for a constant normal force. The groove depth rate is lower when the normal force is decreased. The silicon abraded in the presence of water was chipped as expected for a classical brittle material while the surfaces abraded in the other two fluids showed ductile ploughing as the main mechanism for silicon removal.

38 CFR 4.115a - Ratings of the genitourinary system-dysfunctions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... precluding more than sedentary activity from one of the following: persistent edema and albuminuria; or, BUN... organ systems, estpecially cardiovascular 100 Persistent edema and albuminuria with BUN 40 to 80mg%; or..., or limitation of exertion 80 Constant albuminuria with some edema; or, definite decrease in kidney...

Kinetic and mechanistic analysis of dinucleotide and oligonucleotide formation from the 5'-phosphorimidazolide of adenosine on Na(+)-montmorillonite

NASA Technical Reports Server (NTRS)

Kawamura, K.; Ferris, J. P.

1994-01-01

The rate constants for the condensation reaction of the 5'-phosphorimidazolide of adenosine (ImpA) to form dinucleotides and oligonucleotides have been measured in the presence of Na(+)-volclay (a Na(+)-montmorillonite) in pH 8 aqueous solution at 25 degrees C. The rates of the reaction of ImpA with an excess of adenosine 5'-monophosphoramidate (NH2pA), P1,P2-diadenosine 5',5'-pyrophosphate (A5'ppA), or adenosine 5'-monophosphate (5'-AMP or pA) in the presence of the montmorillonite to form NH2pA3'pA, A5'ppA3'pA, and pA3'pA, respectively, were measured. Only 3',5'-linked products were observed. The magnitude of the rate constants decrease in the order NH2pA3'pA > A5'-ppA3'pA > pA3'pA. The binding of ImpA to montmorillonite was measured, and the adsorption isotherm was determined. The binding of ImpA to montmorillonite and the formation of higher oligonucleotides is not observed in the absence of salts. Mg2+ enhances binding and oligonucleotide formation more than Ca2+ and Na+. The rate constants for the oligonucleotide formation were determined from the reaction products formed from 10 to 40 mM ImpA in the presence of Na(+)-montmorillonite using the computer program SIMFIT. The magnitudes of the rate constants for the formation of oligonucleotides increased in the order 2-mer < 3-mer < 4-mer ... 7-mer. The rate constants for dinucleotide and trinucleotide formation are more than 1000 times larger than those measured in the absence of montmorillonite. The rate constants for the formation of dinucleotide, trinucleotide, and tetranucleotide are 41,2.6, and 3.7 times larger than those for the formation of oligo(G)s with a poly(C) template. The hydrolysis of ImpA was accelerated 35 times in the presence of the montmorillonite. The catalytic ability of montmorillonite to form dinucleotides and oligonucleotides is quantitatively evaluated and possible pathways for oligo(A) formation are proposed.

Determinants of relaxation rate in rabbit skinned skeletal muscle fibres

PubMed Central

Luo, Ye; Davis, Jonathan P; Smillie, Lawrence B; Rall, Jack A

2002-01-01

The influence of Ca2+-activated force, the rate of dissociation of Ca2+ from troponin C (TnC) and decreased crossbridge detachment rate on the time course of relaxation induced by flash photolysis of diazo-2 in rabbit skinned psoas fibres was investigated at 15 °C. The rate of relaxation increased as the diazo-2 chelating capacity (i.e. free [diazo-2]/free [Ca2+]) increased. At a constant diazo-2 chelating capacity, the rate of relaxation was independent of the pre-photolysis Ca2+-activated force in the range 0.3-0.8 of maximum isometric force. A TnC mutant that exhibited increased Ca2+ sensitivity caused by a decreased Ca2+ dissociation rate in solution (M82Q TnC) also increased the Ca2+ sensitivity of steady-state force and decreased the rate of relaxation in fibres by approximately twofold. In contrast, a TnC mutant with decreased Ca2+ sensitivity caused by an increased Ca2+ dissociation rate in solution (NHdel TnC) decreased the Ca2+ sensitivity of steady-state force but did not accelerate relaxation. Decreasing the rate of crossbridge kinetics by reducing intracellular inorganic phosphate concentration ([Pi]) slowed relaxation by approximately twofold and led to two phases of relaxation, a slow linear phase followed by a fast exponential phase. In fibres, M82Q TnC further slowed relaxation in low [Pi] conditions by approximately twofold, whereas NHdel TnC had no significant effect on relaxation. These results are consistent with the interpretation that the Ca2+-dissociation rate and crossbridge detachment rate are similar in fast-twitch skeletal muscle, such that decreasing either rate slows relaxation, but accelerating Ca2+ dissociation has little effect on relaxation. PMID:12482894

Particle loading time and humidity effects on the efficiency of an N95 filtering facepiece respirator model under constant and inhalation cyclic flows.

PubMed

Mahdavi, Alireza; Haghighat, Fariborz; Bahloul, Ali; Brochot, Clothilde; Ostiguy, Claude

2015-06-01

It is necessary to investigate the efficiencies of filtering facepiece respirators (FFRs) exposed to ultrafine particles (UFPs) for long periods of time, since the particle loading time may potentially affect the efficiency of FFRs. This article aims to investigate the filtration efficiency for a model of electrostatic N95 FFRs with constant and 'inhalation-only' cyclic flows, in terms of particle loading time effect, using different humidity conditions. Filters were exposed to generated polydisperse NaCl particles. Experiments were performed mimicking an 'inhalation-only' scenario with a cyclic flow of 85 l min(-1) as the minute volume [or 170 l min(-1) as mean inhalation flow (MIF)] and for two constant flows of 85 and 170 l min(-1), under three relative humidity (RH) levels of 10, 50, and 80%. Each test was performed for loading time periods of 6h and the particle penetration (10-205.4nm in electrical mobility diameter) was measured once every 2h. For a 10% RH, the penetration of smaller size particles (<80nm), including the most penetrating particle size (MPPS), decreased over time for both constant and cyclic flows. For 50 and 80% RH levels, the changes in penetration were typically observed in an opposite direction with less magnitude. The penetrations at MPPS increased with respect to loading time under constant flow conditions (85 and 170 l min(-1)): it did not substantially increase under cyclic flows. The comparison of the cyclic flow (85 l min(-1) as minute volume) and constant flow equal to the cyclic flow minute volume indicated that, for all conditions the penetration was significantly less for the constant flow than that of cyclic flow. The comparison between the cyclic (170 l min(-1) as MIF) and constant flow equal to cyclic flow MIF indicated that, for the initial stage of loading, the penetrations were almost equal, but they were different for the final stages of the loading time. For a 10% RH, the penetration of a wide range of sizes was observed to be higher with the cyclic flow (170 as MIF) than with the equivalent constant flow (170 l min(-1)). For 50 and 80% RH levels, the penetrations were usually greater with a constant flow (170 l min(-1)) than with a cyclic flow (170 l min(-1) as MIF). It is concluded that, for the tested electrostatic N95 filters, the change in penetration as a function of the loading time does not necessarily take place with the same rate under constant (MIF) and cyclic flow. Moreover, for all tested flow rates, the penetration is not only affected by the loading time but also by the RH level. Lower RH levels (10%) have decreasing penetration rates in terms of loading time, while higher RH levels (50 and 80%) have increasing penetration rates. Also, the loading of the filter is normally accompanied with a shift of MPPS towards larger sizes. © The Author 2015. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

Fatigue and Creep Crack Propagation behaviour of Alloy 617 in the Annealed and Aged Conditions

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

Julian K. Benz; Richard N. Wright

2013-10-01

The crack propagation behaviour of Alloy 617 was studied under various conditions. Elevated temperature fatigue and creep-fatigue crack growth experiments were conducted at 650 and 800 degrees C under constant stress intensity (triangle K) conditions and triangular or trapezoidal waveforms at various frequencies on as-received, aged, and carburized material. Environmental conditions included both laboratory air and characteristic VHTR impure helium. As-received Alloy 617 displayed an increase in the crack growth rate (da/dN) as the frequency was decreased in air which indicated a time-dependent contribution component in fatigue crack propagation. Material aged at 650°C did not display any influence on themore » fatigue crack growth rates nor the increasing trend of crack growth rate with decreasing frequency even though significant microstructural evolution, including y’ (Ni3Al) after short times, occurred during aging. In contrast, carburized Alloy 617 showed an increase in crack growth rates at all frequencies tested compared to the material in the standard annealed condition. Crack growth studies under quasi-constant K (i.e. creep) conditions were also completed at 650 degrees C and a stress intensity of K = 40 MPa9 (square root)m. The results indicate that crack growth is primarily intergranular and increased creep crack growth rates exist in the impure helium environment when compared to the results in laboratory air. Furthermore, the propagation rates (da/dt) continually increased for the duration of the creep crack growth either due to material aging or evolution of a crack tip creep zone. Finally, fatigue crack propagation tests at 800 degrees C on annealed Alloy 617 indicated that crack propagation rates were higher in air than impure helium at the largest frequencies and lowest stress intensities. The rates in helium, however, eventually surpass the rates in air as the frequency is reduced and the stress intensity is decreased which was not observed at 650 degrees C.« less

Bioconcentration of perfluoroalkyl substances by Chironomus plumosus larvae in water with different types of dissolved organic matters.

PubMed

Wen, Wu; Xia, Xinghui; Chen, Xi; Wang, Haotian; Zhu, Baotong; Li, Husheng; Li, Yang

2016-06-01

The effects of four types of dissolved organic matters (DOM) on the bioconcentration of perfluoroalkyl substances (PFASs) in Chironomus plumosus larvae have been studied. The PFASs included perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA). The DOM included humic acid (HA), fulvic acid (FA), tannic acid (TA), and a protein, peptone (PEP), and their concentrations ranged from 0 to 50 mg L(-1). The results showed that, upon bioconcentration equilibrium, the body burdens of longer perfluoroalkyl chain PFASs (PFOS, PFDA, PFUnA and PFDoA) decreased with PEP and HA concentrations while increased with FA and TA concentrations. When FA and TA concentrations increased from 0 to 50 mg L(-1), body burdens of these PFASs increased by 7.5%-148.8% and 5.7%-37.1%, respectively. However, the DOM had no significant impact on the body burdens of shorter perfluoroalkyl chain PFASs (PFOA and PFNA). All of the four types of DOM lowered not only the uptake rate constants (ku) of PFASs due to the decrease of freely dissolved PFAS concentrations, but also the elimination rate constants (ke) due to the inhibition effect of DOM on the PFAS elimination from the larvae. The reduction in the two constants varied with both DOM and PFAS types. In the presence of PEP and HA with larger molecular weights, the ku values decreased more than ke, leading to the decreased body burdens of longer perfluoroalkyl chain PFASs. As for FA and TA with smaller molecular weights, the ke values decreased more than ku, resulting in increased body burdens of longer perfluoroalkyl chain PFASs. This study suggests that the effects of DOM on PFAS bioconcentration depend not only on the concentration but also on the molecule weight of DOM, which should be considered in the bioavailability assessment of PFASs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Transient kinetic studies of pH-dependent hydrolyses by exo-type carboxypeptidase P on a 27-MHz quartz crystal microbalance.

PubMed

Furusawa, Hiroyuki; Takano, Hiroki; Okahata, Yoshio

2008-02-15

pH-Dependent kinetic parameters (k(on), k(off), and k(cat)) of protein (myoglobin) hydrolyses catalyzed by exo-enzyme (carboxypeptidase P, CPP) were obtained by using a protein-immobilized quartz crystal microbalance (QCM) in acidic aqueous solutions. The formation of the enzyme-substrate (ES) complex (k(on)), the decay of the ES complex (k(off)), and the formation of the product (k(cat)) could be analyzed by transient kinetics as mass changes on the QCM plate. The Kd (k(off)/k(on)) value was different from the Michaelis constant Km calculated from (k(off) + k(cat))/k(on) due to k(cat) > k(off). The rate-determining step was the binding step (k(on), and the catalytic rate k(cat) was faster than other k(on) and k(off) values. In the range of pH 2.5-5.0, values of k(on) gradually increased with decreasing pH showing a maximum at pH 3.7, values of k(off) were independent of pH, and k(cat) increased gradually with decreasing pH. As a result, the apparent rate constant (k(cat)/Km) showed a maximum at pH 3.7 and gradually increased with decreasing pH. The optimum pH at 3.7 of k(on) is explained by the optimum binding ability of CPP to the COOH terminus of the substrate with hydrogen bonds. The increase of k(cat) at the lower pH correlated with the decrease of alpha-helix contents of the myoglobin substrate on the QCM.

Initial reactive sticking coefficient of O 2 on Si(111)-7 × 7 at elevated temperatures

NASA Astrophysics Data System (ADS)

Shklyaev, A. A.; Suzuki, Takanori

1996-05-01

Kinetics of the initial stage of oxide growth in the reaction of oxygen with Si(111)-7 × 7 at temperatures from room temperature to Ttr, and pressures from 5 × 10 -9 to 2 × 10 -7 Torr are investigated with optical second-harmonic generation, here temperature from oxide growth to Si etching without oxide growth. At a fixed pressure, the initial reactive sticking coefficient ( S0), obtained from the rate of oxide growth, decreases with increasing temperature to S0=0 at Ttr. We have found that the initial reacti sticking coefficient depends on the O 2 pressure. At temperatures above 320°C, the whole temperature dependence of S0 is situated in the region of higher temperatures for higher O 2 pressures ( Pox). Moreover, an additional bend in the temperature dependence of S0 is observed for Pox>1 × 10 -8 Torr near Ttr. A precursor-mediated adsorption model involving the reaction of formation is considered. The parameters of this model, obtained from the best fits to the experimental data, show that oxide growth rate constant increases and volatile SiO formation rate constant decreases as a function of O 2 pressure. At zero oxide coverage, the pressure dependence of the reaction rate constants is suggested to originate from interaction in the layer of the chemisorbed precursor species, whose coverage depends on the O 2 pressure. The volatile SiO formation is described by a three-step sequential two-channel process through the chemisorbed O 2 precursor species, whereas one of the channels with a larger activation energy is suggested to induce the additional bend in S0( T) near Ttr at higher O 2 pressures.

Theoretical Kinetic Study of the Unimolecular Keto-Enol Tautomerism Propen-2-ol ↔ Acetone. Pressure Effects and Implications in the Pyrolysis of tert- and 2-Butanol.

PubMed

Grajales-González, E; Monge-Palacios, M; Sarathy, S Mani

2018-04-12

The need for renewable and cleaner sources of energy has made biofuels an interesting alternative to fossil fuels, especially in the case of butanol isomers, with its favorable blend properties and low hygroscopicity. Although C 4 alcohols are prospective fuels, some key reactions governing their pyrolysis and combustion have not been adequately studied, leading to incomplete kinetic models. Enols are important intermediates in the combustion of C 4 alcohols, as well as in atmospheric processes. Butanol reactions kinetics is poorly understood. Specifically, the unimolecular tautomerism of propen-2-ol ↔ acetone, which is included in butanol combustion kinetic models, is assigned rate parameters based on the tautomerism vinyl alcohol ↔ acetaldehyde as an analogy. In an attempt to update current kinetic models for tert- and 2-butanol, a theoretical kinetic study of the titled reaction was carried out by means of CCSD(T,FULL)/aug-cc-pVTZ//CCSD(T)/6-31+G(d,p) ab initio calculations, with multistructural torsional anharmonicity and variational transition state theory considerations in a wide temperature and pressure range (200-3000 K; 0.1-10 8 kPa). Results differ from vinyl alcohol ↔ acetaldehyde analogue reaction, which shows lower rate constant values. It was observed that decreasing pressure leads to a decrease in rate constants, describing the expected falloff behavior. Tunneling turned out to be important, especially at low temperatures. Accordingly, pyrolysis simulations in a batch reactor for tert- and 2-butanol with computed rate constants showed important differences in comparison with previous results, such as larger acetone yield and quicker propen-2-ol consumption.

Comparison between Slow Components of HR and V[Combining Dot Above]O2 Kinetics: Functional Significance.

PubMed

Zuccarelli, Lucrezia; Porcelli, Simone; Rasica, Letizia; Marzorati, Mauro; Grassi, Bruno

2018-03-22

Aerobic exercise prescription is often based on a linear relationship between pulmonary oxygen consumption (V[Combining Dot Above]O2) and heart rate (HR). The aim of the present study was to test the hypothesis that during constant work rate (CWR) exercises at different intensities the slow component of HR kinetics occurs at lower work rate and is more pronounced that the slow component of V[Combining Dot Above]O2 kinetics. Seventeen male (age, 27±4yr) subjects performed on a cycle ergometer an incremental exercise to voluntary exhaustion and several CWR exercises: 1) moderate CWR exercises (MODERATE), below gas exchange threshold (GET); 2) heavy CWR exercise (HEAVY), at 45% of the difference between GET and V[Combining Dot Above]O2 peak (□); 3) severe CWR exercise (SEVERE), at 95% of Δ; 4) "HRCLAMPED" exercise in which work rate was continuously adjusted to maintain a constant HR, slightly higher than that determined at GET. Breath-by-breath V[Combining Dot Above]O2, HR and other variables were determined. In MODERATE, no slow component of V[Combining Dot Above]O2 kinetics was observed, whereas a slow component with a relative amplitude (with respect to the total response) of 24.8±11.0% was observed for HR kinetics. During HEAVY, the relative amplitude of the HR slow component was more pronounced than that for V[Combining Dot Above]O2 (31.6±11.2 and 23.3±9.0%, respectively). During HRCLAMPED the decrease in work rate (~14%) needed in order to maintain a constant HR was associated with a decreased V[Combining Dot Above]O2 (~10%). The HR slow component occurred at a lower work rate and was more pronounced than the V[Combining Dot Above]O2 slow component. Exercise prescriptions at specific HR values, when carried out for periods longer than a few minutes, could lead to premature fatigue.

The influence of double-diffusive processes on the melting of ice in the Arctic Ocean: laboratory analogue experiments and their interpretation

NASA Astrophysics Data System (ADS)

Turner, J. S.; Veronis, G.

2004-03-01

This study has been motivated by two oceanographic observations: an increased rate of melting of sea ice in the Arctic Ocean, and the advance of an anomalously warm tongue of Atlantic water across the Arctic below the halocline over the last few decades. A series of laboratory experiments has been carried out in order to explore the physical principles underlying these phenomena, and the possibility that the extra heating at depth is responsible for the enhanced melting rate. A tank was filled with salt solution having various constant vertical density gradients. A block of ice one third of the length of the tank was floated on the surface at one end, and the rest of the surface and the walls of the tank were insulated. When no extra heat was supplied the melting rate (loss of weight of the ice in 1 h) systematically decreased as the stratification was changed from homogeneous fluid to increasingly large density gradients, while keeping the salinity of the solution in contact with the ice constant. An analogue of the intruding Atlantic water was produced by heating the lower portion of the vertical end wall at the end of the tank opposite to the ice end, keeping its temperature constant, and using the same range of salinity gradients as in the unheated experiments. Again the melting rate decreased as the density gradient was increased, but for low gradients it was larger than that in the unheated experiments. Above a certain intermediate gradient there was no significant difference in melting rate between the unheated and heated runs. The melting data were supplemented by photographs and vertical temperature and salinity profiles. The upward transfer of heat from the body of the fluid to melt the ice was clearly double-diffusive: overturning layers, separated by 'diffusive' interfaces, were visible on shadowgraphs, and the thickness of the layers decreased as the density gradient increased. The mean thickness of the layers through the depth of the tank also systematically decreased as the density gradient increased. With weak gradients an extra heat flux to the ice came from the intruding heated layer, but at large gradients this tongue of warm water at depth did not add to the flux near the surface. Though they were obtained in a simple, arbitrary and fixed geometry, we believe that the results of these experiments can be used as the basis for a better physical understanding of the melting rates of ice in the Arctic under various conditions.

Exploratory Study on VO2 On-kinetics During Treadmill Walking in Women With Systemic Lupus Erythematosus

PubMed Central

Keyser, Randall E.; Rus, Violeta; Mikdashi, Jamal A.; Handwerger, Barry S.

2010-01-01

Objective To determine if oxygen consumption (VO2) on-kinetics differed between groups of women with systemic lupus erythematosus (SLE) and sedentary but otherwise healthy controls. Design Exploratory case control study. Setting Medical school exercise physiology laboratory. Participants Convenience samples of 12 women with SLE and 10 sedentary but otherwise healthy controls. Intervention None. Main Outcome Measurements VO2 on-kinetics indices including time to steady state, rate constant, mean response time (MRT), transition constant, and oxygen deficit measured during bouts of treadmill walking at intensities of 3-METS and 5-METS. Results Time to steady state and oxygen deficit were increased and rate constant was decreased in the women with SLE compared to controls. At the 5-MET energy demand, the transition constant was lower and MRT was longer in the women with SLE than in the controls. For a comparable, relative energy expenditure that was slightly lower than the anaerobic threshold, the transition constant was higher in the controls than in the women with SLE. Conclusion VO2 on-kinetics was prolonged in the women with SLE. The prolongation was concomitant with an increase in oxygen deficit and may underlie performance fatigability in women with SLE. PMID:20801259

Gamma radiation field intensity meter

DOEpatents

Thacker, Louis H.

1994-01-01

A gamma radiation intensity meter measures dose rate of a radiation field. The gamma radiation intensity meter includes a tritium battery emitting beta rays generating a current which is essentially constant. Dose rate is correlated to an amount of movement of an electroscope element charged by the tritium battery. Ionizing radiation decreases the voltage at the element and causes movement. A bleed resistor is coupled between the electroscope support element or electrode and the ionization chamber wall electrode.

Gamma radiation field intensity meter

DOEpatents

Thacker, Louis H.

1995-01-01

A gamma radiation intensity meter measures dose rate of a radiation field. The gamma radiation intensity meter includes a tritium battery emitting beta rays generating a current which is essentially constant. Dose rate is correlated to an amount of movement of an electroscope element charged by the tritium battery. Ionizing radiation decreases the voltage at the element and causes movement. A bleed resistor is coupled between the electroscope support element or electrode and the ionization chamber wall electrode.

Experimental investigation of time dependent behavior of welded Topopah Spring Tuff

NASA Astrophysics Data System (ADS)

Ma, Lumin

Four types of laboratory tests have been performed. Specimens were attained from four lithophysal zones of the welded Topopah Spring Tuff unit at Yucca Mountain, Nevada: upper lithophysal, middle nonlithophysal, lower lithophysal and lower nonlithophysal zones. Two types of tests are conducted to study time-dependent behavior: constant strain rate and creep tests. Sixty-five specimens from the middle nonlithophysal zone were tested at six strain rates: 10-2, 10-4, 10-5, 10-6, 10-7, and 10-8 s-1. Test durations range from 2 seconds to 7 days. Fourteen specimens from middle nonlithophysal, lower lithophysal and lower nonlithophysal zones are creep tested by incremental stepwise loading. All the tests are conducted under uniaxial compression at room temperature and humidity. Specimens exhibit extremely brittle fracture and fail by axial splitting, and show very little dilatancy if any. It is assumed that microfracturing dominates the inelastic deformation and failure of the tuff. Nonlinear regression is applied to the results of the constant strain rate tests to estimate the relations between peak strength, peak axial strain, secant modulus and strain rate. All three these parameters decrease with a decrease of strain rate and follow power functions: sigmapeak = 271.37 3˙0.0212 0.0212, epsilonpeak = 0.006 3˙0.0083 , ES = 41985.4 3˙0.015 . Secant modulus is introduced mainly as a tool to analyze strain rate dependent axial strain. Two threshold stresses define creep behavior. Below about 50% of peak strength, a specimen does not creep. Above about 94% of peak strength, a specimen creeps at an accelerating rate. Between the two threshold stresses, a power law relates strain rate and stress. One hundred fifty-eight Brazilian (Indirect tensile splitting) tests have been performed at six different constant strain rates. Nineteen lithophysal specimens were tested in uniaxial compression to study their fracture pattern. These specimens have a far less brittle failure mode. They slowly crumble, collapse, and maintain considerable relative strength beyond the peak. Due to the presence of multiple relatively large lithophysal cavities, they are far weaker and softer than the nonlithophysal specimens.

Distribution of tsunami interevent times

NASA Astrophysics Data System (ADS)

Geist, Eric L.; Parsons, Tom

2008-01-01

The distribution of tsunami interevent times is analyzed using global and site-specific (Hilo, Hawaii) tsunami catalogs. An empirical probability density distribution is determined by binning the observed interevent times during a period in which the observation rate is approximately constant. The empirical distributions for both catalogs exhibit non-Poissonian behavior in which there is an abundance of short interevent times compared to an exponential distribution. Two types of statistical distributions are used to model this clustering behavior: (1) long-term clustering described by a universal scaling law, and (2) Omori law decay of aftershocks and triggered sources. The empirical and theoretical distributions all imply an increased hazard rate after a tsunami, followed by a gradual decrease with time approaching a constant hazard rate. Examination of tsunami sources suggests that many of the short interevent times are caused by triggered earthquakes, though the triggered events are not necessarily on the same fault.

A multilevel approach to examining cephalopod growth using Octopus pallidus as a model.

PubMed

Semmens, Jayson; Doubleday, Zoë; Hoyle, Kate; Pecl, Gretta

2011-08-15

Many aspects of octopus growth dynamics are poorly understood, particularly in relation to sub-adult or adult growth, muscle fibre dynamics and repro-somatic investment. The growth of 5 month old Octopus pallidus cultured in the laboratory was investigated under three temperature regimes over a 12 week period: seasonally increasing temperatures (14-18°C); seasonally decreasing temperatures (18-14°C); and a constant temperature mid-way between seasonal peaks (16°C). Differences in somatic growth at the whole-animal level, muscle tissue structure and rate of gonad development were investigated. Continuous exponential growth was observed, both at a group and at an individual level, and there was no detectable effect of temperature on whole-animal growth rate. Juvenile growth rate (from 1 to 156 days) was also monitored prior to the controlled experiment; exponential growth was observed, but at a significantly faster rate than in the older experimental animals, suggesting that O. pallidus exhibit a double-exponential two-phase growth pattern. There was considerable variability in size-at-age even between individuals growing under identical thermal regimes. Animals exposed to seasonally decreasing temperatures exhibited a higher rate of gonad development compared with animals exposed to increasing temperatures; however, this did not coincide with a detectable decline in somatic growth rate or mantle condition. The ongoing production of new mitochondria-poor and mitochondria-rich muscle fibres (hyperplasia) was observed, indicated by a decreased or stable mean muscle fibre diameter concurrent with an increase in whole-body size. Animals from both seasonal temperature regimes demonstrated higher rates of new mitochondria-rich fibre generation relative to those from the constant temperature regime, but this difference was not reflected in a difference in growth rate at the whole-body level. This is the first study to record ongoing hyperplasia in the muscle tissue of an octopus species, and provides further insight into the complex growth dynamics of octopus.

A study of the role of renal nerves in the renal responses to 60° head-up tilt in the anaesthetized dog

PubMed Central

DiBona, G. F.; Johns, E. J.

1980-01-01

1. Renal responses to 10 min of 60° head-up tilt were measured in anaesthetized dogs in which renal perfusion pressure was maintained at a relatively constant value. 2. Tilting was associated with a fall in systemic blood pressure and an increase in heart rate. Renal blood flow and glomerular filtration rate remained constant while there was a significant decrease in both absolute and fractional excretion of sodium. 3. Animals which had undergone acute renal denervation were tilted. The cardiovascular responses were similar to intact animals. A fall in renal blood flow was observed but the glomerular filtration rate was maintained at a steady value during tilting. The decreased renal tubular excretion of sodium measured in intact animals was abolished. 4. Alpha-adrenergic blockade of the kidney was achieved by infusion of phentolamine into the renal artery. Tilting of these animals caused cardiovascular changes similar to those observed in control animals but renal blood flow, glomerular filtration rate and sodium handling remained unchanged. 5. Animals in which both carotid sinuses had been acutely denervated were tilted. Systemic blood pressure fell as in intact animals, but the rise in heart rate was significantly less. Renal blood flow, glomerular filtration rate and the rate of sodium excretion were unchanged. 6. A 10 min period of 60° head-up tilt in anaesthetized dogs resulted in an unchanged renal blood flow and glomerular filtration rate which was associated with a decrease in both fractional excretion of sodium and sodium excretion. The renal sympathetic nerves were shown to be responsible for these changes in tubular sodium handling which appeared to exert their action via renal tubular α-adrenergic receptors. This activation of the renal nerves appeared to be mediated by the carotid sinus baroreceptor reflex. PMID:7381761

A comparison of constant acceleration swimming speeds when acceleration rates are different with critical swimming speeds in Chinese bream under two oxygen tensions.

PubMed

Wang, Jian-Wei; Cao, Zhen-Dong; Fu, Shi-Jian

2016-10-01

To investigate the effect of acceleration rates on the constant acceleration test speed (U cat) and to compare U cat with the critical swimming speed (U crit) in Chinese bream (Parabramis pekinensis), the U cat test at acceleration rates of 0.05, 0.1, 0.2, 0.4 and 0.8 cm s(-2) and the U crit test in juvenile fish at 20 °C in either normoxia (>90 % saturation oxygen tension) or hypoxia (30 % saturation) were compared. The lactate concentration ([lactate]) of white muscle, liver and plasma and the glycogen concentration ([glycogen]) of white muscle and liver were also measured to identify whether tissue substrate depletion or tissue lactate accumulation correlated with exhaustion. The U cat decreased with the acceleration rate, and there was no significant difference between U crit and U cat at lower acceleration rates. Hypoxia resulted in lower U cat and U crit, and the difference increased with decreased acceleration rates of the U cat test, possibly due to the increased contribution of aerobic components in U crit or U cat at low acceleration rates. Hypoxia elicited a significant decrease in muscle [glycogen] and an increase in muscle and liver [lactate] in resting fish. All post-exercise fish had similar muscle [lactate], suggesting that tissue lactate accumulation may correlate with exercise exhaustion. Unlike hypoxia, exercise induced an increase in muscle [lactate] and a significant increase in plasma [lactate], which were worthy of further investigation. The similar swimming speed and biochemical indicators after exercise in the U crit and U cat groups at low acceleration rates suggested that U cat can be an alternative for the more frequently adopted protocols in U crit in Chinese bream and possibly in other cyprinid fish species.

SU-E-T-421: Feasibility Study of Volumetric Modulated Arc Therapy with Constant Dose Rate for Endometrial Cancer

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

Yang, R; Wang, J

2014-06-01

Purpose: To investigate the feasibility, efficiency, and delivery accuracy of volumetric modulated arc therapy with constant dose rate (VMAT-CDR) for whole-pelvic radiotherapy (WPRT) of endometrial cancer. Methods: The nine-Field intensity-modulated radiotherapy (IMRT), VMAT with variable dose-rate (VMAT-VDR), and VMAT-CDR plans were created for 9 patients with endometrial cancer undergoing WPRT. The dose distribution of planning target volume (PTV), organs at risk (OARs), and normal tissue (NT) were compared. The monitor units (MUs) and treatment delivery time were also evaluated. For each VMAT-CDR plan, a dry Run was performed to assess the dosimetric accuracy with MatriXX from IBA. Results: Compared withmore » IMRT, the VMAT-CDR plans delivered a slightly greater V20 of the bowel, bladder, pelvis bone, and NT, but significantly decreased the dose to the high-dose region of the rectum and pelvis bone. The MUs Decreased from 1105 with IMRT to 628 with VMAT-CDR. The delivery time also decreased from 9.5 to 3.2 minutes. The average gamma pass rate was 95.6% at the 3%/3 mm criteria with MatriXX pretreatment verification for 9 patients. Conclusion: VMAT-CDR can achieve comparable plan quality with significant shorter delivery time and smaller number of MUs compared with IMRT for patients with endometrial cancer undergoing WPRT. It can be accurately delivered and be an alternative to IMRT on the linear accelerator without VDR capability. This work is supported by the grant project, National Natural; Science Foundation of China (No. 81071237)« less

[Differences in the rate of establishment of permanent estrus in rats after autotransplantation of the ovaries and as affected by other conditions].

PubMed

Smetanina, M D; Vunder, P A

1985-09-01

In adult female rats, constant light leads to the cessation of the sexual cycle and formation of permanent estrus after 6 to 7 days. In young animals, the sexual cycle was retained despite constant light and only after 3 months when the body weight of the rats reached 200-220 g the estrus became permanent. This happened earlier than in animals with the ovaries autotransplanted to the ears. The combination of constant light and autotransplantation of the ovaries caused an earlier formation of permanent estrus. It is marked that the same mechanism (the age-associated decrease of the cyclic center sensitivity to estrogen) underlies permanent estrus of various etiology.

Separation of Gadolinium (Gd) using Synergic Solvent Mixed Topo-D2EHPA with Extraction Method.

NASA Astrophysics Data System (ADS)

Effendy, N.; Basuki, K. T.; Biyantoro, D.; Perwira, N. K.

2018-04-01

The main problem to obtain Gd with high purity is the similarity of chemical properties and physical properties with the other rare earth elements (REE) such as Y and Dy, it is necessary to do separation by the extraction process. The purpose of this research to determine the best solvent type, amount of solvent, feed and solvent ratio in the Gd extraction process, to determine the rate order and the value of the rate constant of Gd concentration based on experimental data of aqueous phase concentration as a function of time and to know the effect of temperature on the reaction speed constant. This research was conducted on variation of solvent, amount of solvent, feed and solvent ratio in the extraction process of Gd separation, extraction time to determine the order value and the rate constant of Gd concentration in extraction process based on the aqueous phase concentration data as a function of time, to the rate constant of decreasing concentration of Gd. Based on the calculation results, the solvent composition was obtained with the best feed to separate the rare earth elements Gd in the extraction process is 1 : 4 with 15% concentration of TOPO and 10% concentration of D2EHPA. The separation process of Gd using extraction method by solvent TOPO-D2EHPA 2 : 1 comparison is better than single solvent D2EHPA / TOPO because of the synergistic effect. The rate order of separation process of Gd follows order 1. The Arrhenius Gd equation becomes k = 1.46 x 10-7 exp (-6.96 kcal / mol / RT).

Hydrogen transfer reactions of interstellar Complex Organic Molecules

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Deciphering the relative weights of demographic transition and vaccination in the decrease of measles incidence in Italy.

PubMed

Merler, Stefano; Ajelli, Marco

2014-02-22

In Italy, during the course of the past century to the present-day, measles incidence underwent a remarkable decreasing trend that started well before the introduction of the national immunization programme. In this work, we aim at examining to what extent both the demographic transition, characterized by declining mortality and fertility rates over time, and the vaccination programme are responsible for the observed epidemiological pattern. Making use of a non-stationary, age-structured disease transmission model, we show that in the pre-vaccination era, from 1901 to 1982, the decline in birth rates has resulted in a drastic decrease in the effective transmission rate, which in turn has determined a declining trend of measles incidence (from 25.2 to 10.3 infections per 1000 individuals). However, since 1983, vaccination appears to have become the major contributing factor in the decrease of measles incidence, which otherwise would have remained stable as a consequence of the nearly constant birth rates. This led to a remarkable decrease in the effective transmission rate, to a level well below the critical threshold for disease persistence. These findings call for the adoption of epidemiological models, which deviate the age structure from stationary equilibrium solutions, to better understand the biology of infectious diseases and evaluate immunization programmes.

Observations on the methane oxidation capacity of landfill soils

USDA-ARS?s Scientific Manuscript database

Field data and two independent models indicate that landfill cover methane (CH4) oxidation should not be considered as a constant 10% or any other single value. Percent oxidation is a decreasing exponential function of the total methane flux rate into the cover and is also dependent on climate and c...

Edge effects on moisture reduce wood decomposition rate in a temperate forest.

PubMed

Crockatt, Martha E; Bebber, Daniel P

2015-02-01

Forests around the world are increasingly fragmented, and edge effects on forest microclimates have the potential to affect ecosystem functions such as carbon and nutrient cycling. Edges tend to be drier and warmer due to the effects of insolation, wind, and evapotranspiration and these gradients can penetrate hundreds of metres into the forest. Litter decomposition is a key component of the carbon cycle, which is largely controlled by saprotrophic fungi that respond to variation in temperature and moisture. However, the impact of forest fragmentation on litter decay is poorly understood. Here, we investigate edge effects on the decay of wood in a temperate forest using an experimental approach, whereby mass loss in wood blocks placed along 100 m transects from the forest edge to core was monitored over 2 years. Decomposition rate increased with distance from the edge, and was correlated with increasing humidity and moisture content of the decaying wood, such that the decay constant at 100 m was nearly twice that at the edge. Mean air temperature decreased slightly with distance from the edge. The variation in decay constant due to edge effects was larger than that expected from any reasonable estimates of climatic variation, based on a published regional model. We modelled the influence of edge effects on the decay constant at the landscape scale using functions for forest area within different distances from edge across the UK. We found that taking edge effects into account would decrease the decay rate by nearly one quarter, compared with estimates that assumed no edge effect. © 2014 John Wiley & Sons Ltd.

Improving the enzymolysis efficiency of potato protein by simultaneous dual-frequency energy-gathered ultrasound pretreatment: Thermodynamics and kinetics.

PubMed

Cheng, Yu; Liu, Yun; Wu, Juan; Ofori Donkor, Prince; Li, Ting; Ma, Haile

2017-07-01

The thermodynamics and kinetics of traditional and simultaneous dual frequency energy-gathered ultrasound (SDFU) assisted enzymolysis of potato protein were investigated to get the knowledge of the mechanisms on the SDFU's promoting efficiency during enzymolysis. The concentration of potato protein hydrolysate and parameters of thermodynamic and kinetic during traditional and SDFU assisted enzymolysis were determined. The results showed that potato protein hydrolysate concentration of SDFU assisted enzymolysis was higher than traditional enzymolysis at the hydrolysis time of 60min (p<0.05) whereas not significantly different at 120min (p>0.05). In some cases, SDFU assisted enzymolysis took less hydrolysis time than traditional enzymolysis when the similar conversion rates of potato protein were obtained. The thermodynamic papameters including the energy of activation (E a ), enthalpy of activation (△H), entropy of activation (△S) were reduced by ultrasound pretreatment while Gibbs free energy of activation (△G) increased little (1.6%). Also, kinetic papameters including Michaelis constant (K M ) and catalytic rate constant (k cat ) decreased by ultrasound pretreatment. On the contrary, reaction rate constants (k) of SDFU assisted enzymolysis were higher than that of traditional enzymolysis (p<0.05). It was indicated that the efficiency of SDFU assisted enzymolysis was higher than traditional enzymolysis in a limited time. The higher efficiency of SDFU assisted enzymolysis was related with the decrease of E a and K M by lowering the energy barrier between ground and active state and increasing affinity between substrate and enzyme. Copyright © 2017 Elsevier B.V. All rights reserved.

Continuous treatment of high strength wastewaters using air-cathode microbial fuel cells.

PubMed

Kim, Kyoung-Yeol; Yang, Wulin; Evans, Patrick J; Logan, Bruce E

2016-12-01

Treatment of low strength wastewaters using microbial fuel cells (MFCs) has been effective at hydraulic retention times (HRTs) similar to aerobic processes, but treatment of high strength wastewaters can require longer HRTs. The use of two air-cathode MFCs hydraulically connected in series was examined to continuously treat high strength swine wastewater (7-8g/L of chemical oxygen demand) at an HRT of 16.7h. The maximum power density of 750±70mW/m 2 was produced after 12daysof operation. However, power decreased by 85% after 185d of operation due to serious cathode fouling. COD removal was improved by using a lower external resistance, and COD removal rates were substantially higher than those previously reported for a low strength wastewater. However, removal rates were inconsistent with first order kinetics as the calculated rate constant was an order of magnitude lower than rate constant for the low strength wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cardiovascular effects of constant rate infusions of lidocaine, lidocaine and dexmedetomidine, and dexmedetomidine in dogs anesthetized at equipotent doses of sevoflurane.

PubMed

Moran-Muñoz, Rafael; Valverde, Alexander; Ibancovichi, J A; Acevedo-Arcique, Carlos M; Recillas-Morales, Sergio; Sanchez-Aparicio, Pedro; Osorio-Avalos, Jorge; Chavez-Monteagudo, Julio Raul

2017-07-01

This study evaluated the cardiovascular effects of a constant rate infusion (CRI) of lidocaine, lidocaine and dexmedetomidine, and dexmedetomidine in dogs anesthetized with sevoflurane at equipotent doses. Treatments consisted of T1-Lidocaine [loading dose 2 mg/kg body weight (BW), IV, and CRI of 100 μg/kg BW per min] at 1.4% end-tidal of sevoflurane (FE SEV ); T2-Dexmedetomidine (loading dose 2 μg/kg BW, IV, and CRI of 2 μg/kg BW per hour) and FE SEV 1.1%; and T3-Lidocaine-Dexmedetomidine using the same doses of T1 and T2 and FE SEV 0.8%. Constant rate infusion of lidocaine did not induce any cardiovascular changes; lidocaine and dexmedetomidine resulted in cardiovascular effects similar to dexmedetomidine alone. These effects were characterized by a significant ( P < 0.001) decrease in heart rate, cardiac output, cardiac index, oxygen delivery, and pulmonary vascular resistance index, and a significant ( P < 0.001) increase in mean and diastolic arterial pressure, systemic vascular resistance index, pulmonary arterial occlusion pressure and oxygen extraction ratio, compared with baseline values. In conclusion, a CRI of lidocaine combined with dexmedetomidine produces significant cardiovascular changes similar to those observed with dexmedetomidine alone.

Photoactive yellow protein from the purple phototrophic bacterium, Ectothiorhodospira halophila. Quantum yield of photobleaching and effects of temperature, alcohols, glycerol, and sucrose on kinetics of photobleaching and recovery.

PubMed Central

Meyer, T. E.; Tollin, G.; Hazzard, J. H.; Cusanovich, M. A.

1989-01-01

A water-soluble yellow protein from E. halophila was previously shown to be photoactive (Meyer, T. E., E. Yakali, M. A. Cusanovich, and G. Tollin. 1987. Biochemistry. 26:418-423). Pulsed laser excitation in the protein visible absorption band (maximum at 445 nm) causes a rapid bleach of color (k = 7.5 x 10(3) s-1) followed by a slower dark recovery (k = 2.6 s-1). This is analogous to the photocycle of sensory rhodopsin II from Halobacterium (which also has k = 2.6 s-1 for recovery). We have now determined the quantum yield of the photobleaching process to be 0.64, which is comparable with that of bacteriorhodopsin (0.25), and is thus large enough to be biologically significant. Although the photoreactions of yellow protein were previously shown to be relatively insensitive to pH, ionic strength and the osmoregulator betaine, the present experiments demonstrate that temperature, glycerol, sucrose, and various alcohol-water mixtures strongly influence the kinetics of photobleaching and recovery. The effect of temperature follows normal Arrhenius behavior for the bleach reaction (Ea = 15.5 kcal/mol). The rate constant for the recovery reaction increases with temperature between 5 degrees C and 35 degrees C, but decreases above 35 degrees C indicating alternate conformations with differing kinetics. There is an order of magnitude decrease in the rate constant for photobleaching in both glycerol and sucrose solutions that can be correlated with the changes in viscosity. We conclude from this that the protein undergoes a conformational change as a consequence of the photoinduced bleach. Recovery kinetics are affected by glycerol and sucrose to a much smaller extent and in a more complicated manner. Aliphatic, monofunctional alcohol-water solutions increase the rate constant for the bleach reaction and decrease the rate constant for the recovery reaction, each by an order of magnitude. These effects do not correlate with dielectric constant, indicating that the photocycle probably does not involve separation or recombination of charge accessible to the protein surface. However, the effects on both bleaching and recovery correlate well with the relative hydrophobicity(as measured by partition coefficients in detergent/water mixtures), in the order of increasing effectiveness:methanol < ethanol < iso-propanol

Rate variations of a hetero-Diels--Alder reaction in supercritical fluid CO{sub 2}

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

Thompson, R.L.; Glaeser, R.; Bush, D.

1999-11-01

The hetero-Diels-Alder reaction between anthracene and excess 4-phenyl-1,2,4-triazoline-3,5-dione has been investigated in supercritical CO{sub 2} at 40 C and pressures between 75 and 216 bar. Biomolecular reaction rate constants have been measured via fluorescence spectroscopy by following the decrease in anthracene concentration with reaction time. The reaction rate is elevated in the vicinity of the critical pressure. This difference is consistent with local composition enhancement and can be modeled with the Peng-Robinson equation of state.

Development of a 20 mA negative hydrogen ion source for cyclotrons

NASA Astrophysics Data System (ADS)

Etoh, H.; Onai, M.; Arakawa, Y.; Aoki, Y.; Mitsubori, H.; Sakuraba, J.; Kato, T.; Mitsumoto, T.; Yajima, S.; Hatayama, A.; Okumura, Y.

2017-08-01

A cesiated DC negative ion source has been developed for proton cyclotrons in medical applications. A continuous H- beam of 23 mA was stably extracted at an arc power of 3 kW. The beam current gradually decreases with a constant arc power and without additional Cs injection and the decay rate was about 0.03 mA (0.14%) per hour. A feed-back control system that automatically adjusts the arc power to stabilize the beam current is able to keep the beam current constant at ±0.04 mA (±0.2%).

Quantitative relations between fishing mortality, spawning stress mortality and biomass growth rate (computed with numerical model FISHMO)

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

Laevastu, T.

1983-01-01

The effects of fishing on a given species biomass have been quantitatively evaluated. A constant recruitment is assumed in this study, but the evaluation can be computed on any known age distribution of exploitable biomass. Fishing mortality is assumed to be constant with age; however, spawning stress mortality increases with age. When fishing (mortality) increases, the spawning stress mortality decreases relative to total and exploitable biomasses. These changes are quantitatively shown for two species from the Bering Sea - walleye pollock, Theragra chalcogramma, and yellowfin sole, Limanda aspera.

Repetition rate dependency of low-density plasma effects during femtosecond-laser-based surgery of biological tissue

NASA Astrophysics Data System (ADS)

Kuetemeyer, K.; Baumgart, J.; Lubatschowski, H.; Heisterkamp, A.

2009-11-01

Femtosecond laser based nanosurgery of biological tissue is usually done in two different regimes. Depending on the application, low kHz repetition rates above the optical breakdown threshold or high MHz repetition rates in the low-density plasma regime are used. In contrast to the well understood optical breakdown, mechanisms leading to dissection below this threshold are not well known due to the complexity of chemical effects with high numbers of interacting molecules. Furthermore, the laser repetition rate may influence their efficiency. In this paper, we present our study on low-density plasma effects in biological tissue depending on repetition rate by static exposure of porcine corneal stroma to femtosecond pulses. We observed a continuous increase of the laser-induced damage with decreasing repetition rate over two orders of magnitude at constant numbers of applied laser pulses or constant laser pulse energies. Therefore, low repetition rates in the kHz regime are advantageous to minimize the total delivered energy to biological tissue during femtosecond laser irradiation. However, due to frequent excessive damage in this regime directly above the threshold, MHz repetition rates are preferable to create nanometer-sized cuts in the low-density plasma regime.

Trends in Hip Fracture Rates in Canada: An Age-Period-Cohort Analysis

PubMed Central

Jean, Sonia; O’Donnell, Siobhan; Lagacé, Claudia; Walsh, Peter; Bancej, Christina; Brown, Jacques P.; Morin, Suzanne; Papaioannou, Alexandra; Jaglal, Susan B.; Leslie, William D.

2016-01-01

Age-standardized rates of hip fracture in Canada declined during the period 1985 to 2005. We investigated whether this incidence pattern is explained by period effects, cohort effects, or both. All hospitalizations during the study period with primary diagnosis of hip fracture were identified. Age- and sex-specific hip fracture rates were calculated for nineteen 5-year age groups and four 5-year calendar periods, resulting in 20 birth cohorts. The effect of age, calendar period, and birth cohort on hip fracture rates was assessed using age-period-cohort models as proposed by Clayton and Schiffers. From 1985 to 2005, a total of 570,872 hospitalizations for hip fracture were identified. Age-standardized rates for hip fracture have progressively declined for females and males. The annual linear decrease in rates per 5-year period were 12% for females and 7% for males (both p < 0.0001). Significant birth cohort effects were also observed for both sexes (p < 0.0001). Cohorts born before 1950 had a higher risk of hip fracture, whereas those born after 1954 had a lower risk. After adjusting for age and constant annual linear change (drift term common to both period and cohort effects), we observed a significant nonlinear birth cohort effect for males (p = 0.0126) but not for females (p = 0.9960). In contrast, the nonlinear period effect, after adjustment for age and drift term, was significant for females (p = 0.0373) but not for males (p = 0.2515). For males, we observed no additional nonlinear period effect after adjusting for age and birth cohort, whereas for females, we observed no additional nonlinear birth cohort effect after adjusting for age and period. Although hip fracture rates decreased in both sexes, different factors may explain these changes. In addition to the constant annual linear decrease, nonlinear birth cohort effects were identified for males, and calendar period effects were identified for females as possible explanations. PMID:23426882

Is wealthier always healthier? The impact of national income level, inequality, and poverty on public health in Latin America.

PubMed

Biggs, Brian; King, Lawrence; Basu, Sanjay; Stuckler, David

2010-07-01

Despite findings indicating that both national income level and income inequality are each determinants of public health, few have studied how national income level, poverty and inequality interact with each other to influence public health outcomes. We analyzed the relationship between gross domestic product (GDP) per capita in purchasing power parity, extreme poverty rates, the gini coefficient for personal income and three common measures of public health: life expectancy, infant mortality rates, and tuberculosis (TB) mortality rates. Introducing poverty and inequality as modifying factors, we then assessed whether the relationship between GDP and health differed during times of increasing, decreasing, and decreasing or constant poverty and inequality. Data were taken from twenty-two Latin American countries from 1960 to 2007 from the December 2008 World Bank World Development Indicators, World Health Organization Global Tuberculosis Database 2008, and the Socio-Economic Database for Latin America and the Caribbean. Consistent with previous studies, we found increases in GDP have a sizable positive impact on population health. However, the strength of the relationship is powerfully influenced by changing levels of poverty and inequality. When poverty was increasing, greater GDP had no significant effect on life expectancy or TB mortality, and only led to a small reduction in infant mortality rates. When inequality was rising, greater GDP had only a modest effect on life expectancy and infant mortality rates, and no effect on TB mortality rates. In sharp contrast, during times of decreasing or constant poverty and inequality, there was a very strong relationship between increasing GDP and higher life expectancy and lower TB and infant mortality rates. Finally, inequality and poverty were found to exert independent, substantial effects on the relationship between national income level and health. Wealthier is indeed healthier, but how much healthier depends on how increases in wealth are distributed. Copyright 2010 Elsevier Ltd. All rights reserved.

Gamma radiation field intensity meter

DOEpatents

Thacker, L.H.

1995-10-17

A gamma radiation intensity meter measures dose rate of a radiation field. The gamma radiation intensity meter includes a tritium battery emitting beta rays generating a current which is essentially constant. Dose rate is correlated to an amount of movement of an electroscope element charged by the tritium battery. Ionizing radiation decreases the voltage at the element and causes movement. A bleed resistor is coupled between the electroscope support element or electrode and the ionization chamber wall electrode. 4 figs.

Gamma radiation field intensity meter

DOEpatents

Thacker, L.H.

1994-08-16

A gamma radiation intensity meter measures dose rate of a radiation field. The gamma radiation intensity meter includes a tritium battery emitting beta rays generating a current which is essentially constant. Dose rate is correlated to an amount of movement of an electroscope element charged by the tritium battery. Ionizing radiation decreases the voltage at the element and causes movement. A bleed resistor is coupled between the electroscope support element or electrode and the ionization chamber wall electrode. 4 figs.

Electromagnetic Metrics of Mental Workload.

DTIC Science & Technology

1987-09-01

anxiety ). A decrease in performance accuracy has been used in the context of over- load, however it has also been associated with a "high workload". 1.2...heart rate variability ( HRV ) to refer to any varia- tion from a constant heart rate. The term HRV shall not refer to any specific method of numerically...in using HRV as a measure of mental load arose after Kalsbeek & Ettema (1963) reported that HRV was "gradu- ally suppressed when increasing the

Modelling audiovisual integration of affect from videos and music.

PubMed

Gao, Chuanji; Wedell, Douglas H; Kim, Jongwan; Weber, Christine E; Shinkareva, Svetlana V

2018-05-01

Two experiments examined how affective values from visual and auditory modalities are integrated. Experiment 1 paired music and videos drawn from three levels of valence while holding arousal constant. Experiment 2 included a parallel combination of three levels of arousal while holding valence constant. In each experiment, participants rated their affective states after unimodal and multimodal presentations. Experiment 1 revealed a congruency effect in which stimulus combinations of the same extreme valence resulted in more extreme state ratings than component stimuli presented in isolation. An interaction between music and video valence reflected the greater influence of negative affect. Video valence was found to have a significantly greater effect on combined ratings than music valence. The pattern of data was explained by a five parameter differential weight averaging model that attributed greater weight to the visual modality and increased weight with decreasing values of valence. Experiment 2 revealed a congruency effect only for high arousal combinations and no interaction effects. This pattern was explained by a three parameter constant weight averaging model with greater weight for the auditory modality and a very low arousal value for the initial state. These results demonstrate key differences in audiovisual integration between valence and arousal.

Laser flash photolysis and CIDNP studies of steric effects on coupling rate constants of imidazolidine nitroxide with carbon-centered radicals, methyl isobutyrate-2-yl and tert-butyl propionate-2-yl.

PubMed

Zubenko, Dmitry; Tsentalovich, Yuri; Lebedeva, Nataly; Kirilyuk, Igor; Roshchupkina, Galina; Zhurko, Irina; Reznikov, Vladimir; Marque, Sylvain R A; Bagryanskaya, Elena

2006-08-04

Time-resolved chemically induced dynamic nuclear polarization (TR-CIDNP) and laser flash photolysis (LFP) techniques have been used to measure rate constants for coupling between acrylate-type radicals and a series of newly synthesized stable imidazolidine N-oxyl radicals. The carbon-centered radicals under investigation were generated by photolysis of their corresponding ketone precursors RC(O)R (R = C(CH3)2-C(O)OCH3 and CH(CH3)-C(O)-OtBu) in the presence of stable nitroxides. The coupling rate constants kc for modeling studies of nitroxide-mediated polymerization (NMP) experiments were determined, and the influence of steric and electronic factors on kc values was addressed by using a Hammett linear free energy relationship. The systematic changes in kc due to the varied steric (Es,n) and electronic (sigmaL,n) characters of the substituents are well-described by the biparameter equation log(kc/M- 1s(-1)) = 3.52sigmaL,n + 0.47Es,n + 10.62. Hence, kc decreases with the increasing steric demand and increases with the increasing electron-withdrawing character of the substituents on the nitroxide.

Relationship between oxygen concentration, respiration and filtration rate in blue mussel Mytilus edulis

NASA Astrophysics Data System (ADS)

Tang, Baojun; Riisgård, Hans Ulrik

2018-03-01

The large water-pumping and particle-capturing gills of the filter-feeding blue mussel Mytilus edulis are oversized for respiratory purposes. Consequently, the oxygen uptake rate of the mussel has been suggested to be rather insensitive to decreasing oxygen concentrations in the ambient water, since the diffusion rate of oxygen from water flowing through the mussel determines oxygen uptake. We tested this hypothesis by measuring the oxygen uptake in mussels exposed to various oxygen concentrations. These concentrations were established via N2-bubbling of the water in a respiration chamber with mussels fed algal cells to stimulate fully opening of the valves. It was found that mussels exposed to oxygen concentrations decreasing from 9 to 2 mg O2/L resulted in a slow but significant reduction in the respiration rate, while the filtration rate remained high and constant. Thus, a decrease of oxygen concentration by 78% only resulted in a 25% decrease in respiration rate. However, at oxygen concentrations below 2 mg O2/L M. edulis responded by gradually closing its valves, resulting in a rapid decrease of filtration rate, concurrent with a rapid reduction of respiration rate. These observations indicated that M. edulis is no longer able to maintain its normal aerobic metabolism at oxygen concentration below 2 mg O2/L, and there seems to be an energy-saving mechanism in bivalve molluscs to strongly reduce their activity when exposed to low oxygen conditions.

Nucleation kinetics from metastable zone widths for sonocrystallization of l-phenylalanine.

PubMed

Hazi Mastan, T; Lenka, Maheswata; Sarkar, Debasis

2017-05-01

This study investigates the effect of ultrasound on metastable zone width (MSZW) during crystallization of l-phenylalanine from aqueous solution. The solubility of l-phenylalanine in water was measured gravimetrically in the temperature range of 293.15-333.15K. The MSZW was measured by conventional polythermal method for four different cooling rates at five different saturation temperatures in absence and presence of ultrasound. The MSZW increased with increase in cooling rates and decreased with increase in saturation temperature. The application of ultrasound considerably reduced the MSZW for all the experiments. The obtained MSZW data are analysed using four different approaches to calculate various nucleation parameters. In presence of ultrasound, the apparent nucleation order decreased and nucleation rate constant increased significantly. Copyright © 2016 Elsevier B.V. All rights reserved.

Measurement and Modeling of Respiration Rate of Tomato (Cultivar Roma) for Modified Atmosphere Storage.

PubMed

Kandasamy, Palani; Moitra, Ranabir; Mukherjee, Souti

2015-01-01

Experiments were conducted to determine the respiration rate of tomato at 10, 20 and 30 °C using closed respiration system. Oxygen depletion and carbon dioxide accumulation in the system containing tomato was monitored. Respiration rate was found to decrease with increasing CO2 and decreasing O2 concentration. Michaelis-Menten type model based on enzyme kinetics was evaluated using experimental data generated for predicting the respiration rate. The model parameters that obtained from the respiration rate at different O2 and CO2 concentration levels were used to fit the model against the storage temperatures. The fitting was fair (R2 = 0.923 to 0.970) when the respiration rate was expressed as O2 concentation. Since inhibition constant for CO2 concentration tended towards negetive, the model was modified as a function of O2 concentration only. The modified model was fitted to the experimental data and showed good agreement (R2 = 0.998) with experimentally estimated respiration rate.

Identical activation volumes of dislocation mobility in the [100](010) and [001](010) slip systems in natural olivine

NASA Astrophysics Data System (ADS)

Wang, Lin; Blaha, Stephan; Kawazoe, Takaaki; Miyajima, Nobuyoshi; Katsura, Tomoo

2017-03-01

Dislocation recovery experiments were performed on predeformed olivine single crystals at pressures of 2, 7 and 12 GPa and a constant temperature of 1650 K to determine the pressure dependence of the annihilation rate constants for [100](010) edge dislocation (a dislocation) and [001](010) screw dislocation (c dislocation). The constants of both types of dislocations are comparable within 0.3 orders of magnitude. The activation volumes of a and c dislocations are small and identical within error: 2.7 ± 0.2 and 2.5 ± 0.9 cm3/mol, respectively. These values are slightly larger and smaller than those of Si lattice and grain-boundary diffusions in olivine, respectively. The small and identical activation volumes for the a and c dislocations suggest that the pressure-induced fabric transition is unlikely in the asthenosphere. The decrease in seismic anisotropy with depth down in the asthenosphere may be caused by the fabric transition from A type or B type to AG type with decreasing stress with depth.

Human Manganese Superoxide Dismutase Tyrosine 34 Contribution to Structure and Catalysis

PubMed Central

Perry, J. Jefferson P.; Hearn, Amy S.; Cabelli, Diane E.; Nick, Harry S.; Tainer, John A.; Silverman, David N.

2009-01-01

Superoxide dismutase (SOD) enzymes are critical in controlling levels of reactive oxygen species (ROS) that are linked to aging, cancer and neurodegenerative disease. Superoxide (O2 •−) produced during respiration is removed by the product of the SOD2 gene, the homotetrameric manganese superoxide dismutase (MnSOD). Here, we examine the structural and catalytic roles of the highly conserved active-site residue Tyr34, based upon structure-function studies of MnSOD enzymes with mutations at this site. Substitution of Tyr34 with five different amino acids retained the active site protein structure and assembly, but causes a substantial decrease in the catalytic rate constant for the reduction of superoxide. The rate constant for formation of product inhibition complex also decreases but to a much lesser extent, resulting in a net increase in the product inhibition form of the mutant enzymes. Comparisons of crystal structures and catalytic rates also suggest that one mutation, Y34V, interrupts the hydrogen-bonded network, which is associated with a rapid dissociation of the product-inhibited complex. Notably, with three of the Tyr34 mutants we also observe an intermediate in catalysis, which has not been reported previously. Thus, these mutants establish a means to trap a catalytic intermediate that promises to help elucidate the mechanism of catalysis. PMID:19265433

Agarose electrophoresis of DNA in discontinuous buffers, using a horizontal slab apparatus and a buffer system with improved properties.

PubMed

Zsolnai, A; Orbán, L; Chrambach, A

1993-03-01

Using a horizontal slab apparatus with a buffer in the reservoirs at the level of the gel ("sea-level electrophoresis"), the retrograde discontinuous buffer system reported by Wiltfang et al. for sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) of proteins was applied to DNA electrophoresis. This application yielded the advantages of an increased displacement rate of the moving boundary front and a decrease in the concentration of the counterion base in the resolving phase, which yielded reduced relative mobility values at equivalent gel concentrations and practicable low buffer concentrations. The change of relative mobilities (Rf) with a variation of field strength is decreased compared to that of the migration rate in the continuous Tris-boric-acid-EDTA (TBE) buffer and thus the robustness of the system is improved, as well as the efficiency of separation. The system of Wiltfang et al. has in common with previously described discontinuous DNA system, that it is able to stack DNA from dilute samples and is insensitive to sample components with lower net mobilities than DNA, such as acetate. However, the variance of Rf at constant current density in the discontinuous buffer system is not improved over that of the migration rate at constant field strength in the continuous TBE buffer.

Reproduction of bobwhites fed different dietary concentrations of an organophosphate insecticide, methamidophos

USGS Publications Warehouse

Stromborg, K.L.

1986-01-01

Pairs of first-year breeding bobwhites were fed constant or variable concentrations of methamidophos for 15 days, or a control diet in a pair-fed design in which they were matched by body weights to pairs in the constant group. Treatments for the constant group were 5.0, 7.8, 12.3, 19.2, and 30.0 ppm for 5 pairs at each concentration. The number of pairs per concentration and peak concentrations for the variable pairs were identical to the constant dosages. Concentrations for the variable group were increased by a factor of four during two 3-day periods in order to reach the peak concentrations on days 7?9 after which they were decreased by 18% every 3 days to correspond to an environmental half-time of 10.5 days. Food consumption, egg production, hatchability of eggs under artificial incubation, and survival of hatched chicks for 2 weeks were recorded for each pair during 15-day treatment and 21-day posttreatment periods. Mortality was high in the highest constant dosage (2/10) and the associated pair-fed groups (3/10). Food consumption and egg production rates were negatively dose-related during the treatment period in the constant and variable groups. The laying rate of pair-fed hens was reduced to the same extent as in the constant group. Reproductive inhibition was not permanent and pairs resumed laying after a dose-related recovery interval. No dose-related effects on hatchability or chick survival were detected. Furthermore, there was no evidence of a pesticide effect on reproduction in addition to that exerted through pesticide-induced anorexia.

Denitrification potential in stream sediments impacted by acid mine drainage: Effects of pH, various electron donors, and iron

USGS Publications Warehouse

Baeseman, J.L.; Smith, R.L.; Silverstein, J.

2006-01-01

Acid mine drainage (AMD) contaminates thousands of kilometers of stream in the western United States. At the same time, nitrogen loading to many mountain watersheds is increasing because of atmospheric deposition of nitrate and increased human use. Relatively little is known about nitrogen cycling in acidic, heavy-metal-laden streams; however, it has been reported that one key process, denitrification, is inhibited under low pH conditions. The objective of this research was to investigate the capacity for denitrification in acidified streams. Denitrification potential was assessed in sediments from several Colorado AMD-impacted streams, ranging from pH 2.60 to 4.54, using microcosm incubations with fresh sediment. Added nitrate was immediately reduced to nitrogen gas without a lag period, indicating that denitrification enzymes were expressed and functional in these systems. First-order denitrification potential rate constants varied from 0.046 to 2.964 day-1. The pH of the microcosm water increased between 0.23 and 1.49 pH units during denitrification. Additional microcosm studies were conducted to examine the effects of initial pH, various electron donors, and iron (added as ferrous and ferric iron). Decreasing initial pH decreased denitrification; however, increasing pH had little effect on denitrification rates. The addition of ferric and ferrous iron decreased observed denitrification potential rate constants. The addition of glucose and natural organic matter stimulated denitrification potential. The addition of hydrogen had little effect, however, and denitrification activity in the microcosms decreased after acetate addition. These results suggest that denitrification can occur in AMD streams, and if stimulated within the environment, denitrification might reduce acidity. ?? Springer Science+Business Media, Inc. 2006.

Anti-Arrhenius cleavage of covalent bonds in bottlebrush macromolecules on substrate.

PubMed

Lebedeva, Natalia V; Nese, Alper; Sun, Frank C; Matyjaszewski, Krzysztof; Sheiko, Sergei S

2012-06-12

Spontaneous degradation of bottlebrush macromolecules on aqueous substrates was monitored by atomic force microscopy. Scission of C ─ C covalent bonds in the brush backbone occurred due to steric repulsion between the adsorbed side chains, which generated bond tension on the order of several nano-Newtons. Unlike conventional chemical reactions, the rate of bond scission was shown to decrease with temperature. This apparent anti-Arrhenius behavior was caused by a decrease in the surface energy of the underlying substrate upon heating, which results in a corresponding decrease of bond tension in the adsorbed macromolecules. Even though the tension dropped minimally from 2.16 to 1.89 nN, this was sufficient to overpower the increase in the thermal energy (k(B)T) in the Arrhenius equation. The rate constant of the bond-scission reaction was measured as a function of temperature and surface energy. Fitting the experimental data by a perturbed Morse potential V = V(0)(1 - e(-βx))(2) - fx, we determined the depth and width of the potential to be V(0) = 141 ± 19 kJ/mol and β(-1) = 0.18 ± 0.03 Å, respectively. Whereas the V(0) value is in reasonable agreement with the activation energy E(a) = 80-220 kJ/mol of mechanical and thermal degradation of organic polymers, it is significantly lower than the dissociation energy of a C ─ C bond D(e) = 350 kJ/mol. Moreover, the force constant K(x) = 2β(2)V(0) = 1.45 ± 0.36 kN/m of a strained bottlebrush along its backbone is markedly larger than the force constant of a C ─ C bond K(l) = 0.44 kN/m, which is attributed to additional stiffness due to deformation of the side chains.

DESORPTION OF PYRETHROIDS FROM SUSPENDED SOLIDS

PubMed Central

Fojut, Tessa L.; Young, Thomas M.

2014-01-01

Pyrethroid insecticides have been widely detected in sediments at concentrations that can cause toxicity to aquatic organisms. Desorption rates play an important role in determining the bioavailability of hydrophobic organic compounds, such as pyrethroids, because these compounds are more likely to be sorbed to solids in the environment and times to reach sorptive equilibrium can be long. In this study, sequential Tenax desorption experiments were performed with three sorbents, three aging times, and four pyrethroids. A biphasic rate model was fit to the desorption data with r2 > 0.99 and the rapid and slow compartment desorption rate constants and compartment fractions are reported. Suspended solids from irrigation runoff water collected from a field that had been sprayed with permethrin one day prior were used in the experiments to compare desorption rates for field-applied pyrethroids to those for laboratory-spiked materials. Suspended solids were used in desorption experiments because suspended solids can be a key source of hydrophobic compounds to surface waters. The rapid desorption rate parameters of field-applied permethrin were not statistically different than those of laboratory spiked permethrin, indicating that the desorption of the spiked pyrethroids is comparable to those added and aged in the field. Sorbent characteristics had the greatest effect on desorption rate parameters; as organic carbon content of the solids increased, the rapid desorption fractions and rapid desorption rate constants both decreased. The desorption rate constant of the slow compartment for sediment containing permethrin aged for 28 d was significantly different from those aged 1 d and 7 d, while desorption in the rapid and slow compartments did not differ between these treatments. PMID:21538493

Maintenance and constructive respiration, photosynthesis, and net assimilation rate in seedlings of pitch pine (Pinus rigida Mill.)

Treesearch

F. Thomas Ledig; A.P. Drew; J.G. Clark

1976-01-01

Pitch pine seedlins were grown at constant temperature and photoperiod. Net CO2-uptake h-1 g-1 leaves decreased stadily during ontogeny until leaf production ceased. Thereafter, there was no change or a slight increase. Though the 0ntogeneic pattern was the same in populations native to different...

Problems and Alternatives in the Combat Rescue of Navy Aircrewmen

DTIC Science & Technology

1980-11-01

33 Objectives for an Improved Combat Rescue System ................................. 33 Decrease Injury Rate...altitudes as low as 50 feet above ground level. Extremity rest aint systems, constantly being improved, are reducing the number of injuries resulting...These analyses established causal factors associated with the injuries and problems occurring during the ejection-through.survival sequence. Later

Modeling the Motion of an Increasing Mass System

ERIC Educational Resources Information Center

Kunkel, William; Harrington, Randal

2010-01-01

Problems on the dynamics of changing mass systems often call for the more general form of Newton's second law Fnet = dp/dt. These problems usually involve situations where the mass of the system decreases, such as in rocket propulsion. In contrast, this experiment examines a system where the mass "increases" at a constant rate and the net force…

Application of an enthalpy balance model of the relation between growth and respiration to temperature acclimation of Eucalyptus globulus seedlings.

PubMed Central

Macfarlane, Craig; Adams, Mark A; Hansen, Lee D

2002-01-01

The enthalpy balance model of growth uses measurements of the rates of heat and CO(2) production to quantify rates of decarboxylation, oxidative phosphorylation and net anabolism. Enthalpy conversion efficiency (eta(H)) and the net rate of conservation of enthalpy in reduced biosynthetic products (R(SG)DeltaH(B)) can be calculated from metabolic heat rate (q) and CO(2) rate (R(CO2)). eta(H) is closely related to carbon conversion efficiency and the efficiency of conservation of available electrons in biosynthetic products. R(SG)DeltaH(B) and eta(H) can be used, together with biomass composition, to describe the rate and efficiency of growth of plant tissues. q is directly related to the rate of O(2) consumption and the ratio q:R(CO2) is inversely related to the respiratory quotient. We grew seedlings of Eucalyptus globulus at 16 and 28 degrees C for four to six weeks, then measured q and R(CO2) using isothermal calorimetry. Respiratory rate at a given temperature was increased by a lower growth temperature but eta(H) was unaffected. Enthalpy conversion efficiency - and, therefore, carbon conversion efficiency - decreased with increasing temperature from 15 to 35 degrees C. The ratio of oxidative phosphorylation to oxygen consumption (P/O ratio) was inferred in vivo from eta(H) and by assuming a constant ratio of growth to maintenance respiration with changing temperature. The P/O ratio decreased from 2.1 at 10-15 degrees C to less than 0.3 at 35 degrees C, suggesting that decreased efficiency was not only due to activity of the alternative oxidase pathway. In agreement with predictions from non-equilibrium thermodynamics, growth rate was maximal near 25 degrees C, where the calculated P/O ratio was about half maximum. We propose that less efficient pathways, such as the alternative oxidase pathway, are necessary to satisfy the condition of conductance matching whilst maintaining a near constant phosphorylation potential. These conditions minimize entropy production and maximize the efficiency of mitochondrial energy conversions as growing conditions change, while maintaining adequate finite rates of energy processing. PMID:12137581

Time-resolved gas-phase kinetic and quantum chemical studies of the reaction of silylene with oxygen.

PubMed

Becerra, Rosa; Bowes, Sarah-Jane; Ogden, J Steven; Cannady, J Pat; Adamovic, Ivana; Gordon, Mark S; Almond, Matthew J; Walsh, Robin

2005-08-07

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with O(2). The reaction was studied in the gas phase over the pressure range 1-100 Torr in SF(6) bath gas, at five temperatures in the range 297-600 K. The second order rate constants at 10 Torr were fitted to the Arrhenius equation: [see text] The decrease in rate constant values with increasing temperature, although systematic is very small. The rate constants showed slight increases in value with pressure at each temperature, but this was scarcely beyond experimental uncertainty. From estimates of Lennard-Jones collision rates, this reaction is occurring at ca. 1 in 20 collisions, almost independent of pressure and temperature. Ab initio calculations at the G3 level backed further by multi-configurational (MC) SCF calculations, augmented by second order perturbation theory (MRMP2), support a mechanism in which the initial adduct, H(2)SiOO, formed in the triplet state (T), undergoes intersystem crossing to the more stable singlet state (S) prior to further low energy isomerisation processes leading, via a sequence of steps, ultimately to dissociation products of which the lowest energy pair are H2O+SiO. The decomposition of the intermediate cyclo-siladioxirane, via O-O bond fission, plays an important role in the overall process. The bottleneck for the overall process appears to be the T-->S process in H2SiOO. This process has a small spin-orbit coupling matrix element, consistent with an estimate of its rate constant of 1x10(9) s-1 obtained with the aid of RRKM theory. This interpretation preserves the idea that, as in its reactions in general, SiH2 initially reacts at the encounter rate with O2. The low values for the secondary reaction barriers on the potential energy surface account for the lack of an observed pressure dependence. Some comparisons are drawn with the reactions of CH2+O2 and SiCl2+O2.

Synthesis, characterization and sonocatalytic applications of nano-structured carbon based TiO2 catalysts.

PubMed

Choi, Jongbok; Cui, Mingcan; Lee, Yonghyeon; Kim, Jeonggwan; Yoon, Yeomin; Jang, Min; Khim, Jeehyeong

2018-05-01

In order to enhance sonocatalytic oxidation of a recalcitrant organic pollutant, rhodamine B (RhB), it is necessary to study the fundamental aspects of sonocatalysis. In this study, TiO 2 -incorporated nano-structured carbon (i.e., carbon nanotubes (CNTs) or graphene (GR)) composites were synthesized by coating TiO 2 on CNTs or GR of different mass percentages (0.5, 1, 5, and 10 wt%) by a facile hydrothermal method. The sonocatalytic degradation rates of RhB were examined for the effect of ultrasound (US) frequency and calcination temperature by using the prepared TiO 2 -NSC composites. Since US frequency affected the sonoluminescence (SL) intensities, it was proposed that there exists a correlation between the surface area or band-gap of the sonocatalysts and the degradation kinetic constants of RhB. In addition, the reusability of TiO 2 -GR composites was also investigated. Overall, the performance of TiO 2 -GRs prepared by the hydrothermal method was better than that of calcined TiO 2 -CNTs. Among TiO 2 -GRs, 5% GR incorporated media (TiO 2 -GR-5) showed the best performance. Interestingly, the kinetic constants of sonocatalysts prepared under hydrothermal conditions had a negative linear relationship with the band-gap energy for the corresponding media. Furthermore, the strongest SL intensity and highest degradation rates of RhB for both carbonaceous composites were observed at 500 kHz. The kinetic constants of calcined media decreased linearly as the specific area of the media decreased, while the band-gap energy could not be correlated with the kinetic constants. The GR combined TiO 2 composite might be a good sonocatalyst in wastewater treatment using ultrasound-based oxidation because of its high stability. Copyright © 2018 Elsevier B.V. All rights reserved.

[Radial Approach for Percutaneous Coronary Interventions in Patients With Ischemic Heart Disease: Advantages and Disadvantages, Complications Rate in Comparison With Femoral Approach].

PubMed

Fettser, D V; Batyraliev, T A; Pershukov, I V; Vanyukov, A E; Sidorenko, B A

2017-05-01

During recent 10-15 years, percutaneous coronary interventions (PCI) have reached a new level of efficacy and safety. Rate of serious coronary complications has decreased. That to a greater degree exposes the problem of peripheral complications at the site of arterial approach. At the same time portion of patients older than 75 years in the total pool of PCI constantly increases. Number of patients with pronounced obesity also grows each year. Radial approach for PCI allows to substantially decrease rate of peripheral complications at the account of lowered rate of bleedings, and to shorten duration of hospitalization. In this literature review we present results of a number of relevant clinical studies including those which contained groups of elderly patients and of patients with obesity. We also have summarized main advantages and disadvantages of radial approach as compared with femoral approach for coronary angiography and PCI.

Performance Study of Fluidized Bed Dryer with Immersed Heater for Paddy Drying

NASA Astrophysics Data System (ADS)

Suherman, S.; Azaria, N. F.; Karami, S.

2018-03-01

This paper investigated the performance of fluidized bed dryer with immersed heater for paddy drying. The influence of drying temperature and the temperature of immersed heater on drying curve, thermal efficiency, and quality of paddy was investigated. The fixed operating conditions are drying time of 60 minutes, paddy weight of 200 grams and the air velocity of 0.4 m/s. The variables are drying temperature and the temperature immersed heater namely 50, 60, 70, 80, 90 (°C). The results show addition immersed heater will increase drying rates. No constant drying rate was found. Increasing the temperature will decrease the utilized energy. The thermal efficiency decreases with increasing temperature. The increasing temperature and use immersed heater will decrease the residual moisture content, increase damaged and yellow paddy grain, and increase red paddy grain.

Insulin-regulated Glut4 Translocation

PubMed Central

Brewer, Paul Duffield; Habtemichael, Estifanos N.; Romenskaia, Irina; Mastick, Cynthia Corley; Coster, Adelle C. F.

2014-01-01

The trafficking kinetics of Glut4, the transferrin (Tf) receptor, and LRP1 were quantified in adipocytes and undifferentiated fibroblasts. Six steps were identified that determine steady state cell surface Glut4: (i) endocytosis, (ii) degradation, (iii) sorting, (iv) sequestration, (v) release, and (vi) tethering/docking/fusion. Endocytosis of Glut4 is 3 times slower than the Tf receptor in fibroblasts (ken = 0.2 min−1 versus 0.6 min−1). Differentiation decreases Glut4 ken 40% (ken = 0.12 min−1). Differentiation also decreases Glut4 degradation, increasing total and cell surface Glut4 3-fold. In fibroblasts, Glut4 is recycled from endosomes through a slow constitutive pathway (kex = 0.025–0.038 min−1), not through the fast Tf receptor pathway (kex = 0.2 min−1). The kex measured in adipocytes after insulin stimulation is similar (kex = 0.027 min−1). Differentiation decreases the rate constant for sorting into the Glut4 recycling pathway (ksort) 3-fold. In adipocytes, Glut4 is also sorted from endosomes into a second exocytic pathway through Glut4 storage vesicles (GSVs). Surprisingly, transfer from endosomes into GSVs is highly regulated; insulin increases the rate constant for sequestration (kseq) 8-fold. Release from sequestration in GSVs is rate-limiting for Glut4 exocytosis in basal adipocytes. AS160 regulates this step. Tethering/docking/fusion of GSVs to the plasma membrane is regulated through an AS160-independent process. Insulin increases the rate of release and fusion of GSVs (kfuseG) 40-fold. LRP1 cycles with the Tf receptor and Glut4 in fibroblasts but predominantly with Glut4 after differentiation. Surprisingly, AS160 knockdown accelerated LRP1 exocytosis in basal and insulin-stimulated adipocytes. These data indicate that AS160 may regulate trafficking into as well as release from GSVs. PMID:24778187

High modulation bandwidth of a light-emitting diode with surface plasmon coupling (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lin, Chun-Han; Tu, Charng-Gan; Yao, Yu-Feng; Chen, Sheng-Hung; Su, Chia-Ying; Chen, Hao-Tsung; Kiang, Yean-Woei; Yang, Chih-Chung

2017-02-01

Besides lighting, LEDs can be used for indoor data transmission. Therefore, a large modulation bandwidth becomes an important target in the development of visible LED. In this regard, enhancing the radiative recombination rate of carriers in the quantum wells of an LED is a useful method since the modulation bandwidth of an LED is related to the carrier decay rate besides the device RC time constant To increase the carrier decay rate in an LED without sacrificing its output power, the technique of surface plasmon (SP) coupling in an LED is useful. In this paper, the increases of modulation bandwidth by reducing mesa size, decreasing active layer thickness, and inducing SP coupling in blue- and green-emitting LEDs are illustrated. The results are demonstrated by comparing three different LED surface structures, including bare p-type surface, GaZnO current spreading layer, and Ag nanoparticles (NPs) for inducing SP coupling. In a single-quantum-well, blue-emitting LED with a circular mesa of 10 microns in radius, SP coupling results in a modulation bandwidth of 528.8 MHz, which is believed to be the record-high level. A smaller RC time constant can lead to a higher modulation bandwidth. However, when the RC time constant is smaller than 0.2 ns, its effect on modulation bandwidth saturates. The dependencies of modulation bandwidth on injected current density and carrier decay time confirm that the modulation bandwidth is essentially inversely proportional to a time constant, which is inversely proportional to the square-root of carrier decay rate and injected current density.

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

PubMed

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

2018-01-01

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

False CAM alarms from radon fluctuations.

PubMed

Hayes, Robert

2003-11-01

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

Electrochemical characterization and control of triple-layer muscles

NASA Astrophysics Data System (ADS)

Otero, Toribio F.; Cortes, Maria T.

2000-06-01

The electrochemical characterization of triple-layers formed by a EPA (Electroactive Polymer)/double-sided tape/EPA, like artificial muscles is described. Those muscles were characterized working under constant potential or under constant current. Due to the electrochemical nature of the electrochemomechanical property, muscles working under constant current produce constant movements, consuming increasing energies at decreasing temperatures, decreasing concentrations of electrolytes or trailing increasing masses. Muscles working at constant potential response with a faster movement if the temperature or the concentration of the electrolyte increase, or if the trailed weight decreases. Specific charges and specific energies were determined for every experimental condition.

Study of the sonophotocatalytic degradation of basic blue 9 industrial textile dye over slurry titanium dioxide and influencing factors.

PubMed

González, Antonia Sandoval; Martínez, Susana Silva

2008-09-01

The sonophotocatalytic degradation of basic blue 9 industrial textile dye has been studied in the presence of ultrasound (20 kHz) over a TiO(2) slurry employing an UV lamp (15 W, 352 nm). It was observed that the color removal efficiency was influenced by the pH of the solution, initial dye concentration and TiO(2) amount. It was found that the dye degradation followed apparent first order kinetics. The rate constant increased by decreasing dye concentration and was affected by the pH of the solution with the highest degradation obtained at pH 7. The first order rate constants obtained with sonophotocatalysis were twofold and tenfold than those obtained under photocatalysis and sonolysis, respectively. The chemical oxygen demand was abated over 80%.

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

PubMed

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

2009-10-01

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

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

PubMed

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

2014-11-01

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

Biodegradation of propylene glycol and associated hydrodynamic effects in sand.

PubMed

Bielefeldt, Angela R; Illangasekare, Tissa; Uttecht, Megan; LaPlante, Rosanna

2002-04-01

At airports around the world, propylene glycol (PG) based fluids are used to de-ice aircraft for safe operation. PG removal was investigated in 15-cm deep saturated sand columns. Greater than 99% PG biodegradation was achieved for all flow rates and loading conditions tested, which decreased the hydraulic conductivity of the sand by 1-3 orders of magnitude until a steady-state minimum was reached. Under constant loading at 120 mg PG/d for 15-30 d, the hydraulic conductivity (K) decreased by 2-2.5 orders of magnitude when the average linear velocity of the water was 4.9-1.4 cm/h. Variable PG loading in recirculation tests resulted in slower conductivity declines and lower final steady-state conductivity than constant PG feeding. After significant sand plugging, endogenous periods of time without PG resulted in significant but partial recovery of the original conductivity. Biomass growth also increased the dispersivity of the sand.

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

NASA Technical Reports Server (NTRS)

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

2004-01-01

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

Degradation of paracetamol in aqueous solutions by TiO2 photocatalysis.

PubMed

Yang, Liming; Yu, Liya E; Ray, Madhumita B

2008-07-01

In this study, photo/photocatalytic oxidation of common analgesic and antipyretic drug, paracetamol (acetaminophen), was investigated to determine the optimal operating conditions for degradation in water. UVA (365 nm) radiation alone degraded negligible amount of paracetamol, whereas paracetamol concentration decreased substantially under an irradiation of UVC (254 nm) with marginal changes in total organic carbon (TOC). In the presence of TiO2, much faster photodegradation of paracetamol and effective mineralization occurred; more than 95% of 2.0mM paracetamol was degraded within 80 min. The degradation rate constant decreased with an increase in the initial concentration of paracetamol, while it increased with light intensity and oxygen concentration. The degradation rate also increased with TiO2 loading until a concentration of 0.8 g L(-1). The degradation rate slowly increased between pH 3.5 and 9.5, but significantly decreased with increasing pH between 9.5 and 11.0. Based on the experimental data, a kinetic equation describing paracetamol photocatalytic degradation with various process parameters is obtained.

Venus' superrotation, mixing length theory and eddy diffusion - A parametric study

NASA Technical Reports Server (NTRS)

Mayr, H. G.; Harris, I.; Schatten, K. H.; Stevens-Rayburn, D. R.; Chan, K. L.

1988-01-01

The concept of the Hadley mechanism is adopted to describe the axisymmetric circulation of the Venus atmosphere. It is shown that, for the atmosphere of a slowly rotating planet such as Venus, a form of the nonliner 'closure' (self-consistent solution) of the fluid dynamics system which constrains the magnitude of the eddy diffusion coefficients can be postulated. A nonlinear one-layer spectral model of the zonally symmetric circulation was then used to establish the relationship between the heat source, the meridional circulation, and the eddy diffusion coefficients, yielding large zonal velocities. Computer experiments indicated that proportional changes in the heat source and eddy diffusion coefficients do not significantly change the zonal velocities. It was also found that, for large eddy diffusion coefficients, the meridional velocity is virtually constant; below a threshold in the diffusion rate, the meridional velocity decreases; and, for large eddy diffusion and small heating rates, the zonal velocities decrease with decreasing planetary rotation rates.

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.

Mcdonald Observatory 9P/TEMPEL 1 Data V1.0

NASA Astrophysics Data System (ADS)

Cochran, A. L.; Barker, E. S.; Caballero, M. D.; Gyorgey-Ries, J.

2010-01-01

We report on low-spectral resolution observations of comet 9P/Tempel 1 from 1983, 1989, 1994 and 2005 using the 2.7m Harlan J. Smith telescope of McDonald Observatory. This comet was the target of NASA's Deep Impact mission and our observations allowed us to characterize the comet prior to the impact. In the published paper, we showed that the comet decreased in gas production from 1983 to 2005, with the decrease being different factors for different species. OH decreased by a factor 2.7, NH by 1.7, CN by 1.6, C3 by 1.8, CH by 1.4 and C2 by 1.3. Despite the decrease in overall gas production and these slightly different decrease factors, we found that the ratios of the gas production rates of OH, NH, C3, CH and C2 that of CN were constant over all of the apparitions. We saw no change in the production rate ratios after the impact. We found that the peak gas production occurred about two months prior to perihelion. This data set represents the integrated fluxes and column densities, mentioned in the published paper, which were used to derive the production rates in the paper.

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

NASA Astrophysics Data System (ADS)

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

2014-02-01

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

Changes of Photochemical Properties of Dissolved Organic Matter During a Hydrological Year

NASA Astrophysics Data System (ADS)

Porcal, P.; Dillon, P. J.

2009-05-01

The fate of dissolved organic matter (DOM) in lakes and streams is significantly affected by photochemical transformation of DOM. A series of laboratory photochemical experiments has been conducted to describe long term changes in photochemical properties of DOM. The stream samples used in this study originated from three different watersheds in Dorset area (Ontario, Canada), the first watershed has predominantly coniferous cove, the second one is dominated by maple and birch, and a large wetland dominates to the third one. The first order kinetic constant rate was used as a suitable characteristic of photochemical properties of DOM. The higher rates were observed in samples from watershed dominated by coniferous forest while the lower rates were determined in deciduous forest. Kinetic rates from all three watersheds showed sinusoidal pattern during the hydrological year. The rates increased steadily during autumn and winter and decreased during spring and summer. The highest values were observed during the spring melt events when the fresh DOM was flushed out from terrestrial sources. The minimum rate constants were in summer when the discharge was lower. The photochemical properties of DOM changes during the hydrological year and correspond to the seasonal cycles of terrestrial organic matter.

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 in much better agreement with the calculations using the NCRP Report 58 and NNDC(2000) initial spectra with average discrepancies of 0.9% and 1.7% for the (125)I and (103)Pd seeds, respectively. However, there are no differences in the calculated TG-43U1 brachytherapy parameters using either initial spectrum in both cases. Similarly, there were no differences outside the statistical uncertainties of 0.1% or 0.2%, in the average energy, air kerma/history, dose rate/history, and dose rate constant when calculated using either the full photon spectrum or the main-peaks-only spectrum. Our calculated dose rate constants based on using the calculated on-axis spectrum and a line or dual-point source model are in excellent agreement (0.5% on average) with the values of Chen and Nath, verifying the accuracy of their more approximate method of going from the spectrum to the dose rate constant. However, the dose rate constants based on full seed models differ by between +4.6% and -1.5% from those based on the line or dual-point source approximations. These results suggest that the main value of spectroscopic measurements is to verify full Monte Carlo models of the seeds by comparison to the calculated spectra.

Prey and predator emigration responses in the acarine system Tetranychus urticae-Phytoseiulus persimilis.

PubMed

Bernstein, C

1984-01-01

Some of the processes that influence the emigration of prey and predatory mites from bean plants were investigated experimentally. The emigration of the prey depends on the damage they cause to the plants and on predator density. The predator's emigration rate is a decreasing function of prey density, and does not change (or it slightly decreases) when prey and predator numbers are increased maintaining the same prey/predator ratio. The probability of emigration of the predators is independent of their own density when prey are absent and density dependent when prey density is kep constant. Forty three per cent of the variability in the predator's instantaneous rate of emigration in the different experiments is accounted for by a two parameter negative exponential function of capture rate (number of prey eaten per predator and per unit of time).

Control of the Protein Turnover Rates in Lemna minor

PubMed Central

Trewavas, A.

1972-01-01

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

Carbon dioxide exchange of lettuce plants under hypobaric conditions

NASA Technical Reports Server (NTRS)

Corey, K. A.; Bates, M. E.; Adams, S. L.; MacElroy, R. D. (Principal Investigator)

1996-01-01

Growth of plants in a Controlled Ecological Life Support System (CELSS) may involve the use of hypobaric pressures enabling lower mass requirements for atmospheres and possible enhancement of crop productivity. A controlled environment plant growth chamber with hypobaric capability designed and built at Ames Research Center was used to determine if reduced pressures influence the rates of photosynthesis (Ps) and dark respiration (DR) of hydroponically grown lettuce plants. The chamber, referred to as a plant volatiles chamber (PVC), has a growing area of about 0.2 m2, a total gas volume of about 0.7 m3, and a leak rate at 50 kPa of <0.1%/day. When the pressure in the chamber was reduced from ambient to 51 kPa, the rate of net Ps increased by 25% and the rate of DR decreased by 40%. The rate of Ps increased linearly with decreasing pressure. There was a greater effect of reduced pressure at 41 Pa CO2 than at 81 Pa CO2. This is consistent with reports showing greater inhibition of photorespiration (Pr) in reduced O2 at low CO2 concentrations. When the partial pressure of O2 was held constant but the total pressure was varied between 51 and 101 kPa, the rate of CO2 uptake was nearly constant, suggesting that low pressure enhancement of Ps may be mainly attributable to lowered partial pressure of O2 and the accompanying reduction in Pr. The effects of lowered partial pressure of O2 on Ps and DR could result in substantial increases in the rates of biomass production, enabling rapid throughput of crops or allowing flexibility in the use of mass and energy resources for a CELSS.

Assessment of chloroethene degradation rates based on ratios of daughter/parent compounds in groundwater plumes

NASA Astrophysics Data System (ADS)

Höhener, Patrick

2014-05-01

Chlorinated solvent spills at industrial and urban sites create groundwater plumes where tetrachloro- and trichloroethene may degrade to their daughter compounds, dichloroethenes, vinyl chloride and ethane. The assessment of degradation and natural attenuation at such sites may be based on the analysis and inverse modelling of concentration data, on the calculation of mass fluxes in transsects, and/or on the analysis of stable isotope ratios in the ethenes. Relatively few work has investigated the possibility of using ratio of concentrations for gaining information on degradation rates. The use of ratios bears the advantage that dilution of a single sample with contaminant-free water does not matter. It will be shown that molar ratios of daughter to parent compounds measured along a plume streamline are a rapid and robust mean of determining whether degradation rates increase or decrease along the degradation chain, and allow furthermore a quantitation of the relative magnitude of degradation rates compared to the rate of the parent compound. Furthermore, ratios of concentration will become constant in zones where degradation is absent, and this allows to sketching the extension of actively degrading zones. The assessment is possible for pure sources and also for mixed sources. A quantification method is proposed in order to estimate first-order degradation rates in zones of constant degradation activity. This quantification method includes corrections that are needed due to longitudinal and transversal dispersivity. The method was tested on a number of real field sites from literature. At the majority of these sites, the first-order degradation rates were decreasing along the degradation chain from tetrachloroethene to vinyl chloride, meaning that the latter was often reaching important concentrations. This is bad news for site owners due to the increased toxicity of vinyl chloride compared to its parent compounds.

Effects of growth rate, cell size, motion, and elemental stoichiometry on nutrient transport kinetics

PubMed Central

Skibinski, David O. F.

2018-01-01

Nutrient acquisition is a critical determinant for the competitive advantage for auto- and osmohetero- trophs alike. Nutrient limited growth is commonly described on a whole cell basis through reference to a maximum growth rate (Gmax) and a half-saturation constant (KG). This empirical application of a Michaelis-Menten like description ignores the multiple underlying feedbacks between physiology contributing to growth, cell size, elemental stoichiometry and cell motion. Here we explore these relationships with reference to the kinetics of the nutrient transporter protein, the transporter rate density at the cell surface (TRD; potential transport rate per unit plasma-membrane area), and diffusion gradients. While the half saturation value for the limiting nutrient increases rapidly with cell size, significant mitigation is afforded by cell motion (swimming or sedimentation), and by decreasing the cellular carbon density. There is thus potential for high vacuolation and high sedimentation rates in diatoms to significantly decrease KG and increase species competitive advantage. Our results also suggest that Gmax for larger non-diatom protists may be constrained by rates of nutrient transport. For a given carbon density, cell size and TRD, the value of Gmax/KG remains constant. This implies that species or strains with a lower Gmax might coincidentally have a competitive advantage under nutrient limited conditions as they also express lower values of KG. The ability of cells to modulate the TRD according to their nutritional status, and hence change the instantaneous maximum transport rate, has a very marked effect upon transport and growth kinetics. Analyses and dynamic models that do not consider such modulation will inevitably fail to properly reflect competitive advantage in nutrient acquisition. This has important implications for the accurate representation and predictive capabilities of model applications, in particular in a changing environment. PMID:29702650

Effects of multi-frequency power ultrasound on the enzymolysis of corn gluten meal: Kinetics and thermodynamics study.

PubMed

Jin, Jian; Ma, Haile; Qu, Wenjuan; Wang, Kai; Zhou, Cunshan; He, Ronghai; Luo, Lin; Owusu, John

2015-11-01

The effects of multi-frequency power ultrasound (MPU) pretreatment on the kinetics and thermodynamics of corn gluten meal (CGM) were investigated in this research. The apparent constant (KM), apparent break-down rate constant (kA), reaction rate constants (k), energy of activation (Ea), enthalpy of activation (ΔH), entropy of activation (ΔS) and Gibbs free energy of activation (ΔG) were determined by means of the Michaelis-Menten equation, first-order kinetics model, Arrhenius equation and transition state theory, respectively. The results showed that MPU pretreatment can accelerate the enzymolysis of CGM under different enzymolysis conditions, viz. substrate concentration, enzyme concentration, pH, and temperature. Kinetics analysis revealed that MPU pretreatment decreased the KM value by 26.1% and increased the kA value by 7.3%, indicating ultrasound pretreatment increased the affinity between enzyme and substrate. In addition, the values of k for ultrasound pretreatment were increased by 84.8%, 41.9%, 28.9%, and 18.8% at the temperature of 293, 303, 313 and 323 K, respectively. For the thermodynamic parameters, ultrasound decreased Ea, ΔH and ΔS by 23.0%, 24.3% and 25.3%, respectively, but ultrasound had little change in ΔG value in the temperature range of 293-323 K. In conclusion, MPU pretreatment could remarkably enhance the enzymolysis of CGM, and this method can be applied to protein proteolysis industry to produce peptides. Copyright © 2015 Elsevier B.V. All rights reserved.

Cell growth and catecholase production for Polyporus versicolor in submerged culture

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

Carroad, P.A.; Wilke, C.R.

1977-04-01

Cell growth and catecholase production for Polyporus versicolor (ATCC 12679) were studied in mechanically agitated submerged culture, as functions of temperature. The exponential-phase growth rate exhibited a maximum at 28/sup 0/C. Over the range of 20/sup 0/C to approximately 30/sup 0/C, both cell mass and enzyme yield factors were constant. At higher temperatures (30 to 40/sup 0/C) cell mass yield factor decreased and enzyme yield factor increased. Specific respiration rate of P. versicolor was determined. Thermal deactivation of catecholase was investigated between 30 and 50/sup 0/C, and deactivation rates were fit to an Arrhenius rate expression.

[The language of medicine as presented in the references of original articles published in Medicina Clínica for 50 years (1945-1995)].

PubMed

Navarro, F A

1996-11-09

To describe and analyse the frequency of the various languages in the bibliographical references from the original articles published in MEDICINA CLINICA during the past 50 years (1945-1995). The languages of publication of 12,807 references from 540 original works published in MEDICINA CLINICA between 1945 and 1995 were determined (at the rate of near 50 articles per year at intervals of five years). The percentage of references in English increased constantly until 1980, but has decreased since then (26.3% in 1945, 42.1% in 1995, 57.7% in 1970, 84.2% in 1980 and 78.5% in 1995). In contrast, the percentage of references in Spanish decreased until 1980, but has increased since then (27.4% in 1945, 18.4% in 1955, 15.8% in 1970, 8.1% in 1980 and 20.0% in 1995). Initially the percentage of references in French remained more or less constant, but decreased markedly from 1970 on ward (23.1% in 1945, 22.5% in 1955, 17.1% in 1970, 5.9% in 1980 and 0.5% in 1995). The percentage of references in German decreased almost continuously during the whole period studied (19.6% in 1945, 10.7% in 1955, 5.8% in 1970, 0.3% in 1980 and 0.3% also in 1995). In 1965, English became the undisputed language of medicine in Spain. The importance of English increased from 1945, then stabilised and even started to decrease in 1980. The importance of Spanish has evolved inversely to that of English, decreasing until 1980 and increasing since that time. The importance of French remained stable until 1970, since when it has decreased, although it continued to be mentioned relatively frequently until 1990. The importance of German decreased constantly from 1945, until this language almost completely disappeared from 1985 onward.

Use of cellulose-based wastes for adsorption of dyes from aqueous solutions.

PubMed

Annadurai, Gurusamy; Juang, Ruey-Shin; Lee, Duu-Jong

2002-06-10

Low-cost banana and orange peels were prepared as adsorbents for the adsorption of dyes from aqueous solutions. Dye concentration and pH were varied. The adsorption capacities for both peels decreased in the order methyl orange (MO) > methylene blue (MB) > Rhodamine B (RB) > Congo red (CR) > methyl violet (MV) > amido black 10B (AB). The isotherm data could be well described by the Freundlich and Langmuir equations in the concentration range of 10-120 mg/l. An alkaline pH was favorable for the adsorption of dyes. Based on the adsorption capacity, it was shown that banana peel was more effective than orange peel. Kinetic parameters of adsorption such as the Langergren rate constant and the intraparticle diffusion rate constant were determined. For the present adsorption process intraparticle diffusion of dyes within the particle was identified to be rate limiting. Both peel wastes were shown to be promising materials for adsorption removal of dyes from aqueous solutions.

Cold Incineration of Chlorophenols in Aqueous Solution by Advanced Electrochemical Process Electro-Fenton. Effect of Number and Position of Chlorine Atoms on the Degradation Kinetics

NASA Astrophysics Data System (ADS)

Oturan, Nihal; Panizza, Marco; Oturan, Mehmet A.

2009-09-01

This study reports the kinetics of the degradation of several chlorophenols (CPs), such as monochlorophenols (2-chlorophenol and 4-chlorophenol), dichlorophenols (2,4-dichlorophenol and 2,6- dichlorophenol), trichlorophenols (2,3,5- trichlorophenol and 2,4,5-trichlorophenol), 2,3,5,6-tetrachlorophenol, and pentachlorophenol, by the electro-Fenton process using a carbon felt cathode and a Pt anode. The effect of number and the position of the chlorine atoms in the aromatic ring on the oxidative degradation rate was evaluated and discussed. The oxidation reaction of all the CPs with hydroxyl radicals evidenced a pseudo-first-order kinetics and the rate constant decreased with increasing the number of chlorine atoms. The absolute rate constant of second-order reaction kinetics between CPs and •OH was determined by the competition kinetics method in the range of (3.56-7.75) × 109 M-1 s-1 and follows the same sequence of the apparent rate constants. The mineralization of several CPs and of a mixture of all CPs under study was monitored by the total organic carbon (TOC) removal and the chlorine release during mineralization was followed by ion chromatography. Our results demonstrated that more chlorinated phenols are more difficult to mineralize; however for all the tested CPs, almost quantitative release of chloride ions was obtained after 6 h of treatment.

The influence of the position of the oxygen dissociation curve on oxygen-dependent functions of the isolated perfused rat liver. III. Studies at different levels of anaemic hypoxia.

PubMed

Bakker, J C; Gortmaker, G C; de Vries-van Rossen, A; Offerijns, F G

1977-03-11

The influence of a 2,3-diphosphoglycerate (2,3-DPG)-induced displacement of the oxygen dissociation curve (O.D.C.) on the isolated perfused rat liver was studied at different levels of anaemic hypoxia. Rat livers were perfused either with fresh or with 2,3-DPG-depleted human erythrocytes at different haematocrit values (from 30% to 2.5%) at constant Po2 of the inflowing perfusate and at constant blood flow rate. The 2,3-DPG-induced difference in oxygen affinity of the red cells did not cause a significant difference in perfusion pressure during the perfusion experiments. Therefore, there is no evidence that 2,3-DPG did alter the vascular resistance of the liver, since blood flow rate could be adusted at equal values. The decrease in oxygen supply brought about by decrease of haematocrit caused a decrease of O2 consumption, of bile flow rate and of venous Po2 and an increase of lactate/pyruvate (L/P) ratio and of beta-hydroxybutyrate/acetoacetate (betaOH/Acac) ratio. There was no influence of a difference in 2,3-DPG content of the erythrocytes on the above-metioned parameters during severe anaemic hypoxia. At moderate anaemic hypoxia the venous Po2 was higher during perfusion with fresh erythrocytes than during perfusion with 2,3-DPG-depleted erythrocytes. Thus, although 2,3-DPG may play a compensatory role during conditions of mild anaemia, no such effects can be observed during conditions of severe hypoxia.

Creep and intergranular cracking behavior of nickel-chromium-iron-carbon alloys in 360 C water

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

Angeliu, T.M.; Paraventi, D.J.; Was, G.S.

1995-11-01

Mechanical testing of controlled-purity Ni-x% Cr-9% Fe-y% C alloys at 360 C revealed an environmental enhancement in intergranular (IG) cracking and time-dependent deformation in high-purity (HP) and primary water (PW) over that exhibited in argon. Dimples on the IG facets indicated a creep void nucleation and growth failure mode. IG cracking was located primarily in the interior of the specimen and was not necessarily linked to the environment. Controlled-potential constant extension rate tensile (CERT) experiments showed increases in IG cracking as the applied potential decreased, suggesting that hydrogen was detrimental to the mechanical properties. It was proposed that the environment,more » through the presence of hydrogen, enhanced IG cracking by enhancing the matrix dislocation mobility. This conclusion was based on observations that dislocation creep controlled IG cracking of controlled-purity Ni-x% Cr-9% Fe-y% C in argon at 360 C. Grain-boundary cavitation (GBC) and sliding (GBS) results showed environmental enhancement of the creep rate primarily resulted from an increase in matrix plastic deformation. However, controlled-potential constant load tensile (CLT) experiments did not indicate a change in the creep rate as the applied potential decreased. While this result did not support hydrogen-assisted creep, the material already may have been saturated with hydrogen at these applied potentials, and thus, no effect was realized. Chromium and carbon decreased IG cracking in HP and PW by increasing the creep resistance. The surface film did not play a significant role in the creep or IG cracking behavior under the conditions investigated.« less

Substitutions of S101 decrease proton and hydride transfers in the oxidation of betaine aldehyde by choline oxidase.

PubMed

Gadda, Giovanni; Yuan, Hongling

2017-11-15

Choline oxidase oxidizes choline to glycine betaine, with two flavin-mediated reactions to convert the alcohol substrate to the carbon acid product. Proton abstraction from choline or hydrated betaine aldehyde in the wild-type enzyme occurs in the mixing time of the stopped-flow spectrophotometer, thereby precluding a mechanistic investigation. Mutagenesis of S101 rendered the proton transfer reaction amenable to study. Here, we have investigated the aldehyde oxidation reaction catalyzed by the mutant enzymes using steady-state and rapid kinetics with betaine aldehyde. Stopped-flow traces for the reductive half-reaction of the S101T/V/C variants were biphasic, corresponding to the reactions of proton abstraction and hydride transfer. In contrast, the S101A enzyme yielded monophasic traces like wild-type choline oxidase. The rate constants for proton transfer in the S101T/C/V variants decreased logarithmically with increasing hydrophobicity of residue 101, indicating a behavior different from that seen previously with choline for which no correlation was determined. The rate constants for hydride transfer also showed a logarithmic decrease with increasing hydrophobicity at position 101, which was similar to previous results with choline as a substrate for the enzyme. Thus, the hydrophilic character of S101 is necessary not only for efficient hydride transfer but also for the proton abstraction reaction. Copyright © 2017. Published by Elsevier Inc.

Bioavailability of methylmercury to Sacramento blackfish (Orthodon microlepidotus): Dissolved organic carbon effects

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

Choi, M.H.; Cech, J.J. Jr.; Lagunas-Solar, M.C.

1998-04-01

The effect of dissolved organic carbon (DOC) on methylmercury (MeHg) uptake across the gills of Sacramento blackfish (Orthodon microlepidotus) was investigated using the Hg-203 radioisotope. The efficiency of fish gills in extracting MeHg from water was measured using a McKim-type fish respirometer that separated exposure water from expired water. Blackfish gill ventilation and oxygen consumption rates remained constant, while Me{sup 203}Hg uptake was decreased significantly in the presence of DOC. Mean Me{sup 203}Hg extraction efficiency, uptake rate constant, and blood to inspired water ratio decreased 78%, 73%, and 63%, respectively, with 2 mg C/L of DOC, and 85%, 82%, andmore » 70% with 5 mg C/L DOC, compared to the Me{sup 203}Hg reference treatment group. Because respiratory parameters remained unchanged, reductions in Me{sup 203}Hg uptake indicate strong interactions between DOC and Me{sup 203}Hg Methyl{sup 203}Hg levels in fish gills, kidney, and spleen from 2 and 5 mg C/L were significantly lower than those observed from the reference treatment group. These reductions in uptake (bioavailability) support the hypothesis that trans-gill transport of Me{sup 203}Hg is inhibited when it is complexed by DOC in the aqueous medium, decreasing Me{sup 203}Hg uptake and accumulation in fish organs.« less

Responding for sucrose and wheel-running reinforcement: effects of sucrose concentration and wheel-running reinforcer duration.

PubMed

Belke, Terry W; Hancock, Stephanie D

2003-03-01

Six male albino rats were placed in running wheels and exposed to a fixed-interval 30-s schedule of lever pressing that produced either a drop of sucrose solution or the opportunity to run for a fixed duration as reinforcers. Each reinforcer type was signaled by a different stimulus. In Experiment 1, the duration of running was held constant at 15 s while the concentration of sucrose solution was varied across values of 0, 2.5. 5, 10, and 15%. As concentration decreased, postreinforcement pause duration increased and local rates decreased in the presence of the stimulus signaling sucrose. Consequently, the difference between responding in the presence of stimuli signaling wheel-running and sucrose reinforcers diminished, and at 2.5%, response functions for the two reinforcers were similar. In Experiment 2, the concentration of sucrose solution was held constant at 15% while the duration of the opportunity to run was first varied across values of 15, 45, and 90 s then subsequently across values of 5, 10, and 15 s. As run duration increased, postreinforcement pause duration in the presence of the wheel-running stimulus increased and local rates increased then decreased. In summary, inhibitory aftereffects of previous reinforcers occurred when both sucrose concentration and run duration varied; changes in responding were attributable to changes in the excitatory value of the stimuli signaling the two reinforcers.

Decrease of total activity with time at long distances from a nuclear accident or explosion.

PubMed

Dolejs, Josef

2005-05-01

Two data groups were analyzed: (1) the exposure rate in the former Czechoslovakia after the Chernobyl accident in 1986, and (2) the decrease of beta activity of an atmospheric fallout sample taken in Bratislava during 24 h on 30 May 1965. Both quantities decreased with the first power of time. This pattern of decrease is explained by applying the same mathematical formalism as is also used to describe the decrease in postnatal mortality with age. Following this formalism, the decrease of total activity with the first power of time could be seen as a consequence of a log-normal distribution of decay constants in the fallout. This differs slightly from earlier results that show the total activity decreasing with a power of 1.2 immediately after the nuclear explosion.

The mechanism and thermodynamics of transesterification of acetate-ester enolates in the gas phase

NASA Astrophysics Data System (ADS)

Haas, George W.; Giblin, Daryl E.; Gross, Michael L.

1998-01-01

In solution, base-catalyzed hydrolysis and transesterification of esters are initiated by hydroxide- or alkoxide-ion attack at the carbonyl carbon. At low pressures in the gas phase, however, transesterification proceeds by an attack of the enolate anion of an acetate ester on an alcohol. Fourier transform mass spectrometry (FTMS) indicates that the reaction is the second-order process: -CH2-CO2-R + R'-OH --> - CH2-CO2-R' + R-OH and there is little to no detectable production of either alkoxide anion. Labeling studies show that the product and reactant enolate anion esters undergo exchange of hydrogens located [alpha] to the carbonyl carbon with the deuterium of R'-OD. The extent of the H/D exchange increases with reaction time, pointing to a short-lived intermediate. The alcoholysis reaction rate constants increase with increasing acidity of the primary, straight-chained alkyl alcohols, whereas steric effects associated with branched alcohols cause the rate constants to decrease. Equilibrium constants, which were determined directly from measurements at equilibrium and which were calculated from the forward and reverse rate constants, are near unity and show internal consistency. In the absence of steric effects, the larger enolate is always the favored product at equilibrium. The intermediate for the transesterification reaction, which can be generated at a few tenths of a torr in a tandem mass spectrometer, is tetrahedral, but other adducts that are collisionally stabilized under these conditions are principally loosely bound complexes.

The effects of temperature treatment on photosynthesis of pitch pine from northern and southern latitudes

Treesearch

F. Thomas Ledig; Joseph G. Clark; Allen P. Drew

1977-01-01

Pitch pine (Pinus rigida Mill.) seedlings were grown at constant temperatures of either 21 C or 29 C. Photosynthetic temperature and light response curves were determined after 59, 107, and 153 days. Rates of Co2 uptake decreased with age, and the response to changes in light and temperature became less pronounced. Growth...

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...

The influence of the Tbeta level upon fluorescence and laser properties of aromatic compounds.

PubMed

Nijegorodov, N; Winkoun, D P; Nkoma, J S

2004-07-01

The fluorescence and laser properties of seven specially chosen aromatic compounds are studied at 293 degrees C. The quantum yield of fluorescence, gamma, decay times, tauf, of the deaerated and non-deaerated solutions are measured. The oscillator strength, fe, fluorescence rate constants, kf, natural lifetimes, tauT0, and intersystem crossing rate constants, kST, are calculated. Some laser parameters are calculated or measured experimentally. It is found that the position of the Tbeta level plays an important role in the fluorescence and laser properties of aromatic compounds. If the Tbeta level is situated below the Sp level, it decreases the quantum yield of fluorescence and the decay time and increases the threshold of laser action. If, due to some structural changes of a molecule, the Tbeta level is situated higher than the Sp level, then the quantum yield of fluorescence and the decay times are increasing and the threshold of laser action is decreasing. Such influence of the position of the Tbeta level upon fluorescence and laser properties of aromatic compound is explained by the fact that the Sp level mixes with the Tbeta level more readily than with other taupipi* levels.

The effects of temperature on optical properties of InGaN/GaN multiple quantum well light-emitting diodes

NASA Astrophysics Data System (ADS)

Li, Yi; Zhu, Youhua; Huang, Jing; Deng, Honghai; Wang, Meiyu; Yin, HaiHong

2017-02-01

The effects of temperature on the optical properties of InGaN/GaN quantum well (QW) light-emitting diodes have been investigated by using the six-by-six K-P method taking into account the temperature dependence of band gaps, lattice constants, and elastic constants. The numerical results indicate that the increase of temperature leads to the decrease of the spontaneous emission rate at the same injection current density due to the redistribution of carrier density and the increase of the non-radiative recombination rate. The product of Fermi-Dirac distribution functions of electron fc n and hole ( 1 - fv U m ) for the transitions between the three lowest conduction subbands (c1-c3) and the top six valence subbands (v1-v6) is larger at the lower temperature, which indicates that there are more electron-hole pairs distributed on the energy levels. It should be noted that the optical matrix elements of the inter-band transitions slightly increase at the higher temperature. In addition, the internal quantum efficiency of the InGaN/GaN QW structure is evidently decreased with increasing temperature.

Age structure and capital dilution effects in neo-classical growth models.

PubMed

Blanchet, D

1988-01-01

Economists often over estimate capital dilution effects when applying neoclassical growth models which use age structured population and depreciation of capital stock. This occurs because capital stock is improperly characterized. A standard model which assumes a constant depreciation of capital intimates that a population growth rate equal to a negative constant savings ratio is preferable to any higher growth rate. Growth rates which are lower than a negative constant savings ratio suggest an ever growing capital/labor ratio and an ever growing standard of living, even if people do not save. This is suggested because the natural reduction of the capital stock through depreciation is slower than the population decrease which is simply unrealistic. This model overlooks the fact that low or negative growth rates result in an ageing of the capital stock, and this ageing subsequently results in an increase of the overall rate of capital depreciation. In that overly simplistic model, depreciation was assumed independent of the age of the captial stock. Incorporating depreciation as a variable into a model allows a more symmetric treatment of capital. Using models with heterogenous capital, this article explores what occurs when more than 1 kind of capital good is involved in production and when these various captial goods have different lengths of life. Applying economic models, it also examines what occurs when the length of life of capital may vary. These variations correct the negative impact that population growth can have on per capital production and consumption.

The kinetics of competitive antagonists on guinea-pig ileum.

PubMed Central

Roberts, F; Stephenson, R P

1976-01-01

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

The simultaneous discharge of liquid and grains from a silo

NASA Astrophysics Data System (ADS)

Cervantes-Álvarez, A. M.; Hidalgo-Caballero, S.; Pacheco-Vázquez, F.

2018-04-01

The flow rate of water through an orifice at the bottom of a container depends on the hydrostatic pressure whereas for a dry granular material it is nearly constant. But what happens during the simultaneous discharge of grains and liquid from a silo? By measuring the flow rate as a function of time, we found that (i) different regimes appear, going from the constant flow rate to a hydrostatic-like discharge depending on the aperture size and grain diameter, (ii) the mixed material is always discharged faster than dry grains but slower than liquid, (iii) for the mixture, the liquid level drops faster than the grain level, but they are always linearly proportional to one another, and (iv) a sudden growth in the flow rate happens during the transition from a biphasic discharge to a single phase discharge. These results are associated to the competition between the decrease in hydrostatic pressure above the granular bed and the hydrodynamic resistance. A model combining Darcy's law with Bernoulli and mass conservation equations is proposed, and the numerical results are in good agreement with experiments.

The entrance of water into beef and dog red cells.

PubMed

VILLEGAS, R; BARTON, T C; SOLOMON, A K

1958-11-20

The rate constants for diffusion of THO across the red cell membrane of beef and dog, and the rate of entrance of water into the erythrocytes of these species under an osmotic pressure gradient have been measured. For water entrance into the erythrocyte by diffusion the rate constants are 0.10 +/- 0.02 msec.(-1) (beef) and 0.14 +/- 0.03 msec.(-1) (dog); the permeability coefficients for water entrance under a pressure gradient of 1 osmol./cm(3) are 0.28 See PDF for Equation These values permit the calculation of an equivalent pore radius for the erythrocyte membrane of 4.1 A for beef and 7.4 A for dog. In the beef red cell the change in THO diffusion due to osmotically produced cell volume shifts has been studied. The resistance to THO diffusion increases as the cell volume increases. At the maximum volume, (1.06 times normal), THO diffusion is decreased to 0.84 times the normal rate. This change in diffusion is attributed to swelling of the cellular membrane.

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

NASA Astrophysics Data System (ADS)

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

2010-11-01

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

The Henry's constant of monochloramine.

PubMed

Garcia, Miguel A; Anderson, Michael A

2018-02-01

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

Effect of Oxygen Gas on the Decomposition of Dye by Pulsed Discharge in Water Droplet Spray

NASA Astrophysics Data System (ADS)

Nose, Taisuke; Yokoyama, Yuzo; Nakamura, Akira; Minamitani, Yasushi

Effect of O2 on the decolorization of indigo carmine and on the production of dissolved species such as NO2-, NO3-, O3 and H2O2 in the treatment water by pulsed discharge in water droplet spray was investigated by controlling the O2/N2 ratios as carrier gases in the reactor. The decolorization rate gradually increased with rise in O2 ratio, which reached a constant value in the range of 50% to 90% O2 ratio and decreased in pure O2. The maximum value was about 2 times as high as that of 20% O2 ratio. The decolorization efficiency was not affected by gas flow rate in the range of 4 L/min to 50 L/min. NO2- in the treatment water was only detected in pure N2, but NO3- was produced in O2/N2. NO2- added to the treatment water was not oxidized in pure N2, but was perfectly converted to NO3- in O2/N2. These results implied that hydroxyl radical produced in gas phase does not directly contribute to the oxidation of substances in water. O3 concentration gradually increased with rise in O2 ratio, whereas H2O2 concentration decreased. In the range of 50 to 80% O2 ratio, O3 and H2O2 concentrations were approximately constant value, similar to the trend of decolorization rate. Moreover rate constants on various gas mixing ratio of O2/N2 were determined from the kinetics study. These results suggested that hydroxyl radical produced in the treatment water by the chain reactions of O3 and hydroperoxy radical (HO2·) plays an important role of the decomposition of molecules in water.

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

Modeling the influence of preferential flow on the spatial variability and time-dependence of mineral weathering rates

DOE PAGES

Pandey, Sachin; Rajaram, Harihar

2016-12-05

Inferences of weathering rates from laboratory and field observations suggest significant scale and time-dependence. Preferential flow induced by heterogeneity (manifest as permeability variations or discrete fractures) has been suggested as one potential mechanism causing scale/time-dependence. In this paper, we present a quantitative evaluation of the influence of preferential flow on weathering rates using reactive transport modeling. Simulations were performed in discrete fracture networks (DFNs) and correlated random permeability fields (CRPFs), and compared to simulations in homogeneous permeability fields. The simulations reveal spatial variability in the weathering rate, multidimensional distribution of reactions zones, and the formation of rough weathering interfaces andmore » corestones due to preferential flow. In the homogeneous fields and CRPFs, the domain-averaged weathering rate is initially constant as long as the weathering front is contained within the domain, reflecting equilibrium-controlled behavior. The behavior in the CRPFs was influenced by macrodispersion, with more spread-out weathering profiles, an earlier departure from the initial constant rate and longer persistence of weathering. DFN simulations exhibited a sustained time-dependence resulting from the formation of diffusion-controlled weathering fronts in matrix blocks, which is consistent with the shrinking core mechanism. A significant decrease in the domain-averaged weathering rate is evident despite high remaining mineral volume fractions, but the decline does not follow a math formula dependence, characteristic of diffusion, due to network scale effects and advection-controlled behavior near the inflow boundary. Finally, the DFN simulations also reveal relatively constant horizontally averaged weathering rates over a significant depth range, challenging the very notion of a weathering front.« less

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

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

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

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

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

DOE PAGES

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

2016-03-19

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

Modeling the influence of preferential flow on the spatial variability and time-dependence of mineral weathering rates

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

Pandey, Sachin; Rajaram, Harihar

Inferences of weathering rates from laboratory and field observations suggest significant scale and time-dependence. Preferential flow induced by heterogeneity (manifest as permeability variations or discrete fractures) has been suggested as one potential mechanism causing scale/time-dependence. In this paper, we present a quantitative evaluation of the influence of preferential flow on weathering rates using reactive transport modeling. Simulations were performed in discrete fracture networks (DFNs) and correlated random permeability fields (CRPFs), and compared to simulations in homogeneous permeability fields. The simulations reveal spatial variability in the weathering rate, multidimensional distribution of reactions zones, and the formation of rough weathering interfaces andmore » corestones due to preferential flow. In the homogeneous fields and CRPFs, the domain-averaged weathering rate is initially constant as long as the weathering front is contained within the domain, reflecting equilibrium-controlled behavior. The behavior in the CRPFs was influenced by macrodispersion, with more spread-out weathering profiles, an earlier departure from the initial constant rate and longer persistence of weathering. DFN simulations exhibited a sustained time-dependence resulting from the formation of diffusion-controlled weathering fronts in matrix blocks, which is consistent with the shrinking core mechanism. A significant decrease in the domain-averaged weathering rate is evident despite high remaining mineral volume fractions, but the decline does not follow a math formula dependence, characteristic of diffusion, due to network scale effects and advection-controlled behavior near the inflow boundary. Finally, the DFN simulations also reveal relatively constant horizontally averaged weathering rates over a significant depth range, challenging the very notion of a weathering front.« less

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.

The ratio of NPP to GPP: evidence of change over the course of stand development.

PubMed

Mäkelä, A; Valentine, H T

2001-09-01

Using Scots pine (Pinus sylvestris L.) in Fenno-Scandia as a case study, we investigate whether net primary production (NPP) and maintenance respiration are constant fractions of gross primary production (GPP) as even-aged mono-specific stands progress from initiation to old age. A model of the ratio of NPP to GPP is developed based on (1) the classical model of respiration, which divides total respiration into construction and maintenance components, and (2) a process-based model, which derives respiration from processes including construction, nitrate uptake and reduction, ion uptake, phloem loading and maintenance. Published estimates of specific respiration and production rates, and some recent measurements of components of dry matter in stands of different ages, are used to quantify the two approaches over the course of stand development in an average environment. Both approaches give similar results, showing a decrease in the NPP/GPP ratio with increasing tree height. In addition, we show that stand-growth models fitted under three different sets of assumptions-(i) annual specific rates of maintenance respiration of sapwood (mW) and photosynthesis (sC) are constant; (ii) m(W) is constant, but sC decreases with increasing tree height; and (iii) total maintenance respiration is a constant fraction of GPP and s(C) decreases with increasing tree height-can lead to nearly identical model projections that agree with empirical observations of NPP and stand-growth variables. Remeasurements of GPP and respiration over time in chronosequences of stands may be needed to discern which set of assumptions is correct. Total (construction + maintenance) sapwood respiration per unit mass of sapwood (kg C (kg C year)-1) decreased with increasing stand age, sapwood stock, and average tree height under all three assumptions. However, total sapwood respiration (kg C (ha year)-1) increased over the course of stand development under (i) and (ii), contributing to a downward trend in the time course of the NPP/GPP ratio after closure. A moderate decrease in mW with increasing tree height or sapwood cross-sectional area had little effect on the downward trend. On the basis of this evidence, we argue that a significant decline in the NPP/GPP ratio with tree size or age seems highly probable, although the decline may appear insignificant over some segments of stand development. We also argue that, because stand-growth models can give correct answers for the wrong reasons, statistical calibration of such models should be avoided whenever possible; instead, values of physiological parameters should come from measurements of the physiological processes themselves.

Electrosprayed Cerium Oxide Nanoparticles

NASA Astrophysics Data System (ADS)

Azar, Pedram Bagherzadeh; Tavanai, Hossein; Allafchian, Ali Reza

2018-04-01

Cerium oxide nanoparticles were fabricated via the calcination of electrosprayed polyvinyl alcohol (PVA)/cerium nitrate nanoparticles. The effect of material variables of PVA/cerium nitrate electrospraying solution, i.e. viscosity, surface tension and electrical conductivity, as well as important process variables like voltage, nozzle-collector distance and feed rate on cerium oxide nanoparticle size, are investigated. Scanning electron microscopy and Fourier-transform infrared (FTIR) spectroscopy analysis have also been carried out. The results showed that electrospraying of PVA/cerium nitrate (25% w/v) was only possible with PVA concentrations in the range of 5-8% w/v. With other conditions constant, decreasing PVA concentration, decreasing feed rate, increasing nozzle-collector distance and increasing voltage decreased the size of the final cerium oxide nanoparticles. The gross average size of all cerium oxide nanoparticles obtained in this work was about 80 nm. FTIR analysis proved the formation of cerium oxide after the calcination process.

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

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

Cannon, William; Zucker, Jeremy; Baxter, Douglas

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

Improved Efficacy of Synthesizing *MIII-Labeled DOTA Complexes in Binary Mixtures of Water and Organic Solvents. A Combined Radio- and Physicochemical Study.

PubMed

Pérez-Malo, Marylaine; Szabó, Gergely; Eppard, Elisabeth; Vagner, Adrienn; Brücher, Ernő; Tóth, Imre; Maiocchi, Alessandro; Suh, Eul Hyun; Kovács, Zoltán; Baranyai, Zsolt; Rösch, Frank

2018-05-21

Typically, the synthesis of radiometal-based radiopharmaceuticals is performed in buffered aqueous solutions. We found that the presence of organic solvents like ethanol increased the radiolabeling yields of [ 68 Ga]Ga-DOTA (DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacatic acid). In the present study, the effect of organic cosolvents [ethanol (EtOH), isopropyl alcohol, and acetonitrile] on the radiolabeling yields of the macrocyclic chelator DOTA with several trivalent radiometals (gallium-68, scandium-44, and lutetium-177) was systematically investigated. Various binary water (H 2 O)/organic solvent mixtures allowed the radiolabeling of DOTA at a significantly lower temperature than 95 °C, which is relevant for the labeling of sensitive biological molecules. Simultaneously, much lower amounts of the chelators were required. This strategy may have a fundamental impact on the formulation of trivalent radiometal-based radiopharmaceuticals. The equilibrium properties and formation kinetics of [M(DOTA)] - (M III = Ga III , Ce III , Eu III , Y III , and Lu III ) complexes were investigated in H 2 O/EtOH mixtures (up to 70 vol % EtOH). The protonation constants of DOTA were determined by pH potentiometry in H 2 O/EtOH mixtures (0-70 vol % EtOH, 0.15 M NaCl, 25 °C). The log K 1 H and log K 2 H values associated with protonation of the ring N atoms decreased with an increase of the EtOH content. The formation rates of [M(DOTA)] - complexes increase with an increase of the pH and [EtOH]. Complexation occurs through rapid formation of the diprotonated [M(H 2 DOTA)] + intermediates, which are in equilibrium with the kinetically active monoprotonated [M(HDOTA)] intermediates. The rate-controlling step is deprotonation (and rearrangement) of the monoprotonated intermediate, which occurs through H 2 O ( *M(HL) k H 2 O ) and OH - ( *M(HL) k OH ) assisted reaction pathways. The rate constants are essentially independent of the EtOH concentration, but the M(HL) k H2O values increase from Ce III to Lu III . However, the log K M(HL) H protonation constants, analogous to the log K H 2 value, decrease with increasing [EtOH], which increases the concentration of the monoprotonated M(HDOTA) intermediate and accelerates formation of the final complexes. The overall rates of complex formation calculated by the obtained rate constants at different EtOH concentrations show a trend similar to that of the complexation rates determined with the use of radioactive isotopes.

Magnetization Switching of a Co /Pt Multilayered Perpendicular Nanomagnet Assisted by a Microwave Field with Time-Varying Frequency

NASA Astrophysics Data System (ADS)

Suto, Hirofumi; Kanao, Taro; Nagasawa, Tazumi; Mizushima, Koichi; Sato, Rie

2018-05-01

Microwave-assisted magnetization switching (MAS) is attracting attention as a method for reversing nanomagnets with a high magnetic anisotropy by using a small-amplitude magnetic field. We experimentally study MAS of a perpendicularly magnetized nanomagnet by applying a microwave magnetic field with a time-varying frequency. Because the microwave field frequency can follow the nonlinear decrease of the resonance frequency, larger magnetization excitation than that in a constant-frequency microwave field is induced, which enhances the MAS effect. The switching field decreases almost linearly as the start value of the time-varying microwave field frequency increases, and it becomes smaller than the minimum switching field in a constant-frequency microwave field. To obtain this enhancement of the MAS effect, the end value of the time-varying microwave field frequency needs to be almost the same as or lower than the critical frequency for MAS in a constant-frequency microwave field. In addition, the frequency change typically needs to take 1 ns or longer to make the rate of change slow enough for the magnetization to follow the frequency change. This switching behavior is qualitatively explained by the theory based on the macrospin model.

Water-soluble cavitands promote hydrolyses of long-chain diesters

PubMed Central

Shi, Qixun; Mower, Matthew P.; Blackmond, Donna G.; Rebek, Julius

2016-01-01

Water-soluble, deep cavitands serve as chaperones of long-chain diesters for their selective hydrolysis in aqueous solution. The cavitands bind the diesters in rapidly exchanging, folded J-shape conformations that bury the hydrocarbon chain and expose each ester group in turn to the aqueous medium. The acid hydrolyses in the presence of the cavitand result in enhanced yields of monoacid monoester products. Product distributions indicate a two- to fourfold relative decrease in the hydrolysis rate constant of the second ester caused by the confined space in the cavitand. The rate constant for the first acid hydrolysis step is enhanced approximately 10-fold in the presence of the cavitand, compared with control reactions of the molecules in bulk solution. Hydrolysis under basic conditions (saponification) with the cavitand gave >90% yields of the corresponding monoesters. Under basic conditions the cavitand complex of the monoanion precipitates from solution and prevents further reaction. PMID:27482089

Nonlinear Dynamics of Turbulent Thermals in Shear Flow

NASA Astrophysics Data System (ADS)

Ingel, L. Kh.

2018-03-01

The nonlinear integral model of a turbulent thermal is extended to the case of the horizontal component of its motion relative to the medium (e.g., thermal floating-up in shear flow). In contrast to traditional models, the possibility of a heat source in the thermal is taken into account. For a piecewise constant vertical profile of the horizontal velocity of the medium and a constant vertical velocity shear, analytical solutions are obtained which describe different modes of dynamics of thermals. The nonlinear interaction between the horizontal and vertical components of thermal motion is studied because each of the components influences the rate of entrainment of the surrounding medium, i.e., the growth rate of the thermal size and, hence, its mobility. It is shown that the enhancement of the entrainment of the medium due to the interaction between the thermal and the cross flow can lead to a significant decrease in the mobility of the thermal.

Viscosity effects on the thermal decomposition of bis(perfluoro-2-N-propoxypropionyl) peroxide in dense carbon dioxide and fluorinated solvents.

PubMed

Bunyard, W C; Kadla, J F; DeYoung, J; DeSimone, J M

2001-08-01

The thermal decomposition of the free-radical initiator bis(perfluoro-2-N-propoxyprionyl) peroxide (BPPP) was studied in dense carbon dioxide and a series of fluorinated solvents. For the fluorinated solvents, the observed first-order decomposition rate constants, k(obs), increased with decreasing solvent viscosity, suggesting a single-bond decomposition mechanism. The k(obs) values are comparatively larger in dense carbon dioxide and similar to the "zero-viscosity" rate constants extrapolated from the decomposition kinetics in the fluorinated solvents. The decomposition activation parameters demonstrate a compensation behavior of the activation enthalpy with the activation entropy upon change in solvent viscosity. Comparison of the change in activation parameter values upon change in solvent viscosity for BPPP with two additional initiators, acetyl peroxide (AP) and trifluoroacetyl peroxide (TFAP), further suggests that carbon dioxide exerts a very minimal influence on the decomposition mechanism of these initiators through solvent-cage effects.

Microfluidics and Coagulation Biology

PubMed Central

Colace, Thomas V.; Tormoen, Garth W.

2014-01-01

The study of blood ex vivo can occur in closed or open systems, with or without flow. Microfluidic devices facilitate measurements of platelet function, coagulation biology, cellular biorheology, adhesion dynamics, pharmacology, and clinical diagnostics. An experimental session can accommodate 100s to 1000s of unique clotting events. Using microfluidics, thrombotic events can be studied on defined surfaces of biopolymers, matrix proteins, and tissue factor under constant flow rate or constant pressure drop conditions. Distinct shear rates can be created on a device with a single perfusion pump. Microfluidic devices facilitated the determination of intraluminal thrombus permeability and the discovery that platelet contractility can be activated by a sudden decrease in flow. Microfluidics are ideal for multicolor imaging of platelets, fibrin, and phosphatidylserine and provide a human blood analog to the mouse injury models. Overall, microfluidic advances offer many opportunities for research, drug testing under relevant hemodynamic conditions, and clinical diagnostics. PMID:23642241

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Dynamics of Soil Water Evaporation during Soil Drying in the Presence of a Shallow Water Table: Laboratory Experiment and Numerical Analysis

NASA Astrophysics Data System (ADS)

Han, J.; Lin, J.; Liu, P.; Li, W.

2017-12-01

Evaporation from a porous medium plays a key role in hydrological, agricultural, environmental, and engineering applications. Laboratory and numerical experiments were conducted to investigate the evolution of soil water evaporation during a continuous drying event. Simulated soil water contents and temperatures by the calibrated model well reproduced measured values at different depths. Results show that the evaporative drying process could be divided into three stages, beginning with a relatively high evaporation rate during stage 1, followed by a lower rate during transient stage and stage 2, and finally maintaining a very low and constant rate during stage 3. The condensation zone was located immediately below the evaporation zone in the profile. Both peaks of evaporation and condensation rate increased rapidly during stage 1 and transition stage, decreased during stage 2, and maintained constant during stage 3. The width of evaporation zone kept a continuous increase during stages 1 and 2 and maintained a nearly constant value of 0.68 cm during stage 3. When the evaporation zone totally moved into the subsurface, a dry surface layer (DSL) formed above the evaporation zone at the end of stage 2. The width of DSL also presented a continuous increase during stage 2 and kept a constant value of 0.71 cm during stage 3. Although the magnitude of condensation zone was much smaller than that for the evaporation zone, the importance of the contribution of condensation zone to soil water dynamics should not be underestimated. Results from our experiment and numerical simulation show that this condensation process resulted in an unexpected and apparent water content increase in the middle of vadose zone profile.

Quantum dynamics of the C(1D)+HD and C(1D)+n-D2 reactions on the ã 1A' and b 1A" surfaces.

PubMed

Defazio, Paolo; Gamallo, Pablo; González, Miguel; Akpinar, Sinan; Bussery-Honvault, Béatrice; Honvault, Pascal; Petrongolo, Carlo

2010-03-14

We present the Born-Oppenheimer, quantum dynamics of the reactions C((1)D)+HD and C((1)D)+n-D(2) on the uncoupled potential energy surfaces ã (1)A' and b (1)A", considering the Coriolis interactions and the nuclear-spin statistics. Using the real wavepacket method, we obtain initial-state-resolved probabilities, cross sections, isotopic branching ratios, and rate constants. Similarly to the C+n-H(2) reaction, the probabilities present many ã (1)A' or few b (1)A" sharp resonances, and the cross sections are very large at small collision energies and decrease at higher energies. At any initial condition, the C+HD reaction gives preferentially the CD+H products. Thermal cross sections, isotopic branching ratios, and rate constant k vary slightly with temperature and agree very well with the experimental values. At 300 K, we obtain for the various products k(CH+H)=(2.45+/-0.08) x 10(-10), k(CD+H)=(1.19+/-0.04) x 10(-10), k(CH+D)=(0.71+/-0.02) x 10(-10), k(CD+D)=(1.59+/-0.05) x 10(-10) cm(3) s(-1), and k(CD+H)/k(CH+D)=1.68+/-0.01. The b (1)A" contribution to cross sections and rate constants is always large, up to a maximum value of 62% for a rotationally resolved C+D(2) rate constant. The upper b (1)A" state is thus quite important in the C((1)D) collision with H(2) and its deuterated isotopes, as the agreement between theory and experiment shows.

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 violated.

The socio-economic drivers of bushmeat consumption during the West African Ebola crisis.

PubMed

Ordaz-Németh, Isabel; Arandjelovic, Mimi; Boesch, Lukas; Gatiso, Tsegaye; Grimes, Trokon; Kuehl, Hjalmar S; Lormie, Menladi; Stephens, Colleen; Tweh, Clement; Junker, Jessica

2017-03-01

Bushmeat represents an important source of animal protein for humans in tropical Africa. Unsustainable bushmeat hunting is a major threat to wildlife and its consumption is associated with an increased risk of acquiring zoonotic diseases, such as Ebola virus disease (EVD). During the recent EVD outbreak in West Africa, it is likely that human dietary behavior and local attitudes toward bushmeat consumption changed in response to the crisis, and that the rate of change depended on prevailing socio-economic conditions, including wealth and education. In this study, we therefore investigated the effects of income, education, and literacy on changes in bushmeat consumption during the crisis, as well as complementary changes in daily meal frequency, food diversity and bushmeat preference. More specifically, we tested whether wealthier households with more educated household heads decreased their consumption of bushmeat during the EVD crisis, and whether their daily meal frequency and food diversity remained constant. We used Generalized Linear Mixed Models to analyze interview data from two nationwide household surveys across Liberia. We found an overall decrease in bushmeat consumption during the crisis across all income levels. However, the rate of bushmeat consumption in high-income households decreased less than in low-income households. Daily meal frequency decreased during the crisis, and the diversity of food items and preferences for bushmeat species remained constant. Our multidisciplinary approach to study the impact of EVD can be applied to assess how other disasters affect social-ecological systems and improve our understanding and the management of future crises.

The socio-economic drivers of bushmeat consumption during the West African Ebola crisis

PubMed Central

Arandjelovic, Mimi; Boesch, Lukas; Gatiso, Tsegaye; Grimes, Trokon; Kuehl, Hjalmar S.; Lormie, Menladi; Stephens, Colleen; Tweh, Clement; Junker, Jessica

2017-01-01

Bushmeat represents an important source of animal protein for humans in tropical Africa. Unsustainable bushmeat hunting is a major threat to wildlife and its consumption is associated with an increased risk of acquiring zoonotic diseases, such as Ebola virus disease (EVD). During the recent EVD outbreak in West Africa, it is likely that human dietary behavior and local attitudes toward bushmeat consumption changed in response to the crisis, and that the rate of change depended on prevailing socio-economic conditions, including wealth and education. In this study, we therefore investigated the effects of income, education, and literacy on changes in bushmeat consumption during the crisis, as well as complementary changes in daily meal frequency, food diversity and bushmeat preference. More specifically, we tested whether wealthier households with more educated household heads decreased their consumption of bushmeat during the EVD crisis, and whether their daily meal frequency and food diversity remained constant. We used Generalized Linear Mixed Models to analyze interview data from two nationwide household surveys across Liberia. We found an overall decrease in bushmeat consumption during the crisis across all income levels. However, the rate of bushmeat consumption in high-income households decreased less than in low-income households. Daily meal frequency decreased during the crisis, and the diversity of food items and preferences for bushmeat species remained constant. Our multidisciplinary approach to study the impact of EVD can be applied to assess how other disasters affect social-ecological systems and improve our understanding and the management of future crises. PMID:28282378

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

PubMed Central

Mukhtasimova, Nuriya; daCosta, Corrie J.B.

2016-01-01

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

The effects of MgADP on cross-bridge kinetics: a laser flash photolysis study of guinea-pig smooth muscle.

PubMed Central

Nishiye, E; Somlyo, A V; Török, K; Somlyo, A P

1993-01-01

1. The effects of MgADP on cross-bridge kinetics were investigated using laser flash photolysis of caged ATP (P3-1(2-nitrophenyl) ethyladenosine 5'-triphosphate), in guinea-pig portal vein smooth muscle permeabilized with Staphylococcus aureus alpha-toxin. Isometric tension and in-phase stiffness transitions from rigor state were monitored upon photolysis of caged ATP. The estimated concentration of ATP released from caged ATP by high-pressure liquid chromatography (HPLC) was 1.3 mM. 2. The time course of relaxation initiated by photolysis of caged ATP in the absence of Ca2+ was well fitted during the initial 200 ms by two exponential functions with time constants of, respectively, tau 1 = 34 ms and tau 2 = 1.2 s and relative amplitudes of 0.14 and 0.86. Multiple exponential functions were needed to fit longer intervals; the half-time of the overall relaxation was 0.8 s. The second order rate constant for cross-bridge detachment by ATP, estimated from the rate of initial relaxation, was 0.4-2.3 x 10(4) M-1 s-1. 3. MgADP dose dependently reduced both the relative amplitude of the first component and the rate constant of the second component of relaxation. Conversely, treatment of muscles with apyrase, to deplete endogenous ADP, increased the relative amplitude of the first component. In the presence of MgADP, in-phase stiffness decreased during force maintenance, suggesting that the force per cross-bridge increased. The apparent dissociation constant (Kd) of MgADP for the cross-bridge binding site, estimated from its concentration-dependent effect on the relative amplitude of the first component, was 1.3 microM. This affinity is much higher than the previously reported values (50-300 microM for smooth muscle; 18-400 microM for skeletal muscle; 7-10 microM for cardiac muscle). It is possible that the high affinity reflects the properties of a state generated during the co-operative reattachment cycle, rather than that of the rigor bridge. 4. The rate constant of MgADP release from cross-bridges, estimated from its concentration-dependent effect on the rate constant of the second (tau 2) component, was 0.35-7.7 s-1. To the extent that reattachment of cross-bridges could slow relaxation even during the initial 200 ms, this rate constant may be an underestimate. 5. Inorganic phosphate (Pi, 30 mM) did not affect the rate of relaxation during the initial approximately 50 ms, but accelerated the slower phase of relaxation, consistent with a cyclic cross-bridge model in which Pi increases the proportion of cross-bridges in detached ('weakly bound') states.(ABSTRACT TRUNCATED AT 400 WORDS) Images Fig. 1 PMID:8487195

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

DOE PAGES

Song, Bo; Sanborn, Brett

2018-05-07

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

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

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

Song, Bo; Sanborn, Brett

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

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

Eckstein, Sebastian; Hintermeier, Peter H.; Olarte, Mariefel V.

The hydronium ion normalized reaction rate in aqueous phase alkylation of phenol with ethanol on H-MFI zeolites increases with decreasing concentration of acid sites. Higher rates are caused by higher concentrations of phenol in the zeolite pores, as the concentration of hydronium ions generated by zeolite Brønsted acid sites decreases. Considering the different concentrations of reacting species it is shown that the intrinsic rate constant for alkylation is independent of the concentration of hydronium ions in the zeolite pores. Alkylation at the aromatic ring of phenol and of toluene as well as O-alkylation of phenol have the same activation energy,more » 104 ± 5 kJ/mol. This is energetic barrier to form the ethyl carbenium ion from ethanol associated to the hydronium ion. Thus, in both the reaction pathways the catalyst involves a carbenium ion, which forms a bond to a nucleophilic oxygen (ether formation) or carbon (alkylation).« less

Evidence for Solar Cycle Influence on the Infrared Energy Budget and Radiative Cooling of the Thermosphere

NASA Technical Reports Server (NTRS)

Mlynczak, Martin G.; Martin-Torres, F. Javier; Marshall, B. Thomas; Thompson, R. Earl; Williams, Joshua; Turpin, TImothy; Kratz, D. P.; Russell, James M.; Woods, Tom; Gordley, Larry L.

2007-01-01

We present direct observational evidence for solar cycle influence on the infrared energy budget and radiative cooling of the thermosphere. By analyzing nearly five years of data from the Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument, we show that the annual mean infrared power radiated by the nitric oxide (NO) molecule at 5.3 m has decreased by a factor of 2.9. This decrease is correlated (r = 0.96) with the decrease in the annual mean F10.7 solar index. Despite the sharp decrease in radiated power (which is equivalent to a decrease in the vertical integrated radiative cooling rate), the variability of the power as given in the standard deviation of the annual means remains approximately constant. A simple relationship is shown to exist between the infrared power radiated by NO and the F10.7 index, thus providing a fundamental relationship between solar activity and the thermospheric cooling rate for use in thermospheric models. The change in NO radiated power is also consistent with changes in absorbed ultraviolet radiation over the same time period.

Chemical weathering in a tropical watershed, Luquillo Mountains, Puerto Rico III: Quartz dissolution rates

USGS Publications Warehouse

Schulz, M.S.; White, A.F.

1999-01-01

The paucity of weathering rates for quartz in the natural environment stems both from the slow rate at which quartz dissolves and the difficulty in differentiating solute Si contributed by quartz from that derived from other silicate minerals. This study, a first effort in quantifying natural rates of quartz dissolution, takes advantage of extremely rapid tropical weathering, simple regolith mineralogy, and detailed information on hydrologic and chemical transport. Quartz abundances and grain sizes are relatively constant with depth in a thick saprolite. Limited quartz dissolution is indicated by solution rounding of primary angularity and by the formation of etch pits. A low correlation of surface area (0.14 and 0.42 m2 g-1) with grain size indicates that internal microfractures and pitting are the principal contributors to total surface area. Pore water silica concentration increases linearly with depth. On a molar basis, between one and three quarters of pore water silica is derived from quartz with the remainder contributed from biotite weathering. Average solute Si remains thermodynamically undersaturated with respect to recently revised estimates of quartz solubility (17-81 ??M). Etch pitting is more abundant on grains in the upper saprolite and is associated with pore waters lower in dissolved silica. Rate constants describing quartz dissolution increase with decreasing depth (from 10-14.5-10-15.1 mol m-2 s-1), which correlate with both greater thermodynamic undersaturation and increasing etch pit densities. Unlike for many aluminosilicates, the calculated natural weathering rates of quartz fall slightly below the rate constants previously reported for experimental studies (10-12.4-10-14.2 mol m-2 s-1). This agreement reflects the structural simplicity of quartz, dilute solutes, and near-hydrologic saturation.

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.

Continuous cultivation of bakers' yeast: change in cell composition at different dilution rates and effect of heat stress on trehalose level.

PubMed

Ertugay, N; Hamamci, H

1997-01-01

The cell composition of bakers' yeast in a continuous culture was determined for different dilution rates. Also, the cellular response to heat stress in terms of trehalose, RNA, glycogen and protein was determined at a specified dilution rate of 0.1/h. The amount of storage saccharides, trehalose and glycogen, was found to decrease whereas the amount of RNA and protein increased with increasing dilution rates. As the dilution rate was increased from 0.1 to 0.4/h at 0.05 intervals the steady-state trehalose content decreased from 33 to 8.6 mg/g biomass, and glycogen content from 150 to 93 mg/g biomass. On the other hand, the protein content increased from 420 to 530 mg/g biomass and the RNA content from 93 to 113 mg/g biomass. Heat stress was applied by increasing the medium temperature from 30 to 36, 38 or 40 degrees C at constant dilution rates. The highest amount of trehalose accumulation, 108 mg/g biomass, was achieved when heat stress at 38 degrees C was applied. The protein content, on the other hand, decreased from 350 to 325 mg/g biomass at the end of the experiment.

Regression model analysis of the decreasing trend of cesium-137 concentration in the atmosphere since the Fukushima accident.

PubMed

Kitayama, Kyo; Ohse, Kenji; Shima, Nagayoshi; Kawatsu, Kencho; Tsukada, Hirofumi

2016-11-01

The decreasing trend of the atmospheric 137 Cs concentration in two cities in Fukushima prefecture was analyzed by a regression model to clarify the relation between the parameter of the decrease in the model and the trend and to compare the trend with that after the Chernobyl accident. The 137 Cs particle concentration measurements were conducted in urban Fukushima and rural Date sites from September 2012 to June 2015. The 137 Cs particle concentrations were separated in two groups: particles of more than 1.1 μm aerodynamic diameters (coarse particles) and particles with aerodynamic diameter lower than 1.1 μm (fine particles). The averages of the measured concentrations were 0.1 mBq m -3 in Fukushima and Date sites. The measured concentrations were applied in the regression model which decomposed them into two components: trend and seasonal variation. The trend concentration included the parameters for the constant and the exponential decrease. The parameter for the constant was slightly different between the Fukushima and Date sites. The parameter for the exponential decrease was similar for all the cases, and much higher than the value of the physical radioactive decay except for the concentration in the fine particles at the Date site. The annual decreasing rates of the 137 Cs concentration evaluated by the trend concentration ranged from 44 to 53% y -1 with average and standard deviation of 49 ± 8% y -1 for all the cases in 2013. In the other years, the decreasing rates also varied slightly for all cases. These indicated that the decreasing trend of the 137 Cs concentration was nearly unchanged for the location and ground contamination level in the three years after the accident. The 137 Cs activity per aerosol particle mass also decreased with the same trend as the 137 Cs concentration in the atmosphere. The results indicated that the decreasing trend of the atmospheric 137 Cs concentration was related with the reduction of the 137 Cs concentration in resuspended particles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Novel Superdielectric Materials: Aqueous Salt Solution Saturated Fabric

PubMed Central

Phillips, Jonathan

2016-01-01

The dielectric constants of nylon fabrics saturated with aqueous NaCl solutions, Fabric-Superdielectric Materials (F-SDM), were measured to be >105 even at the shortest discharge times (>0.001 s) for which reliable data could be obtained using the constant current method, thus demonstrating the existence of a third class of SDM. Hence, the present results support the general theoretical SDM hypothesis, which is also supported by earlier experimental work with powder and anodized foil matrices: Any material composed of liquid containing dissolved, mobile ions, confined in an electrically insulating matrix, will have a very high dielectric constant. Five capacitors, each composed of a different number of layers of salt solution saturated nylon fabric, were studied, using a galvanostat operated in constant current mode. Capacitance, dielectric constant, energy density and power density as a function of discharge time, for discharge times from ~100 s to nearly 0.001 s were recorded. The roll-off rate of the first three parameters was found to be nearly identical for all five capacitors tested. The power density increased in all cases with decreasing discharge time, but again the observed frequency response was nearly identical for all five capacitors. Operational limitations found for F-SDM are the same as those for other aqueous solution SDM, particularly a low maximum operating voltage (~2.3 V), and dielectric “constants” that are a function of voltage, decreasing for voltages higher than ~0.8 V. Extrapolations of the present data set suggest F-SDM could be the key to inexpensive, high energy density (>75 J/cm3) capacitors. PMID:28774037

Molten salt synthesis of nanocrystalline phase of high dielectric constant material CaCu3Ti4O12.

PubMed

Prakash, B Shri; Varma, K B R

2008-11-01

Nanocrystalline powders of giant dielectric constant material, CaCu3Ti4O12 (CCTO), have been prepared successfully by the molten salt synthesis (MSS) using KCl at 750 degrees C/10 h, which is significantly lower than the calcination temperature (approximately 1000 degrees C) that is employed to obtain phase pure CCTO in the conventional solid-state reaction route. The water washed molten salt synthesized powder, characterized by X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), and Transmission electron microscopy (TEM) confirmed to be a phase pure CCTO associated with approximately 150 nm sized crystallites of nearly spherical shape. The decrease in the formation temperature/duration of CCTO in MSS method was attributed to an increase in the diffusion rate or a decrease in the diffusion length of reacting ions in the molten salt medium. As a consequence of liquid phase sintering, pellets of as-synthesized KCl containing CCTO powder exhibited higher sinterability and grain size than that of KCl free CCTO samples prepared by both MSS method and conventional solid-state reaction route. The grain size and the dielectric constant of KCl containing CCTO ceramics increased with increasing sintering temperature (900 degrees C-1050 degrees C). Indeed the dielectric constants of these ceramics were higher than that of KCl free CCTO samples prepared by both MSS method and those obtained via the solid-state reaction route and sintered at the same temperature. Internal barrier layer capacitance (IBLC) model was invoked to correlate the observed dielectric constant with the grain size in these samples.

Observation of Failure and Domain Switching in Lead Zirconate Titanate Ceramics

NASA Astrophysics Data System (ADS)

Okayasu, Mitsuhiro; Sugiyama, Eriko; Sato, Kazuto; Mizuno, Mamoru

The mechanical and electrical properties (electromechanical coupling coefficient, piezoelectric constant and dielectric constant) of lead zirconate titanate (PZT) ceramics are investigated during mechanical static and cyclic loading. There are several failure characteristics which can alter the material properties of PZT ceramics. The elastic constant increases and electrical properties decrease with increasing the applied load. This is due to the internal strain arising from the domain switching. In this case, 90° domain switching occurs anywhere in the samples as the sample is loaded. It is also apparent that electrogenesis occurs several times during cyclic loading to the final fracture. This occurrence is related to the domain switching. The elastic constant and electrical properties can decrease because of crack generation in the PZT ceramics. Moreover, the elastic constant increases with increase of the mechanical load and decreases with decrease of the load. On the contrary, the opposite sense of change of the electrical properties is observed.

Effects of electronics, aromaticity, and solvent polarity on the rate of azaquinone-methide-mediated depolymerization of aromatic carbamate oligomers.

PubMed

Robbins, Jessica S; Schmid, Kyle M; Phillips, Scott T

2013-04-05

This paper uses physical-organic studies on well-defined oligomers to establish design principles for creating aromatic poly(carbamates) that depolymerize from head-to-tail in low dielectric constant environments when exposed to specific applied signals. We show that either increasing electron density or decreasing the aromaticity of aromatic repeating units in poly(carbamates) increase the overall depolymerization rate. For example, a methoxybenzene-based repeating unit provides depolymerization rates that are 143× faster than oligomers that contain a benzene-based repeating unit. Furthermore, the rate of depolymerization in the methoxybenzene-based system is tolerant to low dielectric environments, whereas the benzene-based oligomers are not.

Compton suppression gamma-counting: The effect of count rate

USGS Publications Warehouse

Millard, H.T.

1984-01-01

Past research has shown that anti-coincidence shielded Ge(Li) spectrometers enhanced the signal-to-background ratios for gamma-photopeaks, which are situated on high Compton backgrounds. Ordinarily, an anti- or non-coincidence spectrum (A) and a coincidence spectrum (C) are collected simultaneously with these systems. To be useful in neutron activation analysis (NAA), the fractions of the photopeak counts routed to the two spectra must be constant from sample to sample to variations must be corrected quantitatively. Most Compton suppression counting has been done at low count rate, but in NAA applications, count rates may be much higher. To operate over the wider dynamic range, the effect of count rate on the ratio of the photopeak counts in the two spectra (A/C) was studied. It was found that as the count rate increases, A/C decreases for gammas not coincident with other gammas from the same decay. For gammas coincident with other gammas, A/C increases to a maximum and then decreases. These results suggest that calibration curves are required to correct photopeak areas so quantitative data can be obtained at higher count rates. ?? 1984.

Influence of Mineralogy, Pressure, Temperature and Stress on Mechanical roperties of shale Rocks

NASA Astrophysics Data System (ADS)

Herrmann, J.; Rybacki, E.; Sone, H.; Dresen, G. H.

2017-12-01

The production of hydrocarbons from unconventional reservoirs, like tight shale plays increased tremendously over the past decade. Hydraulic fracturing is a common method to increase the productivity of a well drilled in these reservoirs. Unfortunately, the production rate decreases over time presumably due to fracture healing. The healing rate induced by proppant embedment depends on pressure (p), temperature (T), stress (σ) - conditions and on shale composition. To improve understanding of the influence of these parameters on fracture healing, we conducted constant strain rate experiments (p = 50 - 100 MPa, T = 50 - 125 °C, ɛ/t = 5 * 10-4 - 5 * 10-6 s-1) on porous ( 8 %), quartz - rich ( 72 vol %) Bowland shale (UK) and on low porosity ( 3 %), clay - rich ( 33 vol %) Posidonia shale (GER), deformed perpendicular to bedding and with as-is water content. Bowland shale showed mainly brittle behaviour with predominantly elastic deformation before failure and a high strength (280 - 350 MPa). In contrast, Posidonia shale deformed semibrittle with pronounced inelastic deformation and low peak strength (165 - 220 MPa). For both shale rocks, static Young's moduli vary between 12 - 18 GPa. In addition, we performed a series of constant stress tests on both shales at p = 30 - 115 MPa, T = 75 - 150 °C and σ = 160 - 450 MPa. Samples showed transient (primary) creep with increasing strain rates for increasing temperature and stress and decreasing pressure. An empirical power law in the form of ɛ = A*tm is used to describe the observed relation between inelastic strain (ɛ) and time (t), where the constant A is mainly affected by temperature and stress and the exponent m accounts for the influence of pressure. Compared to quartz - rich, strong Bowland shale, the creep behaviour of clay - rich, weak Posidonia shale is much more sensitive to changes in pressure, temperature and stress. Electron microscopy suggests that creep was mainly accommodated by deformation of weak phases (TOC, clay, mica). Our results suggest a low fracture healing rate of Bowland shale, whereas fractures within the Posidonia formation tend to close faster.

Estimation of dioxin and furan elimination rates with a pharmacokinetic model.

PubMed

Van der Molen, G W; Kooijman, B A; Wittsiepe, J; Schrey, P; Flesch-Janys, D; Slob, W

2000-01-01

Quantitative description of the pharmacokinetics of dioxins and furans in humans can be of great help for the assessment of health risks posed by these compounds. To that the elimination rates of sixteen 2,3,7,8-chlorinated dibenzodioxins and dibenzofurans are estimated from both a longitudinal and a cross-sectional data set using the model of Van der Molen et al. [Van der Molen G.W., Kooijman S.A.L.M., and Slob W. A generic toxicokinetic model for persistent lipophilic compounds in humans: an application to TCDD. Fundam Appl Toxicol 1996: 31: 83-94]. In this model the elimination rate is given by the (constant) specific elimination rate multiplied with the ratio between the lipid weight of the liver and total body lipid weight. Body composition, body weight and intake are assumed to depend on age. The elimination rate is, therefore, not constant. For 49-year-old males, the elimination rate estimates range between 0.03 per year for 1,2,3,6,7,8-hexaCDF to 1.0 per year for octaCDF. The elimination rates of the most toxic congeners, 2,3,7,8-tetraCDD, 1,2,3,7,8-pentaCDD, and 2,3,4,7,8-pentaCDF, were estimated at 0.09, 0.06, and 0.07, respectively, based on the cross-sectional data, and 0.11, 0.09, and 0.09 based on the longitudinal data. The elimination rates of dioxins decrease with age between 0.0011 per year for 1,2,3,6,7,8-hexaCDD and 0.0035 per year for 1,2,3,4,6,7,8-heptaCDD. For furans the average decrease is 0.0033 per year. The elimination rates were estimated both from a longitudinal and a cross-sectional data set, and agreed quite well with each other, after taking account of historical changes in average intake levels.

Liquid level controller

DOEpatents

Mangus, J.D.; Redding, A.H.

1975-07-15

A system for maintaining two distinct sodium levels within the shell of a heat exchanger having a plurality of J-shaped modular tube bundles each enclosed in a separate shell which extends from a common base portion. A lower liquid level is maintained in the base portion and an upper liquid level is maintained in the shell enwrapping the long stem of the J-shaped tube bundles by utilizing standpipes with a notch at the lower end which decreases in open area the distance from the end of the stand pipe increases and a supply of inert gas fed at a constant rate to produce liquid levels, which will remain generally constant as the flow of liquid through the vessel varies. (auth)

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.

Effect of fast neutron, gamma-ray and combined radiations on the thermal decomposition of ammonium perchlorate single crystals

NASA Technical Reports Server (NTRS)

Herley, P. J.; Wang, C. S.; Varsi, G.; Levy, P. W.

1974-01-01

The thermal decomposition kinetics have been determined for ammonium perchlorate crystals subjected to a fast neutron irradiation or to a fast neutron irradiation followed by a gamma-ray irradiation. Qualitatively, the radiation induced changes are similar to those obtained in this and in previous studies, with samples exposed only to gamma rays. The induction period is shortened and the rate constants, obtained from an Avrami-Erofeyev kinetic analysis, are modified. The acceleratory period constant increases and the decay period constant decreases. When compared on an equal deposited energy basis, the fast neutron induced changes are appreciably larger than the gamma-ray induced changes. Some, or all, of the fast neutron induced effects might be attributable to the introduction of localized regions of concentrated radiation damage ('spikes') by lattice atom recoils which become thermal decomposition sites when the crystals are heated.

Crassulacean Acid Metabolism in the Epiphyte Tillandsia usneoides L. (Spanish Moss) 1

PubMed Central

Martin, Craig E.; Siedow, James N.

1981-01-01

Patterns of CO2 exchange in Spanish moss under various experimental conditions were measured using an infrared gas analysis system. Plants were collected from a study site in North Carolina and placed in a gas exchange chamber for several days of continuous measurements. No substantial seasonal effects on CO2 exchange were observed. High rates of nocturnal CO2 uptake were observed under day/night temperature regimes of 25/10, 25/15, 25/20, 30/20, and 35/20 C; however, daytime temperatures of 40 C eliminated nighttime CO2 uptake and a nighttime temperature of 5 C eliminated nocturnal CO2 uptake, regardless of day temperature. Constant chamber conditions also inhibited nocturnal CO2 uptake. Constant high relative humidity (RH) slightly stimulated CO2 uptake while low nighttime RH reduced nocturnal CO2 uptake. Reductions in daytime irradiance to approximately 25% full sunlight had no effect on CO2 exchange. Continuous darkness resulted in continuous CO2 loss by the plants, but a CO2 exchange pattern similar to normal day/night conditions was observed under constant illumination. High tissue water content inhibited CO2 uptake. Wetting of the tissue at any time of day or night resulted in net CO2 loss. Abrupt increases in temperature or decreases in RH resulted in sharp decreases in net CO2 uptake. The results indicate that Spanish moss is tolerant of a wide range of temperatures, irradiances, and water contents. They also indicate that high nighttime RH is a prerequisite for high rates of CO2 uptake. PMID:16661912

Crassulacean Acid Metabolism in the Epiphyte Tillandsia usneoides L. (Spanish Moss) : RESPONSES OF CO(2) EXCHANGE TO CONTROLLED ENVIRONMENTAL CONDITIONS.

PubMed

Martin, C E; Siedow, J N

1981-08-01

Patterns of CO(2) exchange in Spanish moss under various experimental conditions were measured using an infrared gas analysis system. Plants were collected from a study site in North Carolina and placed in a gas exchange chamber for several days of continuous measurements. No substantial seasonal effects on CO(2) exchange were observed. High rates of nocturnal CO(2) uptake were observed under day/night temperature regimes of 25/10, 25/15, 25/20, 30/20, and 35/20 C; however, daytime temperatures of 40 C eliminated nighttime CO(2) uptake and a nighttime temperature of 5 C eliminated nocturnal CO(2) uptake, regardless of day temperature. Constant chamber conditions also inhibited nocturnal CO(2) uptake. Constant high relative humidity (RH) slightly stimulated CO(2) uptake while low nighttime RH reduced nocturnal CO(2) uptake.Reductions in daytime irradiance to approximately 25% full sunlight had no effect on CO(2) exchange. Continuous darkness resulted in continuous CO(2) loss by the plants, but a CO(2) exchange pattern similar to normal day/night conditions was observed under constant illumination. High tissue water content inhibited CO(2) uptake. Wetting of the tissue at any time of day or night resulted in net CO(2) loss. Abrupt increases in temperature or decreases in RH resulted in sharp decreases in net CO(2) uptake.The results indicate that Spanish moss is tolerant of a wide range of temperatures, irradiances, and water contents. They also indicate that high nighttime RH is a prerequisite for high rates of CO(2) uptake.

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

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

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

1993-10-01

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

Erratum to "The mechanism and thermodynamics of transesterification of acetate-ester enolates in the gas phase" : [Int. J. Mass Spectrom. Ion Process. 172 (1998) 25

NASA Astrophysics Data System (ADS)

Haas, George W.; Giblin, Daryl E.; Gross, Michael L.

1998-02-01

In solution, base-catalyzed hydrolysis and transesterification of esters are initiated by hydroxide- or alkoxide-ion attack at the carbonyl carbon. At low pressures in the gas phase, however, transesterification proceeds by an attack of the enolate anion of an acetate ester on an alcohol. Fourier transform mass spectrometry (FTMS) indicates that the reaction is the second-order process: -CH2-CO2-R+R'-OH-->-CH2-CO2-R'+R-OH and there is little to no detectable production of either alkoxide anion. Labeling studies show that the product and reactant enolate anion esters undergo exchange of hydrogens located [alpha] to the carbonyl carbon with the deuterium of R'--OD. The extent of the H/D exchange increases with reaction time, pointing to a short-lived intermediate. The alcoholysis reaction rate constants increase with increasing acidity of the primary, straight-chained alkyl alcohols, whereas steric effects associated with branched alcohols cause the rate constants to decrease. Equilibrium constants, which were determined directly from measurements at equilibrium and which were calculated from the forward and reverse rate constants, are near unity and show internal consistency. In the absence of steric effects, the larger enolate is always the favored product at equilibrium. The intermediate for the transesterification reaction, which can be generated at a few tenths of a torr in a tandem mass spectrometer, is tetrahedral, but other adducts that are collisionally stabilized under these conditions are principally loosely bound complexes.

Ionizing power and nucleophilicity in water in oil AOT-based microemulsions.

PubMed

García-Río, Luis; Hervella, Pablo; Leis, José Ramón

2005-08-16

A study was carried out on the solvolysis of substituted phenyl chloroformates in AOT/isooctane/water microemulsions. (AOT is the sodium salt of bis(2-ethyhexyl)sulfosuccinate.) The results obtained have been interpreted by taking into account the distribution of the chloroformates between the continuous medium and the interface of the microemulsions, where the reactions take place. The values obtained for the rate constant in the interface, k(i), decreases as the water content of the microemulsions increases, as a consequence of the decrease in its nucleophilic capacity. This behavior is consistent with a rate-determining step of water addition to the carbonyl group. The values of k(i) allow us to obtain the slopes of the Hammett correlations at the interface of the microemulsions, rho = 2.25, whose values are greater than those obtained in an aqueous medium, rho = 0.82. This increase in the Hammett slope is similar to that observed in ethanol/water mixtures and is a consequence of a variation in the structure of the transition state of the reaction where there is a smaller extension of the expulsion of the leaving group. The values of the rate constants at the interface of the microemulsions have allowed us, by means of the Grunwald-Winstein equation, to obtain the solvent ionizing power and the nucleophilicity of the solvent. The values obtained for Y(Cl) increase together with the water content of the microemulsion, whereas the values of N(T) decrease. These variations are a consequence of the interaction between the AOT headgroups and the interfacial water, where the water molecules act like electronic acceptors. The intensity of this interaction is greater if the system has a small water content, which explains the variation of Y(Cl) and N(T).

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.

Temperature-dependent development of Aleyrodes proletella (Homoptera: Aleyrodidae) on two cultivars of broccoli under constant temperatures.

PubMed

Alonso, Daniel; Gómez, Ana Azahara; Nombela, Gloria; Muñiz, Mariano

2009-02-01

Laboratory experiments were conducted to estimate developmental rates and nymphal survival of Aleyrodes proletella Linnaeus (Homoptera: Aleyrodidae) on two broccoli Brassica oleracea L. variety italica Plenck cultivars (Marathon and Agripa) at eight constant temperatures (16, 18, 20, 22, 24, 26, 28, and 30 degrees C). The times required to complete development of egg and first instar decreased with increasing temperature, but the developmental times of second, third, fourth instars, all instars, and egg-adult period were greater at 30 degrees C than at 28degrees C. The relationships between developmental rate of A. proletella and temperature were slightly influenced by broccoli cultivar. The optimal temperatures and thermal constant as well as the lower and upper thresholds of development for all immature stages were estimated by fitting the observed developmental rates versus temperature with a nonlinear model and two linear models. For all stages, graphs obtained by plotting the developmental rates against temperature could be described by the modification two of the Logan's model. Overall, developmental times for immature stages and egg-adult periods were similar on both Agripa and Marathon cultivars. The most favorable temperature range for nymphal development seemed to be 28-29 (second and third instars) and 31-33 degrees C (fourth instar). Mean generation times (egg-adult) ranged from 19 d ('Marathon' and 'Agripa') at 28 degrees C to 47 ('Marathon') and 46 d ('Agripa') at 16 degrees C.

The Trends in Cardiovascular Diseases and Respiratory Diseases Mortality in Urban and Rural China, 1990-2015.

PubMed

Sun, Weiwei; Zhou, Yun; Zhang, Zhuang; Cao, Limin; Chen, Weihong

2017-11-15

With the rapid development of the economy over the past 20 years, the mortality rates from cardiovascular diseases (CVDs) and respiratory diseases (RDs) have changed in China. This study aimed to analyze the trends of mortality rates and years of life lost (YLLs) from CVDs and RDs in the rural and urban population from 1990 to 2015. Using data from Chinese yearbooks, joinpoint regression analysis was employed to estimate the annual percent change (APC) of mortality rates from CVDs and RDs. YLLs due to CVDs and RDs were calculated by a standard method, adopting recommended standard life expectancy at birth values of 80 years for men and 82.5 years for women. Age-standardized mortality rates and YLL rates were calculated by using the direct method based on the Chinese population from the sixth population census of 2010. Age-standardized mortality rates from CVDs for urban residents and from RDs for both urban and rural residents showed decreasing trends in China from 1990 to 2015. Age-standardized mortality rates from CVDs among rural residents remained constant during above period and outstripped those among urban residents gradually. The age-standardized YLL rates of CVDs for urban and rural residents decreased 35.2% and 8.3% respectively. Additionally, the age-standardized YLL rates of RDs for urban and rural residents decreased 64.2% and 79.0% respectively. The age-standardized mortality and YLL rates from CVDs and RDs gradually decreased in China from 1990 to 2015. We observed more substantial declines of the mortality rates from CVDs in urban areas and from RDs in rural areas.

Cosmic ray modulation and turbulent interaction regions near 11 AU

NASA Technical Reports Server (NTRS)

Burlaga, L. F.; Mcdonald, F. B.; Goldstein, M. L.; Lazarus, A. J.

1985-01-01

When Voyager 2 was near 11 AU, the counting rate of nuclei approx 75 MeV/nucleon decreased during the interval from July, 1982 to November, 1982, and it increased thereafter until August, 1983. A decrease in cosmic ray flux was generally associated with the passage of an interaction region in which the magnetic field strength B was higher than that predicted by the spiral field model, B sub p. Several large enhancements in B/B sup p were associated with merged interaction regions which probably resulted from the interaction of two or more distinct flows. During the passage of interaction regions the cosmic ray intensity decreased at a rate proportional to (B/B sup p -1), and during the passage of rarefaction regions (where B/B sup p 1) the cosmic ray intensity increased at a constant rate. The general form of the cosmic ray intensity profile during this approx 13 month minicycle can be described by integrating these relations using the observed B(t). Latitudinal variations of the interaction regions and of the short-term cosmic ray variations were identified.

In Vivo Force Decay of Niti Closed Coil Springs

PubMed Central

Cox, Crystal; Nguyen, Tung; Koroluk, Lorne; Ko, Ching-Chang

2014-01-01

Introduction Nickel-titanium (NiTi) closed coil springs are purported to deliver constant forces over extended ranges of activation and working times. In vivo studies supporting this claim are limited. The objective of this study is to evaluate changes in force decay properties of NiTi closed coil springs after clinical use. Methods Pseudoelastic force-deflection curves for 30 NiTi coil springs (used intra-orally) and 15 matched laboratory control springs (simulated intra-oral conditions - artificial saliva, 37°C) were tested pre- and post-retrieval via Dynamic Mechanical Analysis (DMA) and the Instron machine, respectively, to evaluate amount of force loss and hysteresis change following 4, 8, or 12 weeks of working time (n=10 per group). Effect of the oral environment and clinical use on force properties were evaluated by comparing in vivo and in vitro data. Results The springs studied showed a statistically significant decrease in force (~12%) following 4 weeks of clinical use (p<0.01), with a further significant decrease (~7%) from 4–8 weeks (p=0.03) and force levels appearing to remain steady thereafter. Clinical space closure at an average rate of 0.91mm per month was still observed despite this decrease in force. In vivo and in vitro force loss data were not statistically different. Conclusions NiTi closed coil springs do not deliver constant forces when used intra-orally, but they still allow for space closure rates of ~1mm/month. PMID:24703289

Assimilation efficiency and toxicokinetics of 14C-lindane in the terrestrial isopod Porcellionides pruinosus: the role of isopods in degradation of persistent soil pollutants.

PubMed

Loureiro, Susana; Sousa, J P; Nogueira, A J A; Soares, A M V M

2002-12-01

An achievable way to evaluate the bioavailability of a certain toxic in the environment is to measure the concentration inside soil organisms. Non-target saprotrophic organisms like isopods are often exposed to agrochemicals or other kind of persistent chemicals. In this study the isopod Porcellionides pruinosus was exposed to a constant concentration of Lindane (gamma-HCH) via food. Using toxicokinetic models the bioaccumulation and fate of the pesticide by isopods was assessed and compared with previous studies, where an unexpected decrease in gamma-HCH concentration was observed. Animal body burdens showed higher values, and a lower assimilation rate constant, although the elimination rate constant was twice the value previously observed. It was also observed that a significant amount of gamma-HCH had an unknown fate. To discover its possible destiny, a factorial experiment was carried out using two types of CO2 traps and contaminated leaves in the presence and absence of isopods. It was concluded that isopod activity might have been responsible for a more rapid biotransformation of gamma-HCH in leaves, since the amount of the pesticide is reduced in their presence.

The use of ozone, ozone plus UV radiation, and aerobic microorganisms in the purification of some agro-industrial wastewaters.

PubMed

Benitez, F Javier; Acero, Juan L; Gonzalez, Teresa; Garcia, Juan

2002-08-01

The oxidation of the pollutant organic matter present in wastewaters generated during different stages in the black table-olive industry was investigated by using ozone alone or combined with UV radiation; by using aerobic microorganisms; and finally, by aerobic degradation of the previously ozonated wastewaters. In the ozonation processes, the removal of substrate (COD) and aromatic compounds, the decreases in BOD5 and pH, and the ozone consumed in the reaction were evaluated. A kinetic study was conducted that led to the evaluation of the stoichiometric ratio for the chemical reaction, as well as the rate constants for the substrate reduction and ozone disappearance. In the single aerobic degradation treatment, the evolution of substrate and biomass was monitored during the process, and a kinetic study was performed by applying the Contois model to the experimental data, giving the specific biokinetic constant, the cell yield coefficient, and the rate constant for the microorganism death phase. Finally, a combined process was performed, consisting in the aerobic degradation of pre-ozonated wastewaters, and the effect of such chemical pretreatment on the substrate removal and kinetic parameters of the later biological stage is discussed.

From catastrophic acceleration to deceleration of liquid plugs in prewetted capillary tubes

NASA Astrophysics Data System (ADS)

Magniez, Juan; Baudoin, Michael; Zoueshtiagh, Farzam; Lemac/Lics Team

2016-11-01

Liquid/gas flows in capillaries are involved in a multitude of systems including flow in porous media, petroleum extraction, imbibition of paper or flows in pulmonary airways in pathological conditions. Liquid plugs, witch compose the biphasic flows, can have a dramatic impact on patients with pulmonary obstructive diseases, since they considerably alter the circulation of air in the airways and thus can lead to severe breathing difficulties. Here, the dynamics of liquid plugs in prewetted capillary tube is investigated experimentally and theoretically, with a particular emphasis on the role of the prewetting films and of the driving condition (constant flow rate, constant pressure). For both driving conditions, the plugs can either experience a continuous increase or decrease of their size. While this phenomenon is regular in the case of imposed flow rate, a constant pressure head can lead to a catastrophic acceleration of the plug and eventually its rupture or a dramatic increase of the plug size. A theoretical model is proposed to explain the transition between theses two regimes. These results give a new insight on the critical pressure required for airways obstruction and reopening. IEMN, International Laboratory LEMAC/LICS, UMR CNRS 8520, University of Lille.

Clinical and structural outcomes after arthroscopic repair of full-thickness rotator cuff tears with and without platelet-rich product supplementation: a meta-analysis and meta-regression.

PubMed

Warth, Ryan J; Dornan, Grant J; James, Evan W; Horan, Marilee P; Millett, Peter J

2015-02-01

The purpose of this study was to perform a systematic review, meta-analysis, and meta-regression of all Level I and Level II studies comparing the clinical or structural outcomes, or both, after rotator cuff repair with and without platelet-rich product (PRP) supplementation. A literature search of the PubMed and EMBASE databases was performed to identify all Level I or II studies comparing the clinical or structural outcomes, or both, after arthroscopic repair of full-thickness rotator cuff tears with (PRP+ group) and without (PRP- group) PRP supplementation. Data included outcome scores (American Shoulder and Elbow Surgeons [ASES], University of California Los Angeles [UCLA], Constant, Simple Shoulder Test [SST] and visual analog scale [VAS] scores) and retears diagnosed with imaging studies. Meta-analyses compared preoperative, postoperative, and gain in outcome scores and relative risk ratios for retears. Meta-regression compared the effect of PRP treatment on outcome scores and retear rates according to 6 covariates. Minimum effect sizes that were detectable with 80% power were also calculated for each study. Eleven studies were included in this review and a maximum of 8 studies were used for meta-analyses according to data availability. There were no statistically significant differences between the PRP+ and PRP- groups for overall outcome scores or retear rates (P > .05). Overall gain in the Constant score was decreased when liquid PRP was injected over the tendon surface compared with PRP application at the tendon-bone interface (-6.88 points v +0.78 points, respectively; P = .046); however, this difference did not reach the previously reported minimum clinically important difference (MCID) for Constant scores. When the initial tear size was greater than 3 cm in anterior-posterior length, the PRP+ group exhibited decreased retear rates after double-row repairs when compared with the PRP- group (25.9% v 57.1%, respectively; P = .046). Sensitivity power analyses revealed that most included studies were only powered to detect large differences in outcome scores between groups. There were no statistically significant differences in overall gain in outcome scores or retear rates between treatment groups. Gain in Constant scores was significantly increased when PRPs were applied at the tendon-bone interface when compared with application over the top of the repaired tendon. Retear rates were significantly decreased when PRPs were used for the treatment of tears greater than 3 cm in anterior-posterior length using a double-row technique. Most of the included studies were only powered to detect large differences in outcome scores between treatment groups. In addition, an increased risk for selection, performance, and attrition biases was found. Level II, meta-analysis of Level I and Level II studies. Copyright © 2015 Arthroscopy Association of North America. Published by Elsevier Inc. All rights reserved.

Ratcheting Behavior of a Titanium-Stabilized Interstitial Free Steel

NASA Astrophysics Data System (ADS)

De, P. S.; Chakraborti, P. C.; Bhattacharya, B.; Shome, M.; Bhattacharjee, D.

2013-05-01

Engineering stress-control ratcheting behavior of a titanium-stabilized interstitial free steel has been studied under different combinations of mean stress and stress amplitude at a stress rate of 250 MPa s-1. Tests have been done up to 29.80 pct true ratcheting strain evolution in the specimens at three maximum stress levels. It is observed that this amount of ratcheting strain is more than the uniform tensile strain at a strain rate of 10-3 s-1 and evolves without showing tensile instability of the specimens. In the process of ratcheting strain evolution at constant maximum stresses, the effect of increasing stress amplitude is found to be more than that of increasing the mean stress component. Further, the constant maximum stress ratcheting test results reveal that the number of cycles ( N) required for 29.80 pct. true ratcheting strain evolution exponentially increases with increase of stress ratio ( R). Post-ratcheting tensile test results showing increase of strength and linear decrease in ductility with increasing R at different constant maximum stresses indicate that stress parameters used during ratcheting tests influence the size of the dislocation cell structure of the steel even with the same amount of ratcheting strain evolution. It is postulated that during ratcheting fatigue, damage becomes greater with the increase of R for any fixed amount of ratcheting strain evolution at constant maximum stress.

Effects of changing the ionic environment on passive and active membrane properties of pregnant rat uterus

PubMed Central

Abe, Y.

1971-01-01

1. In pregnant rat myometrium electrotonic potentials, produced by externally applied current, were recorded intracellularly. 2. The space constant, λ, was 1·8 mm, the time constant, τm, 120 msec. The values obtained on the 7th day and on the 20th day of pregnancy were the same. 3. The magnitude of the electrotonic potential and the time constant of the membrane were increased in the absence of potassium from the external solution and decreased by excess potassium. 4. The magnitude of the electrotonic potential and the time constant of the membrane were increased by the replacement of chloride with C6H5SO3- or SO42-, and decreased with NO3- or I- replacement. 5. When the sodium chloride was replaced with sucrose (16·7 mM sodium remaining in the buffers) the spontaneous spikes deteriorated and activity stopped within 30 min. However, for periods up to 4 hr, a spike of larger amplitude and faster rate of rise than in normal solution could be evoked when a depolarizing current was applied. 6. When the external calcium concentration was raised (5 and 10 mM) the amplitude and the rate of rise of the evoked spike were increased. They were decreased by reducing calcium. In zero calcium spontaneous activity stopped within 15 min. 7. The effects of calcium deficiency were much less marked and slower in onset when, simultaneously, the sodium concentration was reduced to 16·7 mM. 8. When calcium was replaced with strontium (2·5 mM), the membrane was depolarized and the duration of the spontaneous and evoked action potential was prolonged, mainly due to a slowed rate of repolarization. When the concentration of strontium was raised to 7·5 or 12·5 mM the membrane was hyperpolarized, the duration of the action potential became short and the amplitude of the spike was increased. 9. Addition of barium or the replacement of calcium with barium caused depolarization and oscillatory membrane activity. However, a spike could be evoked by applying conditioning hyperpolarization. 10. Manganese abolished the spontaneous and evoked spike. Tetrodotoxin had no effect. 11. The results show that rat uterus has cable-like properties. The action potential may be due to calcium entry, while sodium, by influencing the membrane potential in competition with calcium, may be involved in the spontaneous spike generation and the spread of excitation. PMID:5103422

Simulating X-ray bursts during a transient accretion event

NASA Astrophysics Data System (ADS)

Johnston, Zac; Heger, Alexander; Galloway, Duncan K.

2018-06-01

Modelling of thermonuclear X-ray bursts on accreting neutron stars has to date focused on stable accretion rates. However, bursts are also observed during episodes of transient accretion. During such events, the accretion rate can evolve significantly between bursts, and this regime provides a unique test for burst models. The accretion-powered millisecond pulsar SAX J1808.4-3658 exhibits accretion outbursts every 2-3 yr. During the well-sampled month-long outburst of 2002 October, four helium-rich X-ray bursts were observed. Using this event as a test case, we present the first multizone simulations of X-ray bursts under a time-dependent accretion rate. We investigate the effect of using a time-dependent accretion rate in comparison to constant, averaged rates. Initial results suggest that using a constant, average accretion rate between bursts may underestimate the recurrence time when the accretion rate is decreasing, and overestimate it when the accretion rate is increasing. Our model, with an accreted hydrogen fraction of X = 0.44 and a CNO metallicity of ZCNO = 0.02, reproduces the observed burst arrival times and fluences with root mean square (rms) errors of 2.8 h, and 0.11× 10^{-6} erg cm^{-2}, respectively. Our results support previous modelling that predicted two unobserved bursts and indicate that additional bursts were also missed by observations.

Rates of cuticular penetration of chelated Fe(III): role of humidity, concentration, adjuvants, temperature, and type of chelate.

PubMed

Schönherr, Jörg; Fernández, Victoria; Schreiber, Lukas

2005-06-01

Time courses of cuticular penetration of FeCl3 and Fe(III) complexes of citric acid, EDTA, EDDHA (Sequestrene 138Fe), imidodisuccinic acid (IDHA), and ligninsulfonic acid (Natrel) were studied using astomatous cuticular membranes (CMs) isolated from Populus x canescens leaves. At 100% relative humidity, the Fe(III) chelates disappeared exponentially with time from the surface of the CMs; that is, penetration was a first-order process that can be described using rate constants or half-times of penetration (t(1/2)). Half-times ranged from 20 to 30 h. At 90% humidity, penetration rates were insignificant with the exception of Natrel, for which t(1/2) amounted to 58 h. Rate constants were independent of temperature (15, 25, and 35 degrees C). Permeability decreased with increasing Fe chelate concentration (IDHA and EDTA). At 100% humidity, half-times measured with FeIDHA were 11 h (2 mmol L(-1)), 17 h (10 mmol L(-1)) and 36 h (20 mmol L(-1)), respectively. In the presence of FeEDTA, penetration of CaCl2 was slowed greatly. Half-times for penetration of CaCl2, which were 1.9 h in the absence of FeEDTA, rose to 3.12 h in the presence of an equimolar concentration of EDTA and 13.3 h when the FeEDTA concentration was doubled. Hence, Fe chelates reduced permeability of CMs to CaCl2 and to the Fe chelates themselves. It is suggested that Fe chelates reduced the size of aqueous pores. This view is supported by the fact that rate constants for calcium salts were about 5 times higher than for Fe chelates with the same molecular weights. Adding Tween 20 (5 g L(-1)) as a humectant did not increase permeability to FeIDHA at 90% humidity and below, while addition of glycine betaine did. Penetration of FeCl3 applied at 5 g L(-1) (pH 1.5) was not a first order process as rate constants decreased rapidly with time. Only 2% of the dose penetrated during the first 2 h and less than that in the subsequent 8 h. Recovery was only 70%. This was attributed to the formation of insoluble Fe hydroxide precipitates on CMs. These results explain why in the past foliar application of Fe compounds had limited success. Inorganic Fe salts are instable and phytotoxic because of low pH, while Fe chelates penetrate slowly and 100% humidity is required for significant penetration rates. Concentrations as low as reasonably possible should be used. These physical facts are expected to apply to stomatous leaf surfaces as well, but absolute rates probably depend on leaf age and plant species. High humidity in stagnant air layers may favor penetration rates across stomatous leaf surfaces when humidity in bulk air is below 100%.

Atmospheric leakage and condensate production in NASA's biomass production chamber. Effect of diurnal temperature cycles

NASA Technical Reports Server (NTRS)

Wheeler, Raymond M.; Drese, John H.; Sager, John C.

1991-01-01

A series of tests were conducted to monitor atmospheric leakage rate and condensate production in NASA's Biomass Production Chamber (BPC). Water was circulated through the 64 plant culture trays inside the chamber during the tests but no plants were present. Environmental conditions were set to a 12-hr photoperiod with either a matching 26 C (light)/20 C (dark) thermoperiod, or a constant 23 C temperature. Leakage, as determined by carbon dioxide decay rates, averaged about 9.8 percent for the 26 C/20 C regime and 7.3 percent for the constant 23 C regime. Increasing the temperature from 20 C to 26 C caused a temporary increase in pressure (up to 0.5 kPa) relative to ambient, while decreasing the temperature caused a temporary decrease in pressure of similar magnitude. Little pressure change was observed during transition between 23 C (light) and 23 C (dark). The lack of large pressure events under isothermal conditions may explain the lower leakage rate observed. When only the plant support inserts were placed in the culture trays, condensate production averaged about 37 liters per day. Placing acrylic germination covers over the tops of culture trays reduced condensate production to about 7 liters per day. During both tests, condensate production from the lower air handling system was 60 to 70 percent greater than from the upper system, suggesting imbalances exist in chilled and hot water flows for the two air handling systems. Results indicate that atmospheric leakage rates are sufficiently low to measure CO2 exchange rates by plants and the accumulation of certain volatile contaminants (e.g., ethylene). Control system changes are recommended in order to balance operational differences (e.g., humidity and temperature) between the two halves of the chamber.

Effect of confinement on anharmonic phonon scattering and thermal conductivity in pristine silicon nanowires

NASA Astrophysics Data System (ADS)

Rashid, Zahid; Zhu, Liyan; Li, Wu

2018-02-01

The effect of confinement on the anharmonic phonon scattering rates and the consequences thereof on the thermal transport properties in ultrathin silicon nanowires with a diameter of 1-4 nm have been characterized using atomistic simulations and the phonon Boltzmann transport equation. The phonon density of states (PDOS) for ultrathin nanowires approaches a constant value in the vicinity of the Γ point and increases with decreasing diameter, which indicates the increasing importance of the low-frequency phonons as heat carriers. The anharmonic phonon scattering becomes dramatically enhanced with decreasing thickness of the nanowires. In the thinnest nanowire, the scattering rates for phonons above 1 THz are one order of magnitude higher than those in the bulk Si. Below 1 THz, the increase in scattering rates is even much more appreciable. Our numerical calculations revealed that the scattering rates for transverse (longitudinal) acoustic modes follow √{ω } (1 /√{ω } ) dependence at the low-frequency limit, whereas those for the degenerate flexural modes asymptotically approach a constant value. In addition, the group velocities of phonons are reduced compared with bulk Si except for low-frequency phonons (<1 -2 THz depending on the thickness of the nanowires). The increased scattering rates combined with reduced group velocities lead to a severely reduced thermal conductivity contribution from the high-frequency phonons. Although the thermal conductivity contributed by those phonons with low frequencies is instead increased mainly due to the increased PDOS, the total thermal conductivity is still reduced compared to that of the bulk. This work reveals an unexplored mechanism to understand the measured ultralow thermal conductivity of silicon nanowires.

A decade of change: an institutional experience with breast surgery in 1995 and 2005.

PubMed

Guth, Amber A; Shanker, Beth Ann; Roses, Daniel F; Axelrod, Deborah; Singh, Baljit; Toth, Hildegard; Shapiro, Richard L; Hiotis, Karen; Diflo, Thomas; Cangiarella, Joan F

2008-01-01

With the adoption of routine screening mammography, breast cancers are being diagnosed at earlier stages, with DCIS now accouting for 22.5% of all newly diagnosed breast cancers. This has been attributed to both increased breast cancer awareness and improvements in breast imaging techniques. How have these changes, including the increased use of image-guided sampling techniques, influenced the clinical practice of breast surgery? The institutional pathology database was queried for all breast surgeries, including breast reconstruction, performed in 1995 and 2005. Cosmetic procedures were excluded. The results were analysed utilizing the Chi-square test. Surgical indications changed during 10-year study period, with an increase in preoperatively diagnosed cancers undergoing definitive surgical management. ADH, and to a lesser extent, ALH, became indications for surgical excision. Fewer surgical biopsies were performed for indeterminate abnormalities on breast imaging, due to the introduction of stereotactic large core biopsy. While the rate of benign breast biopsies remained constant, there was a higher percentage of precancerous and DCIS cases in 2005. The overall rate of mastectomy decreased from 36.8% in 1995 to 14.5% in 2005. With the increase in sentinel node procedures, the rate of ALND dropped from 18.3% to 13.7%. Accompanying the increased recognition of early-stage cancers, the rate of positive ALND also decreased, from 43.3% to 25.0%. While the rate of benign breast biopsies has remained constant over a recent 10-year period, fewer diagnostic surgical image-guided biopsies were performed in 2005. A greater percentage of patients with breast cancer or preinvasive disease have these diagnoses determined before surgery. More preinvasive and Stage 0 cancers are undergoing surgical management. Earlier stage invasive cancers are being detected, reflected by the lower incidence of axillary nodal metastases.

A Decade of Change: An Institutional Experience with Breast Surgery in 1995 and 2005

PubMed Central

Guth, Amber A.; Shanker, Beth Ann; Roses, Daniel F.; Axelrod, Deborah; Singh, Baljit; Toth, Hildegard; Shapiro, Richard L.; Hiotis, Karen; Diflo, Thomas; Cangiarella, Joan F.

2008-01-01

Introduction: With the adoption of routine screening mammography, breast cancers are being diagnosed at earlier stages, with DCIS now accouting for 22.5% of all newly diagnosed breast cancers. This has been attributed to both increased breast cancer awareness and improvements in breast imaging techniques. How have these changes, including the increased use of image-guided sampling techniques, influenced the clinical practice of breast surgery? Methods: The institutional pathology database was queried for all breast surgeries, including breast reconstruction, performed in 1995 and 2005. Cosmetic procedures were excluded. The results were analysed utilizing the Chi-square test. Results: Surgical indications changed during 10-year study period, with an increase in preoperatively diagnosed cancers undergoing definitive surgical management. ADH, and to a lesser extent, ALH, became indications for surgical excision. Fewer surgical biopsies were performed for indeterminate abnormalities on breast imaging, due to the introduction of stereotactic large core biopsy. While the rate of benign breast biopsies remained constant, there was a higher percentage of precancerous and DCIS cases in 2005. The overall rate of mastectomy decreased from 36.8% in 1995 to 14.5% in 2005. With the increase in sentinel node procedures, the rate of ALND dropped from 18.3% to 13.7%. Accompanying the increased recognition of early-stage cancers, the rate of positive ALND also decreased, from 43.3% to 25.0%. Conclusions: While the rate of benign breast biopsies has remained constant over a recent 10-year period, fewer diagnostic surgical image-guided biopsies were performed in 2005. A greater percentage of patients with breast cancer or preinvasive disease have these diagnoses determined before surgery. More preinvasive and Stage 0 cancers are undergoing surgical management. Earlier stage invasive cancers are being detected, reflected by the lower incidence of axillary nodal metastases. PMID:21655372

Anti-Arrhenius cleavage of covalent bonds in bottlebrush macromolecules on substrate

PubMed Central

Lebedeva, Natalia V.; Nese, Alper; Sun, Frank C.; Matyjaszewski, Krzysztof; Sheiko, Sergei S.

2012-01-01

Spontaneous degradation of bottlebrush macromolecules on aqueous substrates was monitored by atomic force microscopy. Scission of C─C covalent bonds in the brush backbone occurred due to steric repulsion between the adsorbed side chains, which generated bond tension on the order of several nano-Newtons. Unlike conventional chemical reactions, the rate of bond scission was shown to decrease with temperature. This apparent anti-Arrhenius behavior was caused by a decrease in the surface energy of the underlying substrate upon heating, which results in a corresponding decrease of bond tension in the adsorbed macromolecules. Even though the tension dropped minimally from 2.16 to 1.89 nN, this was sufficient to overpower the increase in the thermal energy (kBT) in the Arrhenius equation. The rate constant of the bond-scission reaction was measured as a function of temperature and surface energy. Fitting the experimental data by a perturbed Morse potential V = V0(1 - e-βx)2 - fx, we determined the depth and width of the potential to be V0 = 141 ± 19 kJ/mol and β-1 = 0.18 ± 0.03 Å, respectively. Whereas the V0 value is in reasonable agreement with the activation energy Ea = 80–220 kJ/mol of mechanical and thermal degradation of organic polymers, it is significantly lower than the dissociation energy of a C─C bond De = 350 kJ/mol. Moreover, the force constant Kx = 2β2V0 = 1.45 ± 0.36 kN/m of a strained bottlebrush along its backbone is markedly larger than the force constant of a C─C bond Kl = 0.44 kN/m, which is attributed to additional stiffness due to deformation of the side chains. PMID:22645366

Tweezering the core of dendrimers: medium effect on the kinetic and thermodynamic properties.

PubMed

Giansante, Carlo; Mazzanti, Andrea; Baroncini, Massimo; Ceroni, Paola; Venturi, Margherita; Klärner, Frank-Gerrit; Vögtle, Fritz

2009-10-02

We have investigated the complex formation between dendritic guests and a molecular tweezer host by NMR, absorption, and emission spectroscopy as well as electrochemical techniques. The dendrimers are constituted by an electron-acceptor 4,4'-bipyridinium core appended with one (DnB(2+)) or two (Dn(2)B(2+)) polyaryl-ether dendrons. Tweezer T comprises a naphthalene and four benzene components bridged by four methylene groups. Medium effects on molecular recognition phenomena are discussed and provide insight into the conformation of dendrimers: change in solvent polarity from pure CH(2)Cl(2) to CH(2)Cl(2)/CH(3)CN mixtures and addition of tetrabutylammonium hexafluorophosphate (NBu(4)PF(6), up to 0.15 M), the supporting electrolyte used in the electrochemical measurements, have been investigated. The association constants measured in different media show the following trend: (i) they decrease upon increasing polarity of the solvent, as expected for host-guest complexes stabilized by electron donor-acceptor interactions; (ii) no effect of generation and number of dendrons (one for the DnB(2+) family and two for the Dn(2)B(2+) family) appended to the core is observed in higher polarity media; and (iii) in a low-polarity solvent, like CH(2)Cl(2), the stability of the inclusion complexes is higher for DnB(2+) dendrimers than for Dn(2)B(2+) ones, while within each dendrimer family it increases by decreasing dendron generation, and upon addition of NBu(4)PF(6). The last result has been ascribed to a partial dendron unfolding. Kinetic investigations performed in lower polarity media evidence that the rate constants of complex formation are slower for symmetric Dn(2)B(2+) dendrimers than for the nonsymmetric DnB(2+) ones, and that within the Dn(2)B(2+) family, they decrease by increasing dendron generation. The dependence of the rate constants for the formation and dissociation of the complexes upon addition of NBu(4)PF(6) has also been investigated and discussed.

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

Redies, C.; Hoffer, L.J.; Beil, C.

In prolonged fasting, the brain derives a large portion of its oxidative energy from the ketone bodies, beta-hydroxybutyrate and acetoacetate, thereby reducing whole body glucose consumption. Energy substrate utilization differs regionally in the brain of fasting rat, but comparable information has hitherto been unavailable in humans. We used positron emission tomography (PET) to study regional brain glucose and oxygen metabolism, blood flow, and blood volume in four obese subjects before and after a 3-wk total fast. Whole brain glucose utilization fell to 54% of control (postabsorptive) values (P less than 0.002). The whole brain rate constant for glucose tracer phosphorylationmore » fell to 51% of control values (P less than 0.002). Both parameters decreased uniformly throughout the brain. The 2-fluoro-2-deoxy-D-glucose lumped constant decreased from a control value of 0.57 to 0.43 (P less than 0.01). Regional blood-brain barrier transfer coefficients for glucose tracer, regional oxygen utilization, blood flow, and blood volume were unchanged.« less

Kinetic Studies on Enzyme-Catalyzed Reactions: Oxidation of Glucose, Decomposition of Hydrogen Peroxide and Their Combination

PubMed Central

Tao, Zhimin; Raffel, Ryan A.; Souid, Abdul-Kader; Goodisman, Jerry

2009-01-01

The kinetics of the glucose oxidase-catalyzed reaction of glucose with O2, which produces gluconic acid and hydrogen peroxide, and the catalase-assisted breakdown of hydrogen peroxide to generate oxygen, have been measured via the rate of O2 depletion or production. The O2 concentrations in air-saturated phosphate-buffered salt solutions were monitored by measuring the decay of phosphorescence from a Pd phosphor in solution; the decay rate was obtained by fitting the tail of the phosphorescence intensity profile to an exponential. For glucose oxidation in the presence of glucose oxidase, the rate constant determined for the rate-limiting step was k = (3.0 ± 0.7) ×104 M−1s−1 at 37°C. For catalase-catalyzed H2O2 breakdown, the reaction order in [H2O2] was somewhat greater than unity at 37°C and well above unity at 25°C, suggesting different temperature dependences of the rate constants for various steps in the reaction. The two reactions were combined in a single experiment: addition of glucose oxidase to glucose-rich cell-free media caused a rapid drop in [O2], and subsequent addition of catalase caused [O2] to rise and then decrease to zero. The best fit of [O2] to a kinetic model is obtained with the rate constants for glucose oxidation and peroxide decomposition equal to 0.116 s−1 and 0.090 s−1 respectively. Cellular respiration in the presence of glucose was found to be three times as rapid as that in glucose-deprived cells. Added NaCN inhibited O2 consumption completely, confirming that oxidation occurred in the cellular mitochondrial respiratory chain. PMID:19348778

A kinetic model of the formation of organic monolayers on hydrogen-terminated silicon by hydrosilation of alkenes.

PubMed

Woods, M; Carlsson, S; Hong, Q; Patole, S N; Lie, L H; Houlton, A; Horrocks, B R

2005-12-22

We have analyzed a kinetic model for the formation of organic monolayers based on a previously suggested free radical chain mechanism for the reaction of unsaturated molecules with hydrogen-terminated silicon surfaces (Linford, M. R.; Fenter, P. M.; Chidsey, C. E. D. J. Am. Chem. Soc 1995, 117, 3145). A direct consequence of this mechanism is the nonexponential growth of the monolayer, and this has been observed spectroscopically. In the model, the initiation of silyl radicals on the surface is pseudo first order with rate constant, ki, and the rate of propagation is determined by the concentration of radicals and unreacted Si-H nearest neighbor sites with a rate constant, kp. This propagation step determines the rate at which the monolayer forms by addition of alkene molecules to form a track of molecules that constitute a self-avoiding random walk on the surface. The initiation step describes how frequently new random walks commence. A termination step by which the radicals are destroyed is also included. The solution of the kinetic equations yields the fraction of alkylated surface sites and the mean length of the random walks as a function of time. In mean-field approximation we show that (1) the average length of the random walk is proportional to (kp/ki)1/2, (2) the monolayer surface coverage grows exponentially only after an induction period, (3) the effective first-order rate constant describing the growth of the monolayer and the induction period (kt) is k = (2ki kp)1/2, (4) at long times the effective first-order rate constant drops to ki, and (5) the overall activation energy for the growth kinetics is the mean of the activation energies for the initiation and propagation steps. Monte Carlo simulations of the mechanism produce qualitatively similar kinetic plots, but the mean random walk length (and effective rate constant) is overestimated by the mean field approximation and when kp > ki, we find k approximately ki0.7kp0.3 and Ea = (0.7Ei+ 0.3Ep). However the most striking prediction of the Monte Carlo simulations is that at long times, t > 1/k, the effective first-order rate constant decreases to ki even in the absence of a chemical termination step. Experimental kinetic data for the reaction of undec-1-ene with hydrogen-terminated porous silicon under thermal reflux in toluene and ethylbenzene gave a value of k = 0.06 min(-1) and an activation energy of 107 kJ mol(-1). The activation energy is in reasonable agreement with density functional calculations of the transition state energies for the initiation and propagation steps.

Cadmium removal from wastewater by sponge iron sphere prepared by charcoal direct reduction.

PubMed

Li, Junguo; Li, Jun; Li, Yungang

2009-01-01

Sponge iron sphere (SIS), made of concentrated iron powder and possessed high activity and intension, was prepared through the process of palletizing, roasting and direct reduction by charcoal. The sponge iron sphere could remove most of Cd(2+) from wastewater. The results showed the Cd(2+) removal followed the first order reaction. Initial pH value played an important role in Cd(2+) removal. With original initial pH, Cd(2+) removal decreased to the minimum and then increased slightly with the rising of original concentration. The removal rate constant was -0.1263 and -0.0711 h(-1), respectively, under the Cd(2+) concentration of 50 and 200 mg/L. When the initial pH was adjusted to 3.0, the removal rate constant could increase to -9.896 and -4.351 h(-1), respectively. The removal percentage almost reached to 100% when Cd(2+) concentration was below 100 mg/L. While Cd(2+) concentration was above 100 mg/L, Cd(2+) removal percentage decreased slightly. In dynamic experiments, the column filled with sponge iron sphere exhibited favorable permeability. There was no sphere pulverization and conglutination between spheres. In contrast to the static state experiments, the Cd(2+) removal percentage in dynamic state experiment was lower, and the removal Cd(2+) quantity was 1.749 mg/g.

Uncertainty propagation in modeling of plasma-assisted hydrogen production from biogas

NASA Astrophysics Data System (ADS)

Zaherisarabi, Shadi; Venkattraman, Ayyaswamy

2016-10-01

With the growing concern of global warming and the resulting emphasis on decreasing greenhouse gas emissions, there is an ever-increasing need to utilize energy-production strategies that can decrease the burning of fossil fuels. In this context, hydrogen remains an attractive clean-energy fuel that can be oxidized to produce water as a by-product. In spite of being an abundant species, hydrogen is seldom found in a form that is directly usable for energy-production. While steam reforming of methane is one popular technique for hydrogen production, plasma-assisted conversion of biogas (carbon dioxide + methane) to hydrogen is an attractive alternative. Apart from producing hydrogen, the other advantage of using biogas as raw material is the fact that two potent greenhouse gases are consumed. In this regard, modeling is an important tool to understand and optimize plasma-assisted conversion of biogas. The primary goal of this work is to perform a comprehensive statistical study that quantifies the influence of uncertain rate constants thereby determining the key reaction pathways. A 0-D chemical kinetics solver in the OpenFOAM suite is used to perform a series of simulations to propagate the uncertainty in rate constants and the resulting mean and standard deviation of outcomes.

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

PubMed

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

2016-03-01

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

An Anionic Phospholipid Enables the Hydrophobic Surfactant Proteins to Alter Spontaneous Curvature

PubMed Central

Chavarha, Mariya; Loney, Ryan W.; Rananavare, Shankar B.; Hall, Stephen B.

2013-01-01

The hydrophobic surfactant proteins, SP-B and SP-C, greatly accelerate the adsorption of the surfactant lipids to an air/water interface. Previous studies of factors that affect curvature suggest that vesicles may adsorb via a rate-limiting structure with prominent negative curvature, in which the hydrophilic face of the lipid leaflets is concave. To determine if SP-B and SP-C might promote adsorption by inducing negative curvature, we used small-angle x-ray scattering to test whether the physiological mixture of the two proteins affects the radius of cylindrical monolayers in the inverse hexagonal phase. With dioleoyl phosphatidylethanolamine alone, the proteins had no effect on the hexagonal lattice constant, suggesting that the proteins fail to insert into the cylindrical monolayers. The surfactant lipids also contain ∼10% anionic phospholipids, which might allow incorporation of the cationic proteins. With 10% of the anionic dioleoyl phosphatidylglycerol added to dioleoyl phosphatidylethanolamine, the proteins induced a dose-related decrease in the hexagonal lattice constant. At 30°C, the reduction reached a maximum of 8% relative to the lipids alone at ∼1% (w/w) protein. Variation of NaCl concentration tested whether the effect of the protein represented a strictly electrostatic effect that screening by electrolyte would eliminate. With concentrations up to 3 M NaCl, the dose-related change in the hexagonal lattice constant decreased but persisted. Measurements at different hydrations determined the location of the pivotal plane and proved that the change in the lattice constant produced by the proteins resulted from a shift in spontaneous curvature. These results provide the most direct evidence yet that the surfactant proteins can induce negative curvature in lipid leaflets. This finding supports the model in which the proteins promote adsorption by facilitating the formation of a negatively curved, rate-limiting structure. PMID:23442910

Fire ants perpetually rebuild sinking towers.

PubMed

Phonekeo, Sulisay; Mlot, Nathan; Monaenkova, Daria; Hu, David L; Tovey, Craig

2017-07-01

In the aftermath of a flood, fire ants, Solenopsis invicta , cluster into temporary encampments. The encampments can contain hundreds of thousands of ants and reach over 30 ants high. How do ants build such tall structures without being crushed? In this combined experimental and theoretical study, we investigate the shape and rate of construction of ant towers around a central support. The towers are bell shaped, consistent with towers of constant strength such as the Eiffel tower, where each element bears an equal load. However, unlike the Eiffel tower, the ant tower is built through a process of trial and error, whereby failed portions avalanche until the final shape emerges. High-speed and novel X-ray videography reveal that the tower constantly sinks and is rebuilt, reminiscent of large multicellular systems such as human skin. We combine the behavioural rules that produce rafts on water with measurements of adhesion and attachment strength to model the rate of growth of the tower. The model correctly predicts that the growth rate decreases as the support diameter increases. This work may inspire the design of synthetic swarms capable of building in vertical layers.

Translation and Rotation Trade Off in Human Visual Heading Estimation

NASA Technical Reports Server (NTRS)

Stone, Leland S.; Perrone, John A.; Null, Cynthia H. (Technical Monitor)

1996-01-01

We have previously shown that, during simulated curvilinear motion, humans can make reasonably accurate and precise heading judgments from optic flow without either oculomotor or static-depth cues about rotation. We now systematically investigate the effect of varying the parameters of self-motion. We visually simulated 400 ms of self-motion along curved paths (constant rotation and translation rates, fixed retinocentric heading) towards two planes of random dots at 10.3 m and 22.3 m at mid-trial. Retinocentric heading judgments of 4 observers (2 naive) were measured for 12 different combinations of translation (T between 4 and 16 m/s) and rotation (R either 8 or 16 deg/s). In the range tested, heading bias and uncertainty decrease quasilinearly with T/R, but the bias also appears to depend on R. If depth is held constant, the ratio T/R can account for much of the variation in the accuracy and precision of human visual heading estimation, although further experiments are needed to resolve whether absolute rotation rate, total flow rate, or some other factor can account for the observed -2 deg shift between the bias curves.

Ethanol inhibition kinetics of Kluyveromyces marxianus grown on Jerusalem artichoke juice

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

Bajpai, P.; Margaritis, A.

1982-12-01

The kinetics of ethanol inhibition on cell growth and ethanol production by Kluyveromyces marxianus UCD (FST) 55-82 were studied during batch growth. The liquid medium contained 10% (weight/volume) inulin-type sugars derived from an extract of Jerusalem artichoke (Helianthus tuberosus) tubers, supplemented with small amounts of Tween 80, oleic acid, and corn steep liquor. Initial ethanol concentrations ranging from 0 to 80 g/liter in the liquid medium were used to study the inhibitory effect of ethanol on the following parameters: maximum specific growth rate (mu max), cell and ethanol yields, and sugar utilization. It was found that as the initial ethanolmore » concentration increased from 0 to 80 g/liter, and maximum specific growth rate of K. marxianus cells decreased from 0.42 to 0.09/hour, whereas the ethanol and cell yields and sugar utilization remained almost constant. A simple kinetic model was used to correlate the mu max results and the rates of cell and ethanol production, and the appropriate constants were evaluated. (Refs. 22).« less

Fire ants perpetually rebuild sinking towers

NASA Astrophysics Data System (ADS)

Phonekeo, Sulisay; Mlot, Nathan; Monaenkova, Daria; Hu, David L.; Tovey, Craig

2017-07-01

In the aftermath of a flood, fire ants, Solenopsis invicta, cluster into temporary encampments. The encampments can contain hundreds of thousands of ants and reach over 30 ants high. How do ants build such tall structures without being crushed? In this combined experimental and theoretical study, we investigate the shape and rate of construction of ant towers around a central support. The towers are bell shaped, consistent with towers of constant strength such as the Eiffel tower, where each element bears an equal load. However, unlike the Eiffel tower, the ant tower is built through a process of trial and error, whereby failed portions avalanche until the final shape emerges. High-speed and novel X-ray videography reveal that the tower constantly sinks and is rebuilt, reminiscent of large multicellular systems such as human skin. We combine the behavioural rules that produce rafts on water with measurements of adhesion and attachment strength to model the rate of growth of the tower. The model correctly predicts that the growth rate decreases as the support diameter increases. This work may inspire the design of synthetic swarms capable of building in vertical layers.

Fire ants perpetually rebuild sinking towers

PubMed Central

Phonekeo, Sulisay; Mlot, Nathan; Monaenkova, Daria; Tovey, Craig

2017-01-01

In the aftermath of a flood, fire ants, Solenopsis invicta, cluster into temporary encampments. The encampments can contain hundreds of thousands of ants and reach over 30 ants high. How do ants build such tall structures without being crushed? In this combined experimental and theoretical study, we investigate the shape and rate of construction of ant towers around a central support. The towers are bell shaped, consistent with towers of constant strength such as the Eiffel tower, where each element bears an equal load. However, unlike the Eiffel tower, the ant tower is built through a process of trial and error, whereby failed portions avalanche until the final shape emerges. High-speed and novel X-ray videography reveal that the tower constantly sinks and is rebuilt, reminiscent of large multicellular systems such as human skin. We combine the behavioural rules that produce rafts on water with measurements of adhesion and attachment strength to model the rate of growth of the tower. The model correctly predicts that the growth rate decreases as the support diameter increases. This work may inspire the design of synthetic swarms capable of building in vertical layers. PMID:28791170

Isoprene/methyl acrylate Diels-Alder reaction in supercritical carbon dioxide

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

Lin, B.; Akgerman, A.

1999-12-01

The Diels-Alder reaction between isoprene and methyl acrylate was carried out in supercritical carbon dioxide in the temperature range 110--140 C and the pressure range 95.2--176.9 atm in a 300 cm{sup 3} autoclave. The high-pressure phase behavior of the reaction mixture in the vicinity of its critical region was determined in a mixed vessel with a sight window to ensure that all the experiments were performed in the supercritical single-phase region. Kinetic data were obtained at different temperatures, pressures, and reaction times. It was observed that in the vicinity of the critical point the reaction rate constant decreases with increasingmore » pressure. It was also determined that the reaction selectivity does not change with operating conditions. Transition-state theory was used to explain the effect of pressure on reaction rate and product selectivity. Additional experiments were conducted at constant temperature but different phase behaviors (two-phase region, liquid phase, supercritical phase) by adjusting the initial composition and pressure. It was shown that the highest reaction rate is in the supercritical region.« less

Osmolytic Effect of Sucrose on Thermal Denaturation of Pea Seedling Copper Amine Oxidase.

PubMed

Amani, Mojtaba; Barzegar, Aboozar; Mazani, Mohammad

2017-04-01

Protein stability is a subject of interest by many researchers. One of the common methods to increase the protein stability is using the osmolytes. Many studies and theories analyzed and explained osmolytic effect by equilibrium thermodynamic while most proteins undergo an irreversible denaturation. In current study we investigated the effect of sucrose as an osmolyte on the thermal denaturation of pea seedlings amine oxidase by the enzyme activity, fluorescence spectroscopy, circular dichroism, and differential scanning calorimetry. All experiments are in agreement that pea seedlings amine oxidase denaturation is controlled kinetically and its kinetic stability is increased in presence of sucrose. Differential scanning calorimetry experiments at different scanning rates showed that pea seedlings amine oxidase unfolding obeys two-state irreversible model. Fitting the differential scanning calorimetry data to two-state irreversible model showed that unfolding enthalpy and T * , temperature at which rate constant equals unit per minute, are increased while activation energy is not affected by increase in sucrose concentration. We concluded that osmolytes decrease the molecular oscillation of irreversible proteins which leads to decline in unfolding rate constant.

Viscoplasticity based on overstress with a differential growth law for the equilibrium stress

NASA Technical Reports Server (NTRS)

Krempl, E.; Mcmahon, J. J.; Yao, D.

1985-01-01

Two coupled, nonlinear differential equations are proposed for the modeling of the elastic and rate (time) dependent inelastic behavior of structural metals in the absence of recovery and aging. The structure of the model is close to the unified theories but contains essential differences. It is shown that the model reproduces almost elastic regions upon initial loading and in the unloading regions of the hysteresis loop. Under loading, unloading and reloading in strain control the model simulated the experimentally observed sharp transition from nearly elastic to inelastic behavior. When a formulation akin to existing unified theories is adopted the almost elastic regions reduce the points and the transition upon reloading is very gradual. For different formulations the behavior under sudden in(de)creases of the strain rate by two orders of magnitude is simulated by numerical experiments and differences are noted. The model represents cyclically neutral behavior and contains three constants and two positive, decreasing functions. The determination of constants and functions from monotonic loading with strain rate changes and relaxation periods is described.

High temperature monotonic and cyclic deformation in a directionally solidified nickel-base superalloy

NASA Technical Reports Server (NTRS)

Huron, Eric S.

1986-01-01

Directionally solidified (DS) MAR-M246+Hf was tested in tension and fatigue, at temperatures from 20 C to 1093 C. Tests were performed on (001) oriented specimens at strain rates of 50 % and 0.5 % per minute. In tension, the yield strength was constant up to 704 C, above which the strength dropped off rapidly. A strong dependence of strength on strain rate was seen at the higher temperatures. The deformation mode was observed to change from heterogeneous to homogeneous with increasing temperature. Low Cycle Fatigue tests were done using a fully reversed waveform and total strain control. For a given plastic strain range, lives increased with increasing temperature. For a given temperature strain rate had a strong effect on life. At 704 C, decreasing strain rates decreased life, while at the higher temperatures, decreasing strain rates increased life, for a given plastic strain range. These results could be explained through considerations of the deformation modes and stress levels. At the higher temperatures, marked coarsening caused beneficial stress reductions, but oxidation limited the life. The longitudinal grain boundaries were found to influence slip behavior. The degree of secondary slip adjacent to the boundaries was found to be related to the degree of misorientation between the grains.

Multidimensional Cyclic Voltammetry Simulations of Pseudocapacitive Electrodes with a Conducting Nanorod Scaffold

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

Mei, Bing-Ang; Li, Bin; Lin, Jie

This paper aims to understand the effect of nanoarchitecture on the performance of pseudocapacitive electrodes consisting of conducting scaffold coated with pseudocapacitive material. To do so, two-dimensional numerical simulations of ordered conducting nanorods coated with a thin film of pseudocapacitive material were performed. The simulations reproduced three-electrode cyclic voltammetry measurements based on a continuum model derived from first principles. Two empirical approaches commonly used experimentally to characterize the contributions of surface-controlled and diffusion-controlled charge storage mechanisms to the total current density with respect to scan rate were theoretically validated for the first time. Moreover, the areal capacitive capacitance, attributed tomore » EDL formation, remained constant and independent of electrode dimensions, at low scan rates. However, at high scan rates, it decreased with decreasing conducting nanorod radius and increasing pseudocapacitive layer thickness due to resistive losses. By contrast, the gravimetric faradaic capacitance, due to reversible faradaic reactions, decreased continuously with increasing scan rate and pseudocapacitive layer thickness but was independent of conducting nanorod radius. Note that the total gravimetric capacitance predicted numerically featured values comparable to experimental measurements. Finally, an optimum pseudocapacitive layer thickness that maximizes total areal capacitance was identified as a function of scan rate and confirmed by scaling analysis.« less

Multidimensional Cyclic Voltammetry Simulations of Pseudocapacitive Electrodes with a Conducting Nanorod Scaffold

DOE PAGES

Mei, Bing-Ang; Li, Bin; Lin, Jie; ...

2017-10-27

This paper aims to understand the effect of nanoarchitecture on the performance of pseudocapacitive electrodes consisting of conducting scaffold coated with pseudocapacitive material. To do so, two-dimensional numerical simulations of ordered conducting nanorods coated with a thin film of pseudocapacitive material were performed. The simulations reproduced three-electrode cyclic voltammetry measurements based on a continuum model derived from first principles. Two empirical approaches commonly used experimentally to characterize the contributions of surface-controlled and diffusion-controlled charge storage mechanisms to the total current density with respect to scan rate were theoretically validated for the first time. Moreover, the areal capacitive capacitance, attributed tomore » EDL formation, remained constant and independent of electrode dimensions, at low scan rates. However, at high scan rates, it decreased with decreasing conducting nanorod radius and increasing pseudocapacitive layer thickness due to resistive losses. By contrast, the gravimetric faradaic capacitance, due to reversible faradaic reactions, decreased continuously with increasing scan rate and pseudocapacitive layer thickness but was independent of conducting nanorod radius. Note that the total gravimetric capacitance predicted numerically featured values comparable to experimental measurements. Finally, an optimum pseudocapacitive layer thickness that maximizes total areal capacitance was identified as a function of scan rate and confirmed by scaling analysis.« less

Kinetics of reduction of plutonium(VI) and neptunium(VI) by sulfide in neutral and alkaline solutions

USGS Publications Warehouse

Nash, K.L.; Cleveland, J.M.; Sullivan, J.C.; Woods, M.

1986-01-01

The rate of reduction of plutonium(VI) and neptunium(VI) by bisulfide ion in neutral and mildly alkaline solutions has been investigated by the stopped-flow technique. The reduction of both of these ions to the pentavalent oxidation state appears to occur in an intramolecular reaction involving an unusual actinide(VI)-hydroxide-bisulfide complex. For plutonium the rate of reduction is 27.4 (??4.1) s-1 at 25??C with ??H* = +33.2 (??1.0) kJ/mol and ??S* = -106 (??4) J/(mol K). The apparent stability constant for the transient complex is 4.66 (??0.94) ?? 103 M-1 at 25??C with associated thermodynamic parameters of ??Hc = +27.7 (??0.4) kJ/mol and ??Sc = +163 (??2) J/(mol K). The corresponding rate and stability constants are determined for the neptunium system at 25??C (k3 = 139 (??30) s-1, Kc. = 1.31 (??0.32) ?? 103 M-1), but equivalent parameters cannot be determined at reduced temperatures. The reaction rate is decreased by bicarbonate ion. At pH > 10.5, a second reaction mechanism, also involving a sulfide complex, is indicated. ?? 1986 American Chemical Society.

Constant pressure mode extended simple gradient liquid chromatography system for micro and nanocolumns.

PubMed

Šesták, Jozef; Kahle, Vladislav

2014-07-11

Performing gradient liquid chromatography at constant pressure instead of constant flow rate has serious potential for shortening the analysis time and increasing the productivity of HPLC instruments that use gradient methods. However, in the constant pressure mode the decreasing column permeability during a long period of time negatively affects the repeatability of retention time. Thus a volume-based approach, in which the detector signal is plotted as a function of retention volume, must be taken into consideration. Traditional HPLC equipment, however, requires quite complex hardware and software modifications in order to work at constant pressure and in the volume-based mode. In this short communication, a low cost and easily feasible pressure-controlled extension of the previously described simple gradient liquid chromatography platform is proposed. A test mixture of four nitro esters was separated by 10-60% (v/v) acetone/water gradient and a high repeatability of retention volumes at 20MPa (RSD less than 0.45%) was realized. Separations were also performed at different values of pressure (20, 25, and 31MPa), and only small variations of the retention volumes (up to 0.8%) were observed. In this particular case, the gain in the analysis speed of 7% compared to the constant flow mode was realized at a constant pressure. Copyright © 2014 Elsevier B.V. All rights reserved.

Higher success rate with transcranial electrical stimulation of motor-evoked potentials using constant-voltage stimulation compared with constant-current stimulation in patients undergoing spinal surgery.

PubMed

Shigematsu, Hideki; Kawaguchi, Masahiko; Hayashi, Hironobu; Takatani, Tsunenori; Iwata, Eiichiro; Tanaka, Masato; Okuda, Akinori; Morimoto, Yasuhiko; Masuda, Keisuke; Tanaka, Yuu; Tanaka, Yasuhito

2017-10-01

During spine surgery, the spinal cord is electrophysiologically monitored via transcranial electrical stimulation of motor-evoked potentials (TES-MEPs) to prevent injury. Transcranial electrical stimulation of motor-evoked potential involves the use of either constant-current or constant-voltage stimulation; however, there are few comparative data available regarding their ability to adequately elicit compound motor action potentials. We hypothesized that the success rates of TES-MEP recordings would be similar between constant-current and constant-voltage stimulations in patients undergoing spine surgery. The objective of this study was to compare the success rates of TES-MEP recordings between constant-current and constant-voltage stimulation. This is a prospective, within-subject study. Data from 100 patients undergoing spinal surgery at the cervical, thoracic, or lumbar level were analyzed. The success rates of the TES-MEP recordings from each muscle were examined. Transcranial electrical stimulation with constant-current and constant-voltage stimulations at the C3 and C4 electrode positions (international "10-20" system) was applied to each patient. Compound muscle action potentials were bilaterally recorded from the abductor pollicis brevis (APB), deltoid (Del), abductor hallucis (AH), tibialis anterior (TA), gastrocnemius (GC), and quadriceps (Quad) muscles. The success rates of the TES-MEP recordings from the right Del, right APB, bilateral Quad, right TA, right GC, and bilateral AH muscles were significantly higher using constant-voltage stimulation than those using constant-current stimulation. The overall success rates with constant-voltage and constant-current stimulations were 86.3% and 68.8%, respectively (risk ratio 1.25 [95% confidence interval: 1.20-1.31]). The success rates of TES-MEP recordings were higher using constant-voltage stimulation compared with constant-current stimulation in patients undergoing spinal surgery. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

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.

Simulation of groundwater and surface-water interaction and effects of pumping in a complex glacial-sediment aquifer, east central Massachusetts

USGS Publications Warehouse

Eggleston, Jack R.; Carlson, Carl S.; Fairchild, Gillian M.; Zarriello, Phillip J.

2012-01-01

The effects of groundwater pumping on surface-water features were evaluated by use of a numerical groundwater model developed for a complex glacial-sediment aquifer in northeastern Framingham, Massachusetts, and parts of surrounding towns. The aquifer is composed of sand, gravel, silt, and clay glacial-fill sediments up to 270 feet thick over an irregular fractured bedrock surface. Surface-water bodies, including Cochituate Brook, the Sudbury River, Lake Cochituate, Dudley Pond, and adjoining wetlands, are in hydraulic connection with the aquifer and can be affected by groundwater withdrawals. Groundwater and surface-water interaction was simulated with MODFLOW-NWT under current conditions and a variety of hypothetical pumping conditions. Simulations of hypothetical pumping at reactivated water supply wells indicate that captured groundwater would decrease baseflow to the Sudbury River and induce recharge from Lake Cochituate. Under constant (steady-state) pumping, induced groundwater recharge from Lake Cochituate was equal to about 32 percent of the simulated pumping rate, and flow downstream in the Sudbury River decreased at the same rate as pumping. However, surface water responded quickly to pumping stresses. When pumping was simulated for 1 month and then stopped, streamflow depletions decreased by about 80 percent within 2 months and by about 90 percent within about 4 months. The fast surface water response to groundwater pumping offers the potential to substantially reduce streamflow depletions during periods of low flow, which are of greatest concern to the ecological integrity of the river. Results indicate that streamflow depletion during September, typically the month of lowest flow, can be reduced by 29 percent by lowering the maximum pumping rates to near zero during September. Lowering pumping rates for 3 months (July through September) reduces streamflow depletion during September by 79 percent as compared to constant pumping. These results demonstrate that a seasonal or streamflow-based groundwater pumping schedule can reduce the effects of pumping during periods of low flow.

The impact of neighboring infection on the computer virus spread in packets on scale-free networks

NASA Astrophysics Data System (ADS)

Lazfi, S.; Lamzabi, S.; Rachadi, A.; Ez-Zahraouy, H.

2017-12-01

In this paper, we introduce the effect of neighbors on the infection of packets by computer virus in the SI and SIR models using the minimal traffic routing protocol. We have applied this model to the Barabasi-Albert network to determine how intrasite and extrasite infection rates affect virus propagation through the traffic flow of information packets in both the free-flow and the congested phases. The numerical results show that when we change the intrasite infection rate λ1 while keeping constant the extrasite infection rate λ2, we get normal behavior in the congested phase: in the network, the proportion of infected packets increases to reach a peak and then decreases resulting in a simultaneous increase of the recovered packets. In contrast, when the intrasite infection rate λ1 is kept fixed, an increase of the extrasite infection rate results in two regimes: The first one is characterized by an increase of the proportion of infected packets until reaching some peak value and then decreases smoothly. The second regime is characterized by an increase of infected packets to some stationary value.

Studies on the effect of ammonia flow rate induced defects in gallium nitride grown by MOCVD

NASA Astrophysics Data System (ADS)

Suresh, S.; Lourdudoss, S.; Landgren, G.; Baskar, K.

2010-10-01

Gallium nitride (GaN) epitaxial layers were grown with different V/III ratios by varying the ammonia (NH 3) flow rate, keeping the flow rate of the other precursor, trimethylgallium (TMG), constant, in an MOCVD system. X-ray rocking curve widths of a (1 0 2) reflection increase with an increase in V/III ratio while the (0 0 2) rocking curve widths decrease. The dislocation density was found to increase with an increase in ammonia flow rate, as determined by hot-wet chemical etching and atomic force microscopy. 77 K photoluminescence studies show near band emission at 3.49 eV and yellow luminescence peaking at 2.2 eV. The yellow luminescence (YL) intensity decreases with an increase in V/III ratio. Positron annihilation spectroscopy studies show that the concentration of Ga-like vacancies increases with an increase in ammonia flow rate. This study confirms that the yellow luminescence in the GaN arises due to deep levels formed by gallium vacancies decorated with oxygen atoms.

Population and prehistory I: Food-dependent population growth in constant environments.

PubMed

Lee, Charlotte T; Tuljapurkar, Shripad

2008-06-01

We present a demographic model that describes the feedbacks between food supply, human mortality and fertility rates, and labor availability in expanding populations, where arable land area is not limiting. This model provides a quantitative framework to describe how environment, technology, and culture interact to influence the fates of preindustrial agricultural populations. We present equilibrium conditions and derive approximations for the equilibrium population growth rate, food availability, and other food-dependent measures of population well-being. We examine how the approximations respond to environmental changes and to human choices, and find that the impact of environmental quality depends upon whether it manifests through agricultural yield or maximum (food-independent) survival rates. Human choices can complement or offset environmental effects: greater labor investments increase both population growth and well-being, and therefore can counteract lower agricultural yield, while fertility control decreases the growth rate but can increase or decrease well-being. Finally we establish equilibrium stability criteria, and argue that the potential for loss of local stability at low population growth rates could have important consequences for populations that suffer significant environmental or demographic shocks.

Physiological effects of a bactericidal protein from human polymorphonuclear leukocytes on Pseudomonas aeruginosa.

PubMed

Hovde, C J; Gray, B H

1986-04-01

The physiological changes seen in Pseudomonas aeruginosa after exposure to a bactericidal protein (BP) from the granules of human polymorphonuclear leukocytes were studied. It was demonstrated, using radiolabeled proline or leucine, that both the rate of cellular uptake and amino acid incorporation into trichloroacetic acid-insoluble material were markedly decreased immediately after exposure to BP. The rate of O2 consumption by P. aeruginosa was decreased immediately after exposure to BP and continued to decline exponentially until it ceased completely 30 min after exposure to BP. In the presence of 30 mM CaCl2 or MgCl2, bacteria were protected from death due to BP and respiration rates were unaffected. The cellular ATP pool of P. aeruginosa remained constant for up to 2 h after exposure to BP. Membrane depolarization was measured by the influx of the lipophilic anion thiocyanate. It was shown that the cytoplasmic membrane of P. aeruginosa was partially depolarized after exposure to BP. Purified BP killed 95% of 5 X 10(6) CFU of P. aeruginosa at a concentration of 60 to 100 ng of protein per ml. Although the concentration of bacteria and BP varied with each type of experiment, the BP/bacteria ratio required to cause a 95 to 99% loss in viability remained constant. We propose that cytoplasmic membrane depolarization is the biochemical lesion responsible for the other physiological changes seen and ultimately for the death of P. aeruginosa induced by BP.

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 when calculated with the TG-43U1 rather than the NNDC(2000) initial spectrum. The measured values from three different investigations are in much better agreement with the calculations using the NCRP Report 58 and NNDC(2000) initial spectra with average discrepancies of 0.9% and 1.7% for the {sup 125}I and {sup 103}Pd seeds, respectively. However, there are no differences in the calculated TG-43U1 brachytherapy parameters using either initial spectrum in both cases. Similarly, there were no differences outside the statistical uncertainties of 0.1% or 0.2%, in the average energy, air kerma/history, dose rate/history, and dose rate constant when calculated using either the full photon spectrum or the main-peaks-only spectrum. Conclusions: Our calculated dose rate constants based on using the calculated on-axis spectrum and a line or dual-point source model are in excellent agreement (0.5% on average) with the values of Chen and Nath, verifying the accuracy of their more approximate method of going from the spectrum to the dose rate constant. However, the dose rate constants based on full seed models differ by between +4.6% and -1.5% from those based on the line or dual-point source approximations. These results suggest that the main value of spectroscopic measurements is to verify full Monte Carlo models of the seeds by comparison to the calculated spectra.« less

Aging phenomena in poly(methyl methacrylate) thin films: Memory and rejuvenation effects

NASA Astrophysics Data System (ADS)

Fukao, K.; Sakamoto, A.

2005-04-01

The aging dynamics in thin films of poly(methyl methacrylate) (PMMA) have been investigated through dielectric measurements for different types of aging processes. The dielectric constant was found to decrease with increasing aging time at an aging temperature in many cases. An increase in the dielectric constant was also observed in the long-time region (⩾11h) near the glass transition temperature for thin films with thickness less than 26nm . In the constant-rate mode including a temporary stop at a temperature Ta , the memory of the aging at Ta was found to be kept and then to be recalled during the subsequent heating process. In the negative-temperature cycling process, a strong rejuvenation effect has been observed after a temperature shift from the initial temperature T1 to the second temperature T2 (=T1+ΔT) when ΔT≈-20K . Furthermore, a full memory effect has also been observed for the temperature shift from T2 to T1 . This suggests that the aging at T1 is totally independent of that at T2 for ΔT≈-20K . As ∣ΔT∣ decreases, the independence of the aging between the two temperatures was found to be weakened—i.e., the effective time, which is a measure of the contribution of the aging at T1 to that at T2 , is a decreasing function of ∣ΔT∣ in the negative region of ΔT . As the film thickness decreases from 514nmto26nm , the ∣ΔT∣ dependence of the effective time was found to become much stronger. The contribution of the aging at T2 to that at T1 disappears more rapidly with increasing ∣ΔT∣ in thin-film geometry than in the bulk state.

Global Survey of the Relationship Between Cloud Droplet Size and Albedo Using ISCCP

NASA Technical Reports Server (NTRS)

Han, Qingyuan; Rossow, William B.; Chou, Joyce; Welch, Ronald M.

1997-01-01

Aerosols affect climate through direct and indirect effects. The direct effect of aerosols (e.g., sulfates) includes reflection of sunlight back toward space and for some aerosols (e.g., smoke particles), absorption in the atmosphere; both effects cool the Earth's surface. The indirect effect of aerosols refers to the modification of cloud microphysical properties, thereby affecting the radiation balance. Higher concentrations of Cloud Condensation Nuclei (CCN) generally produce higher concentrations of cloud droplets, which are also usually assumed to lead to decreased cloud droplet sizes. The result is an increase in cloud albedo, producing a net radiative cooling, opposite to the warming caused by greenhouse gases (Charlson et al. 1992). The change in clouds that is directly induced by an increase of aerosol concentration is an increase of cloud droplet number density, N; but is is usually assumed that cloud droplet size decreases as if the water mass density Liquid Water Content (LWC) were constant. There is actually no reason why this should be the case. Shifting the cloud droplet size distribution to more numerous smaller droplets can change the relative rates of condensational and coalescence growth, leading to different LWC (e.g., Rossow 1978). Moreover, the resulting change in cloud albedo is usually ascribed to more efficient scattering by smaller droplets, when in fact it is the increase in droplet number density (assuming constant LWC) that produces the most important change in cloud albedo: e.g., holding N constant and decreasing the droplet size would actually decrease the scattering cross-section and, thus, the albedo much more than it is increased by the increased scattering efficiency.

Natural convection of a two-dimensional Boussinesq fluid does not maximize entropy production.

PubMed

Bartlett, Stuart; Bullock, Seth

2014-08-01

Rayleigh-Bénard convection is a canonical example of spontaneous pattern formation in a nonequilibrium system. It has been the subject of considerable theoretical and experimental study, primarily for systems with constant (temperature or heat flux) boundary conditions. In this investigation, we have explored the behavior of a convecting fluid system with negative feedback boundary conditions. At the upper and lower system boundaries, the inward heat flux is defined such that it is a decreasing function of the boundary temperature. Thus the system's heat transport is not constrained in the same manner that it is in the constant temperature or constant flux cases. It has been suggested that the entropy production rate (which has a characteristic peak at intermediate heat flux values) might apply as a selection rule for such a system. In this work, we demonstrate with Lattice Boltzmann simulations that entropy production maximization does not dictate the steady state of this system, despite its success in other, somewhat similar scenarios. Instead, we will show that the same scaling law of dimensionless variables found for constant boundary conditions also applies to this system.

Kinetic Studies of the Thermal Decomposition of 2-Chloroethylphosphonic Acid in Aqueous Solution

PubMed Central

Biddle, Eric; Kerfoot, Douglas G. S.; Kho, Yioe Hwa; Russell, Kenneth E.

1976-01-01

The decomposition of 2-chloroethylphosphonic acid in aqueous solution has been studied at pH values from 6 to 9 and at temperatures in the 30 to 55 C range. The rate of decomposition is estimated from the rate of formation of ethylene. The rate is proportional to the concentration of the phosphonate dianion and is independent of the hydroxyl ion concentration. The rate constant at 40 C is 1.9 × 10−4 sec−1 and the activation energy is 29.8 kcal mol−1. The rate of reaction is not affected significantly by the presence of potassium iodide or urea (substances which increase the rate of leaf abscission in trees sprayed by 2-chloroethylphosphonic acid). The rate decreases slightly in the presence of low concentrations of magnesium and calcium ions. PMID:16659748

Variability in nest survival rates and implications to nesting studies

USGS Publications Warehouse

Klett, A.T.; Johnson, D.H.

1982-01-01

We used four reasonably large samples (83-213) of Mallard (Anas platyrhynchos) and Blue-winged Teal (A. discors) nests on an interstate highway right-of-way in southcentral North Dakota to evaluate potential biases in hatch-rate estimates. Twelve consecutive, weekly searches for nests were conducted with a cable-chain drag in 1976 and 1977. Nests were revisited at weekly intervals. Four methods were used to estimate hatch rates for the four data sets: the Traditional Method, the Mayfield Method, and two modifications of the Mayfield Method that are sometimes appropriate when daily mortality rates of nests are not constant. Hatch rates and the average age of nests at discovery declined as the interval between searches decreased, suggesting that mortality rates were not constant in our samples. An analysis of variance indicated that daily mortality rates varied with the age of nests in all four samples. Mortality was generally highest during the early laying period, moderately high during the late laying period, and lowest during incubation. We speculate that this relationship of mortality to nest age might be due to the presence of hens at nests or to differences in the vulnerability of nest sites to predation. A modification of the Mayfield Method that accounts for age-related variation in nest mortality was most appropriate for our samples. We suggest methods for conducting nesting studies and estimating nest success for species possessing similar nesting habits.

Effect of Physicochemical Properties of Slag and Flux on the Removal Rate of Oxide Inclusion from Molten Steel

NASA Astrophysics Data System (ADS)

Park, Jun Seok; Park, Joo Hyun

2016-12-01

The slag-metal reaction experiments were carried out using a high-frequency induction furnace to confirm the effect of slag composition on the removal rate of inclusions in molten steel through the CaO-based slags. The apparent rate constant of oxygen removal ( k O) was obtained as a function of slag composition. It increased with increasing basicity, and the content of MgO and CaF2, whereas it decreased by increasing the content of Al2O3 in the slag. The removal rate of inclusions was strongly affected not only by the driving force of the chemical dissolution but also by the viscosity of the slags and fluxes.

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.

Kinetics of oxygen consumption after a single flash of light in photoreceptors of the drone (Apis mellifera)

PubMed Central

1982-01-01

The time course of the rate of oxygen consumption (QO2) after a single flash of light has been measured in 300-micrometers slices of drone retina at 22 degrees C. To measure delta QO2(t), the change in QO2 from its level in darkness, the transients of the partial pressure of O2 (PO2) were recorded with O2 microelectrodes simultaneously in two sites in the slice and delta QO2 was calculated by a computer using Fourier transforms. After a 40-ms flash of intense light, delta QO2, reached a peak of 40 microliters O2/g.min and then declined exponentially to the baseline with a time constant tau 1 = 4.96 +/- 0.49 s (SD, n = 10). The rising phase was characterized by a time constant tau 2 = 1.90 +/- 0.35 s (SD, n = 10). The peak amplitude of delta QO2 increased linearly with the log of the light intensity. Replacement of Na+ by choline, known to decrease greatly the light-induced transmembrane current, caused a 63% decrease of delta QO2. With these changes, however, the kinetics of delta QO2 (t) were unchanged. This suggest that the recovery phase is rate-limited by a single reaction with apparent first-order kinetics. Evidence is provided that suggests that this reaction may be the working of the sodium pump. Exposure of the retina to high concentrations of ouabain or strophanthidin (inhibitors of the sodium pump) reduced the peak amplitude of delta QO2 by approximately 80% and increased tau 1. The increase of tau 1 was an exponential function of the time of exposure to the cardioactive steroids. Hence, it seems likely that the greatest part of delta QO2 is used for the working of the pump, whose activity is the mechanism underlying the rate constant of the descending limb of delta QO2 (t). PMID:6288837

Very high pressure liquid chromatography using core-shell particles: quantitative analysis of fast gradient separations without post-run times.

PubMed

Stankovich, Joseph J; Gritti, Fabrice; Stevenson, Paul G; Beaver, Lois A; Guiochon, Georges

2014-01-17

Five methods for controlling the mobile phase flow rate for gradient elution analyses using very high pressure liquid chromatography (VHPLC) were tested to determine thermal stability of the column during rapid gradient separations. To obtain rapid separations, instruments are operated at high flow rates and high inlet pressure leading to uneven thermal effects across columns and additional time needed to restore thermal equilibrium between successive analyses. The purpose of this study is to investigate means to minimize thermal instability and obtain reliable results by measuring the reproducibility of the results of six replicate gradient separations of a nine component RPLC standard mixture under various experimental conditions with no post-run times. Gradient separations under different conditions were performed: constant flow rates, two sets of constant pressure operation, programmed flow constant pressure operation, and conditions which theoretically should yield a constant net heat loss at the column's wall. The results show that using constant flow rates, programmed flow constant pressures, and constant heat loss at the column's wall all provide reproducible separations. However, performing separations using a high constant pressure with programmed flow reduces the analysis time by 16% compared to constant flow rate methods. For the constant flow rate, programmed flow constant pressure, and constant wall heat experiments no equilibration time (post-run time) was required to obtain highly reproducible data. Copyright © 2013 Elsevier B.V. All rights reserved.

Biogeochemical controls of uranium bioavailability from the dissolved phase in natural freshwaters

USGS Publications Warehouse

Croteau, Marie-Noele; Fuller, Christopher C.; Cain, Daniel J.; Campbell, Kate M.; Aiken, George R.

2016-01-01

To gain insights into the risks associated with uranium (U) mining and processing, we investigated the biogeochemical controls of U bioavailability in the model freshwater speciesLymnaea stagnalis (Gastropoda). Bioavailability of dissolved U(VI) was characterized in controlled laboratory experiments over a range of water hardness, pH, and in the presence of complexing ligands in the form of dissolved natural organic matter (DOM). Results show that dissolved U is bioavailable under all the geochemical conditions tested. Uranium uptake rates follow first order kinetics over a range encompassing most environmental concentrations. Uranium uptake rates in L. stagnalis ultimately demonstrate saturation uptake kinetics when exposure concentrations exceed 100 nM, suggesting uptake via a finite number of carriers or ion channels. The lack of a relationship between U uptake rate constants and Ca uptake rates suggest that U does not exclusively use Ca membrane transporters. In general, U bioavailability decreases with increasing pH, increasing Ca and Mg concentrations, and when DOM is present. Competing ions did not affect U uptake rates. Speciation modeling that includes formation constants for U ternary complexes reveals that the aqueous concentration of dicarbonato U species (UO2(CO3)2–2) best predicts U bioavailability to L. stagnalis, challenging the free-ion activity model postulate.

Preliminary evaluation of a measure for reliable assessment of need for constant visual observation in adults with traumatic brain injury.

PubMed

Moessner, Anne; Malec, James F; Beveridge, Scott; Reddy, Cara Camiolo; Huffman, Tracy; Marton, Julia; Schmerzler, Audrey J

2016-01-01

To develop and provide initial validation of a measure for accurately determining the need for Constant Visual Observation (CVO) in patients with traumatic brain injury (TBI) admitted to inpatient rehabilitation. Rating scale development and evaluation through Rasch analysis and assessment of concurrent validity. One hundred and thirty-four individuals with moderate-severe TBI were studied in seven inpatient brain rehabilitation units associated with the National Institute for Disability, Independent Living and Rehabilitation Research (NIDILRR) TBI Model System. Participants were rated on the preliminary version of the CVO Needs Assessment scale (CVONA) and, by independent raters, on the Levels of Risk (LoR) and Supervision Rating Scale (SRS) at four time points during inpatient rehabilitation: admission, Days 2-3, Days 5-6 and Days 8-9. After pruning misfitting items, the CVONA showed satisfactory internal consistency (Person Reliability = 0.85-0.88) across time points. With reference to the LoR and SRS, low false negative rates (sensitivity > 90%) were associated with moderate-to-high false positive rates (29-56%). The CVONA may be a useful objective metric to complement clinical judgement regarding the need for CVO; however, further prospective study is desirable to further assess its utility in identifying at-risk patients, reducing adverse events and decreasing CVO costs.

Factors controlling the abiotic photo-degradation of monomethylmercury in surface waters

NASA Astrophysics Data System (ADS)

Black, Frank J.; Poulin, Brett A.; Flegal, A. Russell

2012-05-01

Photo-decomposition is among the most important mechanisms responsible for degrading monomethylmercury (MMHg) in aquatic systems, but this process is not fully understood. We investigated the relative importance of different factors in controlling the rate of MMHg photo-decomposition in surface waters in experiments using DOM isolated from natural waters. We found no evidence of net abiotic production of MMHg in any dark or light exposed treatments. The average (mean ± s.d.) MMHg photo-decomposition rate constant for all light exposed samples using DOM concentrated from three coastal wetlands was 0.0099 ± 0.0020 E-1m2 (range of 0.006-0.015 E-1m2) when expressed in photon flux from 330-700 nm. This was roughly 3-fold higher than the average MMHg photo-decomposition rate constant in coastal seawater of 0.0032 ± 0.0010 E-1m2. MMHg photo-degradation was highly wavelength dependent. The ratio of MMHg photo-decomposition rate constants, with respect to photon flux, was 400:37:1 for UVB:UVA:PAR. However, when integrated across the entire water column over which MMHg photo-demethylation occurs, PAR was responsible for photo-degrading more MMHg than UVB and UVA combined in the three wetland sites because of the more rapid attenuation of UV light with depth. MMHg half-lives in the wetlands were calculated for the upper 250 cm where photo-degradation occurred, and ranged from 7.6 to 20 days under typical summer sunlight conditions at 37°N. Rates of MMHg photo-decomposition decreased with increasing salinity, and were 27% higher at a salinity of 5 than those at a salinity of 25. This difference could not be accounted for by changes in the complexation of MMHg by DOM and chloride. Differences in MMHg photo-degradation rate constants of up to 18% were measured between treatments using DOM concentrated from three different wetlands. Surprisingly, increasing DOM concentration from 1.5 to 11.3 mg OC L-1 had only a small (6%) effect on MMHg photo-decomposition, which was much smaller than the 34% decrease predicted due to the attenuation of light at the higher DOM levels. This suggests that DOM plays an important role in MMHg photo-decomposition apart from mediating light levels and MMHg complexation. Experiments employing various scavengers implied that singlet oxygen and hydroxyl radicals were not involved in the photo-degradation of MMHg in the natural waters used. Varying concentrations of Fe, Cu, and Mn had only small (⩽11%) effects on rates of MMHg photo-decomposition, and relatively high rates were measured in high purity water with no trace metals or DOM. These results demonstrate that MMHg photo-decomposition can occur via pathways not involving Fe, the photo-Fenton reaction, nitrate photolysis, or thiol complexation. Taken with previous studies, multiple reaction pathways appear to exist, and their importance varies as a function of water chemistry and light wavelength.

Homogeneous production and removal of NO/sub x/ from combustion exhaust gases. Fifth quarterly technical summary report, September 1-November 30, 1979

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

Silver, J.A.; Gozewski, C.M.; Kilb, C.E.

1979-12-01

The rate constant for the reaction of NH/sub 2/ + NO has been measured over the temperature range of 294 to 1200/sup 0/K. It exhibits a decrease in value with increasing temperatures. An upper limit to the rate of reaction of NH/sub 3/ + NO ..-->.. NH/sub 2/ + HNO is also reported. The hydroxyl radical has been identified as one of the products of the NH/sub 2/ + NO reaction, and the implications of this upon the modeling is discussed.

Infant homicide and accidental death in the United States, 1940-2005: ethics and epidemiological classification.

PubMed

Riggs, Jack E; Hobbs, Gerald R

2011-07-01

Potential ethical issues can arise during the process of epidemiological classification. For example, unnatural infant deaths are classified as accidental deaths or homicides. Societal sensitivity to the physical abuse and neglect of children has increased over recent decades. This enhanced sensitivity could impact reported infant homicide rates. Infant homicide and accident mortality rates in boys and girls in the USA from 1940 to 2005 were analysed. In 1940, infant accident mortality rates were over 20 times greater than infant homicide rates in both boys and girls. After about 1980, when the ratio of infant accident mortality rates to infant homicide rates decreased to less than five, and the sum of infant accident and homicide rates became relatively constant, further decreases in infant accident mortality rates were associated with increases in reported infant homicide rates. These findings suggest that the dramatic decline of accidental infant mortality and recent increased societal sensitivity to child abuse may be related to the increased infant homicide rates observed in the USA since 1980 rather than an actual increase in societal violence directed against infants. Ethical consequences of epidemiological classification, involving the principles of beneficence, non-maleficence and justice, are suggested by observed patterns in infant accidental deaths and homicides in the USA from 1940 to 2005.

The kinetics and mechanism of the organo-iridium-catalysed enantioselective reduction of imines.

PubMed

Stirling, Matthew J; Sweeney, Gemma; MacRory, Kerry; Blacker, A John; Page, Michael I

2016-04-14

The iridium complex of pentamethylcyclopentadiene and (S,S)-1,2-diphenyl-N'-tosylethane-1,2-diamine is an effective catalyst for the asymmetric transfer hydrogenation of imine substrates under acidic conditions. Using the Ir catalyst and a 5 : 2 ratio of formic acid : triethylamine as the hydride source for the asymmetric transfer hydrogenation of 1-methyl-3,4-dihydroisoquinoline and its 6,7-dimethoxy substituted derivative, in either acetonitrile or dichloromethane, shows unusual enantiomeric excess (ee) profiles for the product amines. The reactions initially give predominantly the (R) enantiomer of the chiral amine products with >90% ee but which then decreases significantly during the reaction. The decrease in ee is not due to racemisation of the product amine, but because the rate of formation of the (R)-enantiomer follows first-order kinetics whereas that for the (S)-enantiomer is zero-order. This difference in reaction order explains the change in selectivity as the reaction proceeds - the rate formation of the (R)-enantiomer decreases exponentially with time while that for the (S)-enantiomer remains constant. A reaction scheme is proposed which requires rate-limiting hydride transfer from the iridium hydride to the iminium ion for the first-order rate of formation of the (R)-enantiomer amine and rate-limiting dissociation of the product for the zero-order rate of formation of the (S)-enantiomer.

Entropy generation of nanofluid flow in a microchannel heat sink

NASA Astrophysics Data System (ADS)

Manay, Eyuphan; Akyürek, Eda Feyza; Sahin, Bayram

2018-06-01

Present study aims to investigate the effects of the presence of nano sized TiO2 particles in the base fluid on entropy generation rate in a microchannel heat sink. Pure water was chosen as base fluid, and TiO2 particles were suspended into the pure water in five different particle volume fractions of 0.25%, 0.5%, 1.0%, 1.5% and 2.0%. Under laminar, steady state flow and constant heat flux boundary conditions, thermal, frictional, total entropy generation rates and entropy generation number ratios of nanofluids were experimentally analyzed in microchannel flow for different channel heights of 200 μm, 300 μm, 400 μm and 500 μm. It was observed that frictional and total entropy generation rates increased as thermal entropy generation rate were decreasing with an increase in particle volume fraction. In microchannel flows, thermal entropy generation could be neglected due to its too low rate smaller than 1.10e-07 in total entropy generation. Higher channel heights caused higher thermal entropy generation rates, and increasing channel height yielded an increase from 30% to 52% in thermal entropy generation. When channel height decreased, an increase of 66%-98% in frictional entropy generation was obtained. Adding TiO2 nanoparticles into the base fluid caused thermal entropy generation to decrease about 1.8%-32.4%, frictional entropy generation to increase about 3.3%-21.6%.

Effect of limb immobilization on skeletal muscle

NASA Technical Reports Server (NTRS)

Booth, F. W.

1982-01-01

Current knowledge and questions remaining concerning the effects of limb immobilization on skeletal muscle is reviewed. The most dramatic of these effects is muscle atrophy, which has been noted in cases of muscles fixed at or below their resting length. Immobilization is also accompanied by a substantial decrease in motoneuronal discharges, which results in the conversion of slow-twitch muscle to muscle with fast-twitch characteristics. Sarcolemma effects include no change or a decrease in resting membrane potential, the appearance of extrajunctional acetylcholine receptors, and no change in acetylcholinesterase activity. Evidence of changes in motoneuron after hyperpolarization characteristics suggests that the muscle inactivity is responsible for neuronal changes, rather than vice versa. The rate of protein loss from atrophying muscles is determined solely by the first-order rate constant for degradation. Various other biochemical and functional changes have been noted, including decreased insulin responsiveness and protein synthesis. The model of limb immobilization may also be useful for related studies of muscle adaptation.

Auto-Ignition and Combustion of Diesel Fuel in a Constant-Volume Bomb

NASA Technical Reports Server (NTRS)

Selden, Robert F

1938-01-01

Report presents the results of a study of variations in ignition lag and combustion associated with changes in air temperature and density for a diesel fuel in a constant-volume bomb. The test results have been discussed in terms of engine performance wherever comparisons could be drawn. The most important conclusions drawn from this investigation are: the ignition lag was essentially independent of the injected fuel quantity. Extrapolation of the curves for the fuel used shows that the lag could not be greatly decreased by exceeding the compression-ignition engines. In order to obtain the best combustion and thermal efficiency, it was desirable to use the longest ignition lag consistent with a permissible rate of pressure rise.

On rate-state and Coulomb failure models

USGS Publications Warehouse

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

2000-01-01

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

Stochastic von Bertalanffy models, with applications to fish recruitment.

PubMed

Lv, Qiming; Pitchford, Jonathan W

2007-02-21

We consider three individual-based models describing growth in stochastic environments. Stochastic differential equations (SDEs) with identical von Bertalanffy deterministic parts are formulated, with a stochastic term which decreases, remains constant, or increases with organism size, respectively. Probability density functions for hitting times are evaluated in the context of fish growth and mortality. Solving the hitting time problem analytically or numerically shows that stochasticity can have a large positive impact on fish recruitment probability. It is also demonstrated that the observed mean growth rate of surviving individuals always exceeds the mean population growth rate, which itself exceeds the growth rate of the equivalent deterministic model. The consequences of these results in more general biological situations are discussed.

Effect of electrode mass ratio on aging of activated carbon based supercapacitors utilizing organic electrolytes

NASA Astrophysics Data System (ADS)

Cericola, D.; Kötz, R.; Wokaun, A.

2011-03-01

The accelerated degradation of carbon based supercapacitors utilizing 1 M Et4NBF4 in acetonitrile and in propylene carbonate as electrolyte is investigated for a constant cell voltage of 3.5 V as a function of the positive over total electrode mass ratio. The degradation rate of the supercapacitor using acetonitrile as a solvent can be decreased by increasing the mass of the positive electrode. With a mass ratio (positive electrode mass/total electrode mass) of 0.65 the degradation rate is minimum. For the capacitor utilizing propylene carbonate as a solvent a similar effect was observed. The degradation rate was smallest for a mass ratio above 0.5.

Oxidation of the odorous compound 2,4,6-trichloroanisole by UV activated persulfate: Kinetics, products, and pathways.

PubMed

Luo, Congwei; Jiang, Jin; Ma, Jun; Pang, Suyan; Liu, Yongze; Song, Yang; Guan, Chaoting; Li, Juan; Jin, Yixin; Wu, Daoji

2016-06-01

The transformation efficiency and products of an odorous compound 2,4,6-trichloroanisole (TCA) at the wavelength of 254 nm in the presence of persulfate were investigated for the first time. The effects of water matrix (i.e., natural organic matter (NOM), pH, carbonate/bicarbonate (HCO3(-)/CO3(2-)), and chloride ions (Cl(-))) were evaluated. The second order rate constant of TCA reacting with sulfate radical (SO4(-)) was determined to be (3.72 ± 0.10) × 10(9) M(-1) s(-1). Increasing dosage of persulfate increased the observed pseudo-first-order rate constant for TCA degradation (kobs), and the contribution of SO4(-) to TCA degradation was much higher than that of HO at each experimental condition. Degradation rate of TCA decreased with pH increasing from 4.0 to 9.0, which could be explained by the lower radical scavenging effect of dihydrogen phosphate than hydrogen phosphate in acidic condition (pH < 6). NOM significantly decreased kobs due to the effects of radical scavenging and UV absorption with the former one being dominant. kobs decreased from 2.32 × 10(-3) s(-1) to 0.92 × 10(-3) s(-1) with the CO3(2-)/HCO3(-) concentration increased from 0.5 mM to 10 mM in the UV/persulfate process, while kobs slightly decreased from 2.54 × 10(-3) s(-1) in the absence of Cl(-) to 2.10 × 10(-3) s(-1) in the presence of 10 mM Cl(-). Most of these kinetic results could be described by a steady-state kinetic model. Furthermore, liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry at powerful precursor ion scan approach was used to selectively detect oxidation products of TCA. It was found that 2,4,6-trichorophenol (TCP) was the major oxidation product (i.e., the initial yield of TCP was above 90%). The second order rate constant between TCP and SO4(-) was estimated to be (4.16 ± 0.20) × 10(9) M(-1) s(-1). In addition, three products (i.e., 2,6-dichloro-1,4-benzoquinone and two aromatic ring-opening products) were detected in the reaction of TCP with SO4(-), which also appeared in the oxidation of TCA in the UV/persulfate process. A tentative pathway was proposed, where the initial one-electron oxidation of TCA by SO4(-) and further reactions (e.g., ipso-hydroxylation and aromatic ring-cleavage) of the formed cation intermediate TCA were involved. Copyright © 2016. Published by Elsevier Ltd.

Placing the Deep Impact Mission into context: Two decades of observations of 9P/Tempel 1 from McDonald Observatory

NASA Astrophysics Data System (ADS)

Cochran, A. L.; Barker, E. S.; Caballero, M. D.; Györgey-Ries, J.

2009-01-01

We report on low-spectral resolution observations of Comet 9P/Tempel 1 from 1983, 1989, 1994 and 2005 using the 2.7 m Harlan J. Smith telescope of McDonald Observatory. This comet was the target of NASA's Deep Impact mission and our observations allowed us to characterize the comet prior to the impact. We found that the comet showed a decrease in gas production from 1983 to 2005, with the decrease being different factors for different species. OH decreased by a factor 2.7, NH by 1.7, CN by 1.6, C 3 by 1.8, CH by 1.4 and C 2 by 1.3. Despite the decrease in overall gas production and these slightly different decrease factors, we find that the gas production rates of OH, NH, C 3, CH and C 2 ratioed to that of CN were constant over all of the apparitions. We saw no change in the production rate ratios after the impact. We found that the peak gas production occurred about two months prior to perihelion. Comet Tempel 1 is a "normal" comet.

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

The fate of polar trace organic compounds in the hyporheic zone.

PubMed

Schaper, Jonas L; Seher, Wiebke; Nützmann, Gunnar; Putschew, Anke; Jekel, Martin; Lewandowski, Jörg

2018-04-18

The hyporheic zone (HZ) is often considered to efficiently remove polar trace organic compounds (TrOCs) from lotic systems, mitigating potential adverse effects of TrOCs on ecosystem functioning and drinking water production. Predicting the fate of TrOCs in the hyporheic zone (HZ) is difficult as the in-situ removal rate constants are not known and the biogeochemical factors as well as hydrological conditions controlling the removal efficiency are not fully understood. To determine the in-situ removal efficiency of the HZ for a variety of TrOCs as a function of the biogeochemical milieu, we conducted a field study in an urban river near Berlin, Germany. Subsurface flow was studied by time series of temperature depth profiles and the biogeochemical milieu of the HZ by concentration depth profiles. These results, in conjunction with a 1D advection-dispersion transport model, were used to calculate first-order removal rate constants of several polar TrOCs in the HZ. For the majority of TrOCs investigated, removal rate constants were strongly dependent on redox conditions, with significantly higher removal rates observed under predominantly suboxic (i.e. denitrifying) compared to anoxic (i.e. Fe and Mn reducing) conditions. Compared to previous studies on the fate of TrOCs in saturated sediments, half-lives within oxic/suboxic sections of the HZ were relatively low, attributable to the site-specific characteristics of the HZ in a stream dominated by wastewater treatment plant effluent. For nine out of thirteen investigated TrOCs, concentrations decreased significantly in the HZ with relative removal percentages ranging from 32% for primidone to 77% for gabapentin. For many TrOCs, removal efficiency decreased drastically as redox conditions became anoxic. For the majority of compounds investigated here, the HZ indeed acts as an efficient bioreactor that is capable of removing TrOCs along relatively short flow paths. Depending on the TrOC, removal capacity may be enhanced by either increasing the magnitude of groundwater-surface exchange fluxes, by increasing the total residence time in the HZ or the exposure time to suboxic zones, respectively. Copyright © 2018 Elsevier Ltd. All rights reserved.

Kinetic analysis of volatile formation in milk subjected to pressure-assisted thermal treatments.

PubMed

Vazquez-Landaverde, P A; Qian, M C; Torres, J A

2007-09-01

Volatile formation in milk subjected to pressure-assisted thermal processing (PATP) was investigated from a reaction kinetic analysis point of view to illustrate the advantages of this technology. The concentration of 27 volatiles of different chemical class in milk subjected to pressure, temperature, and time treatments was fitted to zero-, 1st-, and 2nd-order chemical reaction models. Temperature and pressure effects on rate constants were analyzed to obtain activation energy (E(a)) and activation volume (deltaV*) values. Hexanal, heptanal, octanal, nonanal, and decanal followed 1st-order kinetics with rate constants characterized by E(a) values decreasing with pressure reflecting negative deltaV* values. Formation of 2-methylpropanal, 2,3-butanedione, and hydrogen sulfide followed zero-order kinetics with rate constants increasing with temperature but with unclear pressure effects. E(a) values for 2-methylpropanal and 2,3-butanedione increased with pressure, that is, deltaV* > 0, whereas values for hydrogen sulfide remained constant, that is, deltaV* = 0. The concentration of all other volatiles, including methanethiol, remained unchanged in pressure-treated samples, suggesting large negative deltaV* values. The concentration of methyl ketones, including 2-pentanone, 2-hexanone, 2-heptanone, 2-octanone, 2-nonanone, 2-decanone, and 2-undecanone, was independent of pressure and pressure-holding time. PATP promoted the formation of few compounds, had no effect on some, and inhibited the formation of volatiles reported to be factors of the consumer rejection of "cooked" milk flavor. The kinetic behavior observed suggested that new reaction formation mechanisms were not likely involved in volatile formation in PATP milk. The application of the Le Chatelier principle frequently used to explain the high quality of pressure-treated foods, often with no supporting experimental evidence, was not necessary.

Nanoindentation on SnAgCu lead-free solder joints and analysis

NASA Astrophysics Data System (ADS)

Xu, Luhua; Pang, John H. L.

2006-12-01

The lead-free SnAgCu (SAC) solder joint on copper pad with organic solderability preservative (Cu-OSP) and electroless nickel and immersion gold (ENIG) subjected to thermal testing leads to intermetallic growth. It causes corresponding reliability concerns at the interface. Nanoindentation characterization on SnAgCu solder alloy, intermetallic compounds (IMCs), and the substrates subjected to thermal aging is reported. The modulus and hardness of thin IMC layers were measured by nanoindentation continuous stiffness measurement (CSM) from planar IMC surface. When SAC/Ni(Au) solder joints were subject to thermal aging, the Young’s modulus of the NiCuSn IMC at the SAC/ENIG specimen changed from 207 GPa to 146 GPa with different aging times up to 500 h. The hardness decreased from 10.0 GPa to 7.3 GPa. For the SAC/Cu-OSP reaction couple, the Young’s modulus of Cu6Sn5 stayed constant at 97.0 GPa and hardness about 5.7 GPa. Electron-probe microanalysis (EPMA) was used to thermal aging. The creep effect on the measured result was analyzed when measuring SnAgCu solder; it was found that the indentation penetration, and thus the hardness, is loading rate dependent. With the proposed constant P/P experiment, a constant indentation strain rate h/h and hardness could be achieved. The log-log plot of indentation strain rate versus hardness for the data from the constant P/P experiments yields a slope of 7.52. With the optimized test method and CSM Technique, the Modulus of SAC387 solder alloy and all the layers in a solder joint were investigated.

Transformation of Pb(II) from Cerrusite to Chloropyromorphite in the Presence of Hydroxyapatite under Varying Conditions of pH

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

Ryan, J.A.; Zhang, P.

1998-10-14

Cerrusite (PbC03) is soluble under acidic conditions and considered to be a highly bioavailable soil Pb species. In this study, synthetic cerrusite and hydroxyapatite [Ca5(P04)30H] were reacted under constant and dynamic pH conditions with various P/Pb molar ratios in an attempt to evaluate the effect of reaction kinetics on the formation of chloropyromorphite (Pb5(P04)3Cl) and solubilization of Pb. Under constant pH conditions, dissolution rates of both cerrusite and apatite were rapid when pH was low. Complete conversion of Pb from cerrusite to chloropyromorphite occurred within 60 tin at pH 4 and below when the amount of phosphate in the addedmore » apatite was stoichoimetrically equal to that needed to transform all added Pb into chloropyromorphite. The concentration of soluble Pb depended upon the volubility of chloropyromorphite. The dissolution rates of apatite and cerrusite decreased with increasing pH, and the transformation was incomplete at pH 5 and above in the 60 rnin reaction period. The soluble Pb level, therefore, was determined by the volubility of cerrusite. In the dynamic pH system which simulated the gastrointestinal tract (GI tract) system, a complete transformation of Pb from cerrusite to chloropyromorphite was achieved due to the complete dissolution of apatite and cerrusite at the initial low pHs. Chloropyromorphite was the exclusive reaction product in both constant and dynamic pH systems as indicated by XRD analysis. The differences in transformation rate and the control of Pb volubility between the reactions occurring in constant and dynamic pH systems indicate the significance of kinetics in controlling the bioavailability of Pb and the potential for the reaction to occur during ingestion.« less

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.

Photoinduced electron transfer in fixed distance chlorophyll-quinone donor-acceptor molecules

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

Wasielewski, M.R.; Johnson, D.G.; Svec, W.A.

1987-01-01

A series of fixed distance chlorophyll-quinone donor-acceptor molecules have been prepared. The donor consists of either methyl pyropheophorbide a or methyl pyrochlorophyllide a, while the acceptor is either benzoquinone or naphthoquinone. The acceptors are fused to a triptycene spacer group, which in turn is attached to the donors at their vinyl groups. Picosecond transient absorption measurements have been used to identify electron transfer from the lowest excited singlet state of the donor to the acceptor as the mechanism of fluorescence quenching in these molecules. The charge separation rate constants increase from 2 x 10/sup 10/ s/sup -1/ to 4 xmore » 10/sup 11/ s/sup -1/ as the free energy of charge separation increases, while the radical pair recombination rate constants decrease from 1.2 x 10/sup 11/ s/sup -1/ to 2 x 10/sup 9/ s/sup -1/ as the free energy of recombination increases. The resulting total reorganization energy lambda = 0.9 eV.« less

Is the continuous matter creation cosmology an alternative to ΛCDM?

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

Fabris, J.C.; Pacheco, J.A. de Freitas; Piattella, O.F., E-mail: fabris@pq.cnpq.br, E-mail: pacheco@oca.eu, E-mail: oliver.piattella@pq.cnpq.br

2014-06-01

The matter creation cosmology is revisited, including the evolution of baryons and dark matter particles. The creation process affects only dark matter and not baryons. The dynamics of the ΛCDM model can be reproduced only if two conditions are satisfied: 1) the entropy density production rate and the particle density variation rate are equal and 2) the (negative) pressure associated to the creation process is constant. However, the matter creation model predicts a present dark matter-to-baryon ratio much larger than that observed in massive X-ray clusters of galaxies, representing a potential difficulty for the model. In the linear regime, amore » fully relativistic treatment indicates that baryons are not affected by the creation process but this is not the case for dark matter. Both components evolve together at early phases but lately the dark matter density contrast decreases since the background tends to a constant value. This behaviour produces a negative growth factor, in disagreement with observations, being a further problem for this cosmology.« less

Energetics of sodium transport in toad urinary bladder.

PubMed Central

Canessa, M; Labarca, P; DiBona, D R; Leaf, A

1978-01-01

The ratio of the rate of transepithelial sodium transport, JNa, across the isolated toad urinary bladder to the simultaneously measured rate of transport-dependent metabolism, JsbCO2, has been measured as a function of the transepithelial electrical voltage, deltapsi. The ratio remains constant with a mean value of 18 to 20 over the range of imposed voltages of 0 to +70 mV. With increasing hyperpolarization of the bladder, JNa decreases and the calculated electromotive force or apparent "ENa" of the sodium pump increases. From thermodynamic and kinetic arguments it is shown that the apparent "ENa" approaches the maximal electrochemical potential gradient, ENa, against which sodium can be transported by this tissue only when JNa approximately 0. At this unique condition F ENa (in which F is the Faraday constant) is the maximal free energy of the chemical reaction driving sodium transport and thus equal to the maximal extramitochondrial phosphorylation potential and the maximal free energy of the mitochondrial respiratory chain within the transporting cells. PMID:100789

Biodegradation of high concentrations of hexadecane by Aspergillus niger in a solid-state system: kinetic analysis.

PubMed

Volke-Sepúlveda, Tania; Gutiérrez-Rojas, Mariano; Favela-Torres, Ernesto

2006-09-01

Solid-state microcosms were used to assess the influence of constant and variable C/N ratios on the biodegradation efficiency by Aspergillus niger at high hexadecane (HXD) concentrations (180-717 mg g-1). With a constant C/N ratio, 100% biodegradation (33-44% mineralization) was achieved after 15 days, at rates increasing as the HXD concentration increased. Biomass yields (YX/S) remained almost independent (approximately 0.77) of the carbon-source amount, while the specific growth rates (mu) decreased with increasing concentrations of HXD. With C/N ratios ranging from 29 to 115, complete degradation was only attained at 180 mg g-1, corresponding to 46% mineralization. YX/S diminished (approximately 0.50 units) as the C/N ratio increased. The highest values of mu (1.08 day-1) were obtained at low C/N values. Our results demonstrate that, under balanced nutritional conditions, high HXD concentrations can be completely degraded in solid-state microcosms, with a negligible (<10%) formation of by-products.

Electrochemical characteristics of flexible micro supercapacitors with reduced graphene oxide-carbon nanotubes composite electrodes

NASA Astrophysics Data System (ADS)

Yang, Kyungwhan; Cho, Kyoungah; Kim, Sangsig

2018-06-01

In this study, we fabricate solid-state flexible micro-supercapacitors (MSCs) with reduced graphene oxide-carbon nanotube (rGO-CNT) composite electrodes and investigate the electrochemical characteristics by comparing with those of an MSC with rGO electrodes. Regarding the resistance-capacitance time constant and IR drop, the addition of CNTs into the rGO electrodes shows a significant effect owing to both the decrease in the resistance and the increase in the permeability of the electrolytes. Compared to the rGO MSCs, the rGO-CNT MSCs show an excellent areal capacitance of 2.6 mF/cm2, a smaller IR drop of 11 mV, a lower RC time constant of 6 ms, and faster charging/discharging rates with a high scan rate ability up to 100 V/s. The mechanical stability of the flexible rGO-CNT MSCs is verified by 1000 bending cycles. In addition, the electrochemical characteristics of the flexible rGO-CNT MSCs are maintained regardless of the MSC array type.

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

Mercury methylation and demethylation in Hg-contaminated lagoon sediments (Marano and Grado Lagoon, Italy)

NASA Astrophysics Data System (ADS)

Hines, Mark E.; Poitras, Erin N.; Covelli, Stefano; Faganeli, Jadran; Emili, Andrea; Žižek, Suzana; Horvat, Milena

2012-11-01

Mercury (Hg) transformation activities and sulfate (SO42-) reduction were studied in sediments of the Marano and Grado Lagoons in the Northern Adriatic Sea region as part of the "MIRACLE" project. The lagoons, which are sites of clam (Tapes philippinarum) farming, have been receiving excess Hg from the Isonzo River for centuries. Marano Lagoon is also contaminated from a chlor-alkali plant. Radiotracer methods were used to measure mercury methylation (230Hg, 197Hg), methylmercury (MeHg) demethylation (14C-MeHg) and SO42- reduction (35S) in sediment cores collected in autumn, winter and summer. Mercury methylation rate constants ranged from near zero to 0.054 day-1, generally decreased with depth, and were highest in summer. Demethylation rate constants were much higher than methylation reaching values of ˜0.6 day-1 in summer. Demethylation occurred via the oxidative pathway, except in winter when the reductive pathway increased in importance in surficial sediments. Sulfate reduction was also most active in summer (up to 1600 nmol mL-1 day-1) and depth profiles reflected seasonally changing redox conditions near the surface. Methylation and demethylation rate constants correlated positively with SO42- reduction and pore-water Hg concentrations, and inversely with Hg sediment-water partition coefficients indicating the importance of SO42- reduction and Hg dissolution on Hg cycling. Hg transformation rates were calculated using rate constants and concentrations of Hg species. In laboratory experiments, methylation was inhibited by amendments of the SO42--reduction inhibitor molybdate and by nitrate. Lagoon sediments displayed a dynamic seasonal cycle in which Hg dissolution in spring/summer stimulated Hg methylation, which was followed by a net loss of MeHg in autumn from demethylation. Sulfate-reducing bacteria (SRB) tended to be responsible for methylation of Hg and the oxidative demethylation of MeHg. However, during winter in surficial sediments, iron-reducing bacteria seemed to contribute to methylation and Hg-resistant bacteria increased in importance in the reductive demethylation of MeHg. The high rates of MeHg demethylation in lagoon sediments may diminish the accumulation of MeHg.

Effect of salicylate on outer hair cell plasma membrane viscoelasticity: studies using optical tweezers

NASA Astrophysics Data System (ADS)

Ermilov, Sergey A.; Brownell, William E.; Anvari, Bahman

2004-06-01

The plasma membrane (PM) of mammalian outer hair cells (OHCs) generates mechanical forces in response to changes in the transmembrane electrical potential. The resulting change in the cell length is known as electromotility. Salicylate (Sal), the anionic, amphipathic derivative of aspirin induces reversible hearing loss and decreases electromotile response of the OHCs. Sal may change the local curvature and mechanical properties of the PM, eventually resulting in reduced electromotility or it may compete with intracellular monovalent anions, particularly Cl-, which are essential for electromotility. In this work we have used optical tweezers to study the effects of Sal on viscoelastic properties of the OHC PM when separated from the underlying composite structures of the cell wall. In this procedure, an optically trapped microsphere is brought in contact with PM and subsequently pulled away to form a tether. We measured the force exerted on the tether as a function of time during the process of tether growth at different pulling rates. Effective tether viscosity, steady-state tethering force extrapolated to zero pulling rate, and the time constant for tether growth were estimated from the measurements of the instantaneous tethering force. The time constant for the tether growth measured for the OHC basal end decreased 1.65 times after addition of 10 mM Sal, which may result from an interaction between Sal and cholesterol, which is more prevalent in the PM of OHC basal end. The time constants for the tether growth calculated for the OHC lateral wall and control human embryonic kidney cells as well as the other calculated viscoelastic parameters remained the same after Sal perfusion, favoring the hypothesis of competitive inhibition of electromotility by salicylate.

On the unsteady decline of atmospheric CFC-11: Bumps in the road to ozone recovery or variations in atmospheric transport and/or loss?

NASA Astrophysics Data System (ADS)

Montzka, Stephen; Dutton, Geoff; Yu, Pengfei; Portmann, Bob; Ray, Eric; Daniel, John; Moore, Fred; Nance, David; Hall, Brad; Siso, Carolina; Miller, Ben; Mondeel, Debra; Kuijpers, Lambert; Hu, Lei; Elkins, James

2017-04-01

Atmospheric mole fractions of the ozone-depleting and greenhouse gas CFC-11 have declined since 1995 owing to global controls on production associated with the fully adjusted and amended Montreal Protocol on Substances that Deplete the Ozone Layer. From 2002 to 2012, CFC-11 mole fractions in both hemispheres decreased at a near-constant rate of 2.2 ± 0.2 ppt/yr. Assuming a constant atmospheric loss frequency, these results suggest that CFC-11 emissions did not decrease over this 11-yr period. This conclusion is difficult to reconcile with an idealized model of emissions being sustained by leaks from a shrinking reservoir of CFC-11 (reported global production has been negligible since 2007). Even more surprising, from 2013 to 2015 the atmospheric decline slowed appreciably (mean global rate was -1.3 ± 0.1 ppt/yr) and the hemispheric difference (N - S) increased by 50%. Here we consider the implications of these atmospheric changes. When analyzed with a simple 3-box model and constant loss frequency or a 3-D climate model (WACCM) with specified dynamics, the observations suggest global CFC-11 emissions in 2014-2015 that were 30% (15 Gg/yr) larger in 2014 and 2015 compared to the 2002-2012 mean. Are emissions of this globally controlled Class 1 ozone-depleting substance actually increasing despite global reported production being negligible for nearly a decade? Or do anomalies observed for multiple trace gases during these periods suggest significant changes in stratospheric loss and mixing processes that are not captured by global models using estimates of actual meteorology?

[Does intraoperative nerve monitoring reduce the rate of recurrent nerve palsies during thyroid surgery?].

PubMed

Timmermann, W; Dralle, H; Hamelmann, W; Thomusch, O; Sekulla, C; Meyer, Th; Timm, S; Thiede, A

2002-05-01

Two different aspects of the influence of neuromonitoring on the possible reduction of post-operative recurrent laryngeal nerve palsies require critical examination: the nerve identification and the monitoring of it's functions. Due to the additional information from the EMG signals, neuromonitoring is the best method for identifying the nerves as compared to visual identification alone. There are still no randomized studies available that compare the visual and electrophysiological recurrent laryngeal nerve detection in thyroid operations with respect to the postoperative nerve palsies. Nevertheless, comparisons with historical collectives show that a constant low nerve-palsy-rate was achieved with electrophysiological detection in comparison to visual detection. The rate of nerve identification is normally very high and amounts to 99 % in our own patients. The data obtained during the "Quality assurance of benign and malignant Goiter" study show that in hemithyreoidectomy and subtotal resection, lower nerve-palsy-rates are achieved with neuromonitoring as compared to solely visual detection. Following subtotal resection, this discrepancy becomes even statistically significant. While monitoring the nerve functions with the presently used neuromonitoring technique, it is possible to observe the EMG-signal remaining constant or decreasing in volume. Assuming that a constant neuromonitoring signal represents a normal vocal cord, our evaluation shows that there is a small percentage of false negative and positive results. Looking at the permanent recurrent nerve palsy rates, this method has a specificity of 98 %, a sensitivity of 100 %, a positive prognostic value of 10 %, and a negative prognostic value of 100 %. Although an altered neuromonitoring signal can be taken as a clear indication of eventual nerve damage, an absolutely reliable statement about the postoperative vocal cord function is presently not possible with intraoperative neuromonitoring.

Constant-Differential-Pressure Two-Fluid Accumulator

NASA Technical Reports Server (NTRS)

Piecuch, Benjamin; Dalton, Luke T.

2010-01-01

A two-fluid accumulator has been designed, built, and demonstrated to provide an acceptably close approximation to constant differential static pressure between two fluids over the full ranges of (1) accumulator stroke, (2) rates of flow of the fluids, and (3) common static pressure applied to the fluids. Prior differential- pressure two-fluid accumulators are generally not capable of maintaining acceptably close approximations to constant differential pressures. The inadequacies of a typical prior differential-pressure two-fluid accumulator can be summarized as follows: The static differential pressure is governed by the intrinsic spring rate (essentially, the stiffness) of an accumulator tank. The spring rate can be tailored through selection of the tank-wall thickness, selection of the number and/or shape of accumulator convolutions, and/or selection of accumulator material(s). Reliance on the intrinsic spring rate of the tank results in three severe limitations: (1) The spring rate and the expulsion efficiency tend to be inversely proportional to each other: that is to say, as the stiffness (and thus the differential pressure) is increased, the range of motion of the accumulator is reduced. (2) As the applied common static pressure increases, the differential pressure tends to decrease. An additional disadvantage, which may or may not be considered limiting, depending on the specific application, is that an increase in stiffness entails an increase in weight. (3) The additional weight required by a low expulsion efficiency accumulator eliminates the advantage given to such gas storage systems. The high expulsion efficiency provided by this two-fluid accumulator allows for a lightweight, tightly packaged system, which can be used in conjunction with a fuel cell-based system.

Distribution of crystalloid fluid changes with the rate of infusion: a population-based study.

PubMed

Hahn, R G; Drobin, D; Zdolsek, J

2016-05-01

Crystalloid fluid requires 30 min for complete distribution throughout the extracellular fluid space and tends to cause long-standing peripheral edema. A kinetic analysis of the distribution of Ringer's acetate with increasing infusion rates was performed to obtain a better understanding of these characteristics of crystalloids. Data were retrieved from six studies in which 76 volunteers and preoperative patients had received between 300 ml and 2375 ml of Ringer's acetate solution at a rate of 20-80 ml/min (0.33-0.83 ml/min/kg). Serial measurements of the blood hemoglobin concentration were used as inputs in a kinetic analysis based on a two-volume model with micro-constants, using software for nonlinear mixed effects. The micro-constants describing distribution (k12) and elimination (k10) were unchanged when the rate of infusion increased, with half-times of 16 and 26 min, respectively. In contrast, the micro-constant describing how rapidly the already distributed fluid left the peripheral space (k21) decreased by 90% when the fluid was infused more rapidly, corresponding to an increase in the half-time from 3 to 30 min. The central volume of distribution (V(c)) doubled. The return of Ringer's acetate from the peripheral fluid compartment to the plasma was slower with high than with low infusion rates. Edema is a normal consequence of plasma volume expansion with this fluid, even in healthy volunteers. The results are consistent with the view that the viscoelastic properties of the interstitial matrix are responsible for the distribution and redistribution characteristics of crystalloid fluid. © 2016 The Acta Anaesthesiologica Scandinavica Foundation. Published by John Wiley & Sons Ltd.

Environmental and genetic influences on flight metabolic rate in the honey bee, Apis mellifera.

PubMed

Harrison, Jon F; Fewell, Jennifer H

2002-10-01

Flying honey bees demonstrate highly variable metabolic rates. The lowest reported values (approximately 0.3 Wg(-1)) occur in tethered bees generating the minimum lift to support their body weight, free-flying 2-day old bees, winter bees, or bees flying at high air temperatures (45 degrees C). The highest values (approximately 0.8 Wg(-1)) occur in foragers that are heavily loaded or flying in low-density air. In different studies, flight metabolic rate has increased, decreased, or remained constant with air temperature. Current research collectively suggests that this variation occurs because flight metabolic rates decrease at thorax temperatures above or below 38 degrees C. At 30 degrees C, approximately 30% of colonial energy is spent during typical foraging, so variation in flight metabolic rate can strongly affect colony-level energy balance. Higher air temperatures tend to increase colonial net gain rates, efficiencies and honey storage rates due to lower metabolic rates during flight and in the hive. Variation in flight metabolism has a clear genetic basis. Different genetic strains of honey bees often differ in flight metabolic rate, and these differences in flight physiology can be correlated with foraging effort, suggesting a possible pathway for selection effects on flight metabolism.

A meta-analysis of oceanic DMS and DMSP cycling processes: Disentangling the summer paradox

NASA Astrophysics Data System (ADS)

Galí, Martí; Simó, Rafel

2015-04-01

The biogenic volatile compound dimethylsulfide (DMS) is produced in the ocean mainly from the ubiquitous phytoplankton osmolyte dimethylsulfoniopropionate (DMSP). In the upper mixed layer, DMS concentration and the daily averaged solar irradiance are roughly proportional across latitudes and seasons. This translates into a seasonal mismatch between DMS and phytoplankton biomass at low latitudes, termed the "DMS summer paradox," which remains difficult to reproduce with biogeochemical models. Here we report on a global meta-analysis of DMSP and DMS cycling processes and their relationship to environmental factors. We show that DMS seasonality reflects progressive changes in a short-term dynamic equilibrium, set by the quotient between gross DMS production rates and the sum of biotic and abiotic DMS consumption rate constants. Gross DMS production is the principal driver of DMS seasonality, due to the synergistic increases toward summer in two of its underlying factors: phytoplankton DMSP content (linked to species succession) and short-term community DMSP-to-DMS conversion yields (linked to physiological stress). We also show that particulate DMSP transformations (linked to grazing-induced phytoplankton mortality) generally contribute a larger share of gross DMS production than dissolved-phase DMSP metabolism. The summer paradox is amplified by a decrease in microbial DMS consumption rate constants toward summer. However, this effect is partially compensated by a concomitant increase in abiotic DMS loss rate constants. Besides seasonality, we identify consistent covariation between key sulfur cycling variables and trophic status. These findings should improve the modeling projections of the main natural source of climatically active atmospheric sulfur.

Diminished glucose transport and phosphorylation in Alzheimer`s disease determined by dynamic FDG-PET

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

Piert, M.; Koeppe, R.A.; Giordani, B.

1996-02-01

Using dynamic [{sup 18}F] fluorodeoxyglucose (FDG) and PET, kinetic rate constants that describe influx (K{sub 1}) and efflux (k{sub 2}) of FDG as well s phosphorylation (k{sub 3}) and dephosphorylation (k{sub 4}) were determined in patients with probable Alzheimer`s disease and similarly aged normal controls. The regional cerebral metabolic rate for glucose (CMR{sub glu}) was calculated from individually fitted rate constants in frontal, temporal, parietal and occipital cerebral cortex, caudate nucleus, putamen, thalamus and cerebellar cortex. Dynamic PET scans were obtained in normal controls (n = 10, mean age = 67) and Alzheimer`s disease patients (n = 8, mean agemore » = 67) for 60 min following injection of 10 mCi of FDG. The Alzheimer`s disease group was characterized by decreases of the CMR{sub glu} ranging from 13.3% in the frontal to 40.9% in the parietal cortex, which achieved significance in all regions except the thalamus. K{sub 1} was significantly reduced in the parietal (p < 0.01) and temporal cortices (p < 0.005), temporal and occipital cortex, and in the putamen and cerebellum (p < 0.05). The rate constants k{sub 2} and k{sub 4} were unchanged in the Alzheimer`s disease group. These data suggest that hypometabolism in Alzheimer`s disease is related to reduced glucose phosphorylation activity as well as diminished glucose transport, particularly in the most metabolically affected areas of the brain, the parietal and temporal cortex. 60 refs., 2 figs., 2 tabs.« less

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.

Methane steam reforming rates over Pt, Rh and Ni(111) accounting for H tunneling and for metal lattice vibrations

NASA Astrophysics Data System (ADS)

German, Ernst D.; Sheintuch, Moshe

2017-02-01

Microkinetic models of methane steam reforming (MSR) over bare platinum and rhodium (111) surfaces are analyzed in present work using calculated rate constants. The individual rate constants are classified into three different sets: (i) rate constants of adsorption and desorption steps of CH4, H2O, CO and of H2; (ii) rate constants of dissociation and formation of A-H bonds (A = C, O, and H), and (iii) rate constants of dissociation and formation of C-O bond. The rate constants of sets (i) and (iii) are calculated using transition state theory and published thermochemical data. The rate constants of H-dissociation reactions (set (ii)) are calculated in terms of a previously-developed approach that accounts for thermal metal lattice vibrations and for H tunneling through a potential barrier of height which depends on distance of AH from a surface. Pre-exponential factors of several group (ii) steps were calculated to be usually lower than the traditional kBT/h due to tunneling effect. Surface composition and overall MSR rates over platinum and rhodium surfaces are compared with those over nickel surface showing that operating conditions strongly affect on the activity order of the catalysts.

Effect of sputtering parameters on optical and electrical properties of ITO films on PET substrates

NASA Astrophysics Data System (ADS)

Tseng, Kun-San; Lo, Yu-Lung

2013-11-01

The optical and electrical properties of indium tin oxide (ITO) thin films deposited on flexible polyethylene terephthalate (PET) substrates using a DC magnetron sputtering technique are investigated as a function of the deposition time, the argon flow rate and the target-substrate distance. It is found that all of the ITO films contain a high fraction of amorphous phase. The volume fraction of crystallite precipitates in the amorphous host increases with an increasing deposition time or a reducing argon flow rate. The deposition time and argon flow rate have higher effects on the optical transparency of the ITO films than the target-substrate distance has. Increasing film thickness is not the only reason for the transmittance reduced. It is found that an increase of the extinction coefficient by increasing deposition time or an increase of the refractive index by decreasing argon flow rate also reduces the transmittance of thin film. For a constant deposition time, the resistivity of the ITO films reduces with a reducing argon flow rate or a reducing target-substrate distance. For a constant argon flow rate, a critical value of the deposition time exists at which both the resistivity and the effect of the target-substrate distance are minimized. Finally, it is concluded that the film resistivity has low sensitivity to the target-substrate distance if the best deposition conditions which mostly attain the lowest resistivity are matched.

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.

Probing effect of solvent concentration on glass transition and sub-T{sub g} structural relaxation in polymer solvent mixtures: The case of polystyrene-toluene system

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

Pierleoni, Davide; Minelli, Matteo; Doghieri, Ferruccio

A novel experimental method for the analysis of volume relaxation induced by solvents in glassy polymers is presented. A gravimetric technique is used to evaluate the isothermal solvent mass uptake at controlled increasing/decreasing solvent pressure at constant rate. Fundamental properties of the solvent/polymer system can be obtained directly, and models can be applied, combining both nonequilibrium thermodynamics and mechanics of volume relaxation contribution. The fundamental case of polystyrene and toluene mixtures are thus accounted for, and various experimental conditions have been explored, varying the temperature, and spanning over different pressure increase/decrease rates. The results obtained allowed to evaluate the isothermalmore » second order transition induced by solvent sorption, as well as the determination of the effect of the pressure rate. Therefore, this work proposes a new standard for the characterization and the understanding of the relaxational behavior of glassy polymers.« less

[Effects of wind speed on drying processes of fuelbeds composed of Mongolian oak broad-leaves.

PubMed

Zhang, Li Bin; Sun, Ping; Jin, Sen

2016-11-18

Water desorption processes of fuel beds with Mongolian oak broad-leaves were observed under conditions with various wind speeds but nearly constant air temperature and humidity. The effects of wind speed on drying coefficients of fuel beds with various moisture contents were analyzed. Three phases of drying process, namely high initial moisture content (>75%) of phase 1, transition state of phase 2, and equilibrium phase III could be identified. During phase 1, water loss rate under higher wind speed was higher than that under lower wind speed. Water loss rate under higher wind speed was lower than that under lower wind speed during phase 2. During phase 3, water loss rates under different wind speeds were similar. The wind effects decreased with the decrease of fuel moisture. The drying coefficient of the Mongolian oak broad-leaves fuel beds was affected by wind speed and fuel bed compactness, and the interaction between these two factors. The coefficient increased with wind speed roughly in a monotonic cubic polynomial form.

Response to glucose and lipid infusions in sepsis: a kinetic analysis

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

Shaw, J.H.; Wolfe, R.R.

The kinetics and oxidation of glucose and free fatty acid (FFA) metabolism were assessed in control and Escherichia coli septicemic dogs by using primed, constant infusions of U-/sup 14/C-glucose and 1,2, /sup 13/C-palmitic acid. In the controls, the infusion of glucose suppressed endogenous glucose production completely, whereas, in the septic dogs, only a 30% suppression of glucose production occurred. The ability of the septic dogs to oxidize endogenous or exogenous glucose was decreased significantly. The basal rate of appearance of FFA was significantly higher in the septic dogs, but their ability to oxidize FFA was comparable to that of themore » control dogs; therefore, the basal rate of FFA oxidation was higher in the septic dogs. These studies indicate that septic dogs have a decreased capacity to oxidize glucose, but that they retain their ability to oxidize long-chain fatty acids. Because the rate of lipolysis was increased in sepsis, lipid was the predominate energy substrate in this septic model.« less

Femtosecond Heterodyne Transient Grating Detection of Conformational Dynamics in the S0 (11Ag-) State of Carotenoids After Nonradiative Decay of the S2 (11Bu+) State

NASA Astrophysics Data System (ADS)

Roscioli, Jerome D.; Ghosh, Soumen; Bishop, Michael M.; Lafountain, Amy M.; Frank, Harry A.; Beck, Warren F.

Transient grating spectroscopy was used to study the dynamics of nonradiative decay of the S1 (21Ag-) state in ß-carotene and peridinin after optical preparation of the S2) state. The kinetics of the recovery of the absorption and dispersion components of the third-order signal exhibit significantly different time constants. For β-carotene in benzonitrile, the absorption and dispersion recovery time constants are 11.6 and 10.2 ps. For peridinin in methanol, the time constants are 9.9 and 7.4 ps. These results indicate that the initial product of the decay of the S1 state is a conformationally displaced structure. The decay rate for the S1 state and the conformational relaxation rate are both slowed in peridinin as the polarity of the solvent decreases; in ethyl acetate, the conformational relaxation time constant is 45 ps, which rules out a dominant contribution from vibrational cooling. These results indicate that the S1 state develops intramolecular charge transfer character owing to distortions along torsional and out-of-plane coordinates, with a pyramidal structure favored as the most stable conformation. Recovery of the photoselected ground state conformation involves a reverse charge-transfer event followed by relaxation to a planar structure. Work supported by Photosynthetic Systems Program of the U.S. Department of Energy under Grant DE-SC0010847.

Microcomputer-Based Programs for Pharmacokinetic Simulations.

ERIC Educational Resources Information Center

Li, Ronald C.; And Others

1995-01-01

Microcomputer software that simulates drug-concentration time profiles based on user-assigned pharmacokinetic parameters such as central volume of distribution, elimination rate constant, absorption rate constant, dosing regimens, and compartmental transfer rate constants is described. The software is recommended for use in undergraduate…

In-vivo force decay of nickel-titanium closed-coil springs.

PubMed

Cox, Crystal; Nguyen, Tung; Koroluk, Lorne; Ko, Ching-Chang

2014-04-01

Nickel-titanium closed-coil springs are purported to deliver constant forces over extended ranges of activation and working times. In-vivo studies supporting this claim are limited. The objective of this study was to evaluate changes in force-decay properties of nickel-titanium closed-coil springs after clinical use. Pseudoelastic force-deflection curves for 30 nickel-titanium coil springs (used intraorally) and 15 matched laboratory control springs (simulated intraoral conditions: artificial saliva, 37°C) were tested before and after retrieval via dynamic mechanical analysis and a testing machine, respectively, to evaluate the amounts of force-loss and hysteresis change after 4, 8, or 12 weeks of working time (n = 10 per group). The effects of the oral environment and clinical use on force properties were evaluated by comparing in-vivo and in-vitro data. The springs studied showed a statistically significant decrease in force (approximately 12%) after 4 weeks of clinical use (P <0.01), with a further significant decrease (approximately 7%) from 4 to 8 weeks (P = 0.03), and force levels appearing to remain steady thereafter. Clinical space closure at an average rate of 0.91 mm per month was still observed despite this decrease in force. In-vivo and in-vitro force-loss data were not statistically different. Nickel-titanium closed-coil springs do not deliver constant forces when used intraorally, but they still allow for space-closure rates of approximately 1 mm per month. Copyright © 2014 American Association of Orthodontists. Published by Mosby, Inc. All rights reserved.

A parametric study of the microwave plasma-assisted combustion of premixed ethylene/air mixtures

NASA Astrophysics Data System (ADS)

Fuh, Che A.; Wu, Wei; Wang, Chuji

2017-11-01

A parametric study of microwave argon plasma assisted combustion (PAC) of premixed ethylene/air mixtures was carried out using visual imaging, optical emission spectroscopy and cavity ringdown spectroscopy as diagnostic tools. The parameters investigated included the plasma feed gas flow rate, the plasma power, the fuel equivalence ratio and the total flow rate of the fuel/air mixture. The combustion enhancement effects were characterized by the minimum ignition power, the flame length and the fuel efficiency of the combustor. It was found that: (1) increasing the plasma feed gas flow rate resulted in a decrease in the flame length, an increase in the minimum ignition power for near stoichiometric fuel equivalence ratios and a corresponding decrease in the minimum ignition power for ultra-lean and rich fuel equivalence ratios; (2) at a constant plasma power, increasing the total flow rate of the ethylene/air mixture from 1.0 slm to 1.5 slm resulted in an increase in the flame length and a reduction in the fuel efficiency; (3) increasing the plasma power resulted in a slight increase in flame length as well as improved fuel efficiency with fewer C2(d) and CH(A) radicals present downstream of the flame; (4) increasing the fuel equivalence ratio caused an increase in flame length but at a reduced fuel efficiency when plasma power was kept constant; and (5) the ground state OH(X) number density was on the order of 1015 molecules/cm3 and was observed to drop downstream along the propagation axis of the flame at all parameters investigated. Results suggest that each of the parameters independently influences the PAC processes.

Estimates of cancer burden in Abruzzo and Molise.

PubMed

Foschi, Roberto; Viviano, Lorena; Rossi, Silvia

2013-01-01

Abruzzo and Molise are two regions located in the south of Italy, currently without population-based cancer registries. The aim of this paper is to provide estimates of cancer incidence, mortality and prevalence for the Abruzzo and Molise regions combined. The MIAMOD method, a back-calculation approach to estimate and project the incidence of chronic diseases from mortality and patient survival, was used for the estimation of incidence and prevalence by calendar year (from 1970 to 2015) and age (from 0 to 99). The survival estimates are based on cancer registry data of southern Italy. The most frequently diagnosed cancers were those of the colon and rectum, breast and prostate, with 1,394, 1,341 and 698 new diagnosed cases, respectively, estimated in 2012. Incidence rates were estimated to increase constantly for female breast cancer, colorectal cancer in men and melanoma in both sexes. For prostate cancer and male lung cancer, the incidence rates increased, reaching a peak, and then decreased. In women the incidence of colorectal and lung cancer stabilized after an initial increase. For stomach and cervical cancers, the incidence rates showed a constant decrease. Prevalence was increasing for all the considered cancer sites with the exception of the cervix uteri. The highest prevalence values were estimated for breast and colorectal cancer with about 12,300 and over 8,200 cases in 2012, respectively. In the 2000s the mortality rates declined for all cancers except skin melanoma and female lung cancer, for which the mortality was almost stable. This paper provides a description of the burden of the major cancers in Abruzzo and Molise until 2015. The increase in cancer survival, added to population aging, will inflate the cancer prevalence. In order to better evaluate the cancer burden in the two regions, it would be important to implement cancer registration.

Recovery of cat retinal ganglion cell sensitivity following pigment bleaching.

PubMed Central

Bonds, A B; Enroth-Cugell, C

1979-01-01

1. The threshold illuminance for small spot stimulation of on-centre cat retinal ganglion cells was plotted vs. time after exposure to adapting light sufficiently strong to bleach significant amounts of rhodopsin. 2. When the entire receptive field of an X- or Y-type ganglion cell is bleached by at most 40%, recovery of the cell's rod-system proceeds in two phases: an early relatively fast one during which the response appears transient, and a late, slower one during which responses become more sustained. Log threshold during the later phase is well fit by an exponential in time (tau = 11.5-38 min). 3. After bleaches of 90% of the underlying pigment, threshold is cone-determined for as long as 40 min. Rod threshold continues to decrease for at least 85 min after the bleach. 4. The rate of recovery is slower after strong than after weak bleaches; 10 and 90% bleaches yield time constants for the later phase of 11.5 and 38 min, respectively. This contrasts with an approximate time constant of 11 min for rhodopsin regeneration following any bleach. 5. The relationship between the initial elevation of log rod threshold extrapolated from the fitted exponential curves and the initial amount of pigment bleached is monotonic, but nonlinear. 6. After a bleaching exposure, the maintained discharge is initially very regular. The firing rate first rises, then falls to the pre-bleach level, with more extended time courses of change in firing rate after stronger exposures. The discharge rate is restored before threshold has recovered fully. 7. The change in the response vs. log stimulus relationship after bleaching is described as a shift of the curve to the right, paired with a decrease in slope of the linear segment of the curve. PMID:521963

Creep and intergranular cracking of Ni-Cr-Fe-C in 360[degree]C argon

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

Angeliu, T.M.; Was, G.S.

1994-06-01

The influence of carbon and chromium on the creep and intergranular (IG) cracking behavior of controlled-purity Ni-xCr-9Fe-yC alloys in 360 C argon was investigated using constant extension rate tension (CERT) and constant load tension (CLT) testing. The CERT test results at 360 C show that the degree of IG cracking increases with decreasing bulk chromium or carbon content. The CLT test results at 360 C and 430 C reveal that, as the amounts of chromium and carbon in solution decrease, the steady-state creep rate increases. The occurrence of severe IG cracking correlates with a high steady-state creep rate, suggesting thatmore » creep plays a role in the IG cracking behavior in argon at 360 C. The failure mode of IG cracking and the deformation mode of creep are coupled through the formation of grain boundary voids that interlink to form grain boundary cavities, resulting in eventual failure by IG cavitation and ductile overload of the remaining ligaments. Grain boundary sliding may be enhancing grain boundary cavitation by redistributing the stress from inclined to more perpendicular boundaries and concentrating stress at discontinuities for the boundaries oriented 45 deg with respect to the tensile axis. Additions of carbon or chromium, which reduce the creep rate over all stress levels, also reduce the amount of IG fracture in CERT experiments. A damage accumulation model was formulated and applied to CERT tests to determine whether creep damage during a CERT test controls failure. Results show that, while creep plays a significant role in CERT experiments, failure is likely controlled by ductile overload caused by reduction in area resulting from grain boundary void formation and interlinkage.« less

Liquid Jet Cavitation via Molecular Dynamics

NASA Astrophysics Data System (ADS)

Ashurst, W. T.

1997-11-01

A two-dimensional molecular dynamics simulation of a liquid jet is used to investigate cavitation in a diesel-like fuel injector. A channel with a length four times its width has been examined at various system sizes (widths of 20 to 160 σ, where σ is the zero energy location in the Lennard-Jones potential). The wall boundary condition is Maxwell's diffuse reflection, similar to the work by Sun & Ebner (Phys. Rev A 46, 4813, 1992). Currently, the jet exhausts into a vacuum, but a second, low density gas will be incorporated to represent the compressed air in a diesel chamber. Four different flow rates are examined. With ρ U equal to √mɛ/σ^2 (the largest flow rate) the static pressure decreases by a factor of twenty between the channel entrance and exit. The largest flow rate has a parabolic velocity profile with almost constant density across the channel. The smallest flow rate has the same velocity profile but the density exhibits a large variation, with the minimum value in the channel center. Thus, the product ρ U is nearly constant across the channel at this flow rate. The discharge coefficient CD has a small variation with flow rate, but the velocity coefficient CV varies with the amount of two-phase fluid within the channel. The ratio of CV to CD varies from 1.3 (largest flow rate) to 2.0 (the smallest flow rate, which is one-eighth of the largest).

Mass transfer equation for proteins in very high-pressure liquid chromatography.

PubMed

Gritti, Fabrice; Guiochon, Georges

2009-04-01

The mass transfer kinetics of human insulin was investigated on a 50 mm x 2.1 mm column packed with 1.7 microm BEH-C(18) particles, eluted with a water/acetonitrile/trifluoroacetic acid (TFA) (68/32/0.1, v/v/v) solution. The different contributions to the mass transfer kinetics, e.g., those of longitudinal diffusion, eddy dispersion, the film mass transfer resistance, cross-particle diffusivity, adsorption-desorption kinetics, and transcolumn differential sorption, were incorporated into a general mass transfer equation designed to account for the mass transfer kinetics of proteins under high pressure. More specifically, this equation includes the effects of pore size exclusion, pressure, and temperature on the band broadening of a protein. The flow rate was first increased from 0.001 to 0.250 mL/min, the pressure drop increasing from 2 to 298 bar, and the column being placed in stagnant air at 296.5 K, in order to determine the effective diffusivity of insulin through the porous particles, the mass transfer rate constants, and the adsorption equilibrium constant in the low-pressure range. Then, the column inlet pressure was increased by using capillary flow restrictors downstream the column, at the constant flow rate of 0.03 mL/min. The column temperature was kept uniform by immersing the column in a circulating water bath thermostatted at 298.7 and 323.15 K, successively. The results showed that the surface diffusion coefficient of insulin decreases faster than its bulk diffusion coefficient with increasing average column pressure. This is consistent with the adsorption energy of insulin onto the BEH-C(18) surface increasing strongly with increasing pressure. In contrast, given the precision of the height equivalent to a theoretical plate (HETP) measurement (+/-12%), the adsorption kinetics of insulin appears to be rather independent of the pressure. On average, the adsorption rate constant of insulin is doubled from about 40 to 80 s(-1) when the temperature increases from 298.7 to 323.15 K.

Kinetic Analysis of Haloacetonitrile Stability in Drinking Waters.

PubMed

Yu, Yun; Reckhow, David A

2015-09-15

Haloacetonitriles (HANs) are an important class of drinking water disinfection byproducts (DBPs) that are reactive and can undergo considerable transformation on time scales relevant to system distribution (i.e., from a few hours to a week or more). The stability of seven mono-, di-, and trihaloacetonitriles was examined under a variety of conditions including different pH levels and disinfectant doses that are typical of drinking water distribution systems. Results indicated that hydroxide, hypochlorite, and their protonated forms could react with HANs via nucleophilic attack on the nitrile carbon, forming the corresponding haloacetamides (HAMs) and haloacetic acids (HAAs) as major reaction intermediates and end products. Other stable intermediate products, such as the N-chloro-haloacetamides (N-chloro-HAMs), may form during the course of HAN chlorination. A scheme of pathways for the HAN reactions was proposed, and the rate constants for individual reactions were estimated. Under slightly basic conditions, hydroxide and hypochlorite are primary reactants and their associated second-order reaction rate constants were estimated to be 6 to 9 orders of magnitude higher than those of their protonated conjugates (i.e., neutral water and hypochlorous acid), which are much weaker but more predominant nucleophiles at neutral and acidic pHs. Developed using the estimated reaction rate constants, the linear free energy relationships (LFERs) summarized the nucleophilic nature of HAN reactions and demonstrated an activating effect of the electron withdrawing halogens on nitrile reactivity, leading to decreasing HAN stability with increasing degree of halogenation of the substituents, while subsequent shift from chlorine to bromine atoms has a contrary stabilizing effect on HANs. The chemical kinetic model together with the reaction rate constants that were determined in this work can be used for quantitative predictions of HAN concentrations depending on pH and free chlorine contact times (CTs), which can be applied as an informative tool by drinking water treatment and system management engineers to better control these emerging nitrogenous DBPs, and can also be significant in making regulatory decisions.

Population pharmacokinetics of olmesartan following oral administration of its prodrug, olmesartan medoxomil: in healthy volunteers and hypertensive patients.

PubMed

Yoshihara, Kazutaka; Gao, Yuying; Shiga, Hiroshi; Wada, D Russell; Hisaoka, Masafumi

2005-01-01

Olmesartan medoxomil (CS-866) is a new orally active angiotensin II receptor antagonist that is highly selective for the AT1 receptor subtype. To develop a population pharmacokinetic model for olmesartan (RNH-6270), the active metabolite of olmesartan medoxomil, in healthy volunteers and hypertensive patients, and to evaluate effects of covariates on the apparent oral clearance (CL/F), with particular emphasis on the effect of race. Retrospective analysis of data from 12 phase I-III trials in the US, Europe and Japan. Eighty-nine healthy volunteers and 383 hypertensive patients. Nonlinear mixed-effects modelling was used to evaluate 7911 olmesartan plasma sample concentrations. The covariates included age, bodyweight, sex, race (Westerners [including Caucasians and Hispanics] versus Japanese), patient status (hypertensive patients versus healthy volunteers), serum creatinine level as an index of renal function and serum chemistry data as indices of hepatic function. The pharmacokinetic data of olmesartan were well described by a two-compartment linear model with first-order absorption and an absorption lag-time, parameterised in terms of CL/F (6.66 L/h for a typical male Western hypertensive patient), absorption rate constant (1.46h-1), elimination rate constant (0.193h-1), rate constant from the central to peripheral compartment (0.061h-1), rate constant from the peripheral to central compartment (0.079h-1) and absorption lag-time (0.427h). Analysis of covariates showed that age, bodyweight, sex, patient status and renal function were factors influencing the clearance of olmesartan. The population pharmacokinetic analysis of olmesartan showed that: (i) severe renal impairment (serum creatinine >265 micromol/L [approximately 3 mg/dL]) could cause a clearance decrease of > or =30%; (ii) older age, lower bodyweight and being female were determinants of lower clearance but their effects on olmesartan clearance were within 20%; (iii) no statistically significant difference in clearance was found between Westerners and Japanese.

Mortality rates in OECD countries converged during the period 1990-2010.

PubMed

Bremberg, Sven G

2017-06-01

Since the scientific revolution of the 18th century, human health has gradually improved, but there is no unifying theory that explains this improvement in health. Studies of macrodeterminants have produced conflicting results. Most studies have analysed health at a given point in time as the outcome; however, the rate of improvement in health might be a more appropriate outcome. Twenty-eight OECD member countries were selected for analysis in the period 1990-2010. The main outcomes studied, in six age groups, were the national rates of decrease in mortality in the period 1990-2010. The effects of seven potential determinants on the rates of decrease in mortality were analysed in linear multiple regression models using least squares, controlling for country-specific history constants, which represent the mortality rate in 1990. The multiple regression analyses started with models that only included mortality rates in 1990 as determinants. These models explained 87% of the intercountry variation in the children aged 1-4 years and 51% in adults aged 55-74 years. When added to the regression equations, the seven determinants did not seem to significantly increase the explanatory power of the equations. The analyses indicated a decrease in mortality in all nations and in all age groups. The development of mortality rates in the different nations demonstrated significant catch-up effects. Therefore an important objective of the national public health sector seems to be to reduce the delay between international research findings and the universal implementation of relevant innovations.

[Response of alfalfa seed to stress storage conditions].

PubMed

Li, Chunjie; Wang, Yanrong; Zhu, Tingheng; Yu, Ling

2002-08-01

The seed germination rate, seed mortality, seedling length, and infection rate of alfalfa (Medicago sativa L. cv. 'Longdong') were measured at constant temperature 20 degrees C every 60 days during one year storage period after inoculated or no inoculated by Fusarium avenaceum under room temperature (RT), 35 degrees C, and 35 degrees C and +10% seed moisture content (SMC) conditions. Field emergence rates of seeds under above treatments were also observed, and seed-borne fungi were detected under the conditions mentioned above and controlled deterioration (CD) as well. The results showed that the percentage of isolated alfalfa seed-borne fungi was increased from 10% under room temperature and 35 degrees C to 29% under 35 degrees C + 10% SMC. Disease resistance was declined, and seed mortality and seedling infection rate under 35 degrees C + 10% SMC were significantly higher than those under room temperature and 35 degrees C respectively (P < 0.05). The seed germination rate and field emergence rate were also decreased significantly (P < 0.05). Seedling shoot and root length under 35 degrees C + 10% SMC were significantly less than those under RT and 35 degrees C respectively (P < 0.05). The percentages of both seed-borne fungi isolated and field emergence were decreased, and that of seedling infection was increased with storage period extending from 60 to 360 days. Compared to no inoculated control, the percentage of seed germination, seedling shoot and root length were decreased, and seed mortality and seedling infection rate were increased after inoculated by F. avenaceum.

Fractional time-dependent apparent viscosity model for semisolid foodstuffs

NASA Astrophysics Data System (ADS)

Yang, Xu; Chen, Wen; Sun, HongGuang

2017-10-01

The difficulty in the description of thixotropic behaviors in semisolid foodstuffs is the time dependent nature of apparent viscosity under constant shear rate. In this study, we propose a novel theoretical model via fractional derivative to address the high demand by industries. The present model adopts the critical parameter of fractional derivative order α to describe the corresponding time-dependent thixotropic behavior. More interestingly, the parameter α provides a quantitative insight into discriminating foodstuffs. With the re-exploration of three groups of experimental data (tehineh, balangu, and natillas), the proposed methodology is validated in good applicability and efficiency. The results show that the present fractional apparent viscosity model performs successfully for tested foodstuffs in the shear rate range of 50-150 s^{ - 1}. The fractional order α decreases with the increase of temperature at low temperature, below 50 °C, but increases with growing shear rate. While the ideal initial viscosity k decreases with the increase of temperature, shear rate, and ingredient content. It is observed that the magnitude of α is capable of characterizing the thixotropy of semisolid foodstuffs.

Oligonucleotide facilitators may inhibit or activate a hammerhead ribozyme.

PubMed Central

Jankowsky, E; Schwenzer, B

1996-01-01

Facilitators are oligonucleotides capable of affecting hammerhead ribozyme activity by interacting with the substrate at the termini of the ribozyme. Facilitator effects were determined in vitro using a system consisting of a ribozyme with 7 nucleotides in every stem sequence and two substrates with inverted facilitator binding sequences. The effects of 9mer and 12mer RNA as well as DNA facilitators which bind either adjacent to the 3'- or 5'-end of the ribozyme were investigated. A kinetic model was developed which allows determination of the apparent dissociation constant of the ribozyme-substrate complex from single turnover reactions. We observed a decreased dissociation constant of the ribozyme-substrate complex due to facilitator addition corresponding to an additional stabilization energy of delta delta G=-1.7 kcal/mol with 3'-end facilitators. The cleavage rate constant was increased by 3'-end facilitators and decreased by 5'-end facilitators. Values for Km were slightly lowered by all facilitators and kcat was increased by 3'-end facilitators and decreased by 5'-end facilitators in our system. Generally the facilitator effects increased with the length of the facilitators and RNA provided greater effects than DNA of the same sequence. Results suggest facilitator influences on several steps of the hammerhead reaction, substrate association, cleavage and dissociation of products. Moreover, these effects are dependent in different manners on ribozyme and substrate concentration. This leads to the conclusion that there is a concentration dependence whether activation or inhibition is caused by facilitators. Conclusions are drawn with regard to the design of hammerhead ribozyme facilitator systems. PMID:8602353

A cell impedance measurement device for the cytotoxicity assay dependent on the velocity of supplied toxic fluid

NASA Astrophysics Data System (ADS)

Kang, Yoon-Tae; Kim, Min-Ji; Cho, Young-Ho

2018-04-01

We present a cell impedance measurement chip capable of characterizing the toxic response of cells depending on the velocity of the supplied toxic fluid. Previous impedance-based devices using a single open-top chamber have been limited to maintaining a constant supply velocity, and devices with a single closed-top chamber present difficulties in simultaneous cytotoxicity assay for varying levels of supply velocities. The present device, capable of generating constant and multiple levels of toxic fluid velocity simultaneously within a single stepwise microchannel, performs a cytotoxicity assay dependent on toxic fluid velocity, in order to find the effective velocity of toxic fluid to cells for maximizing the cytotoxic effect. We analyze the cellular toxic response of 5% ethanol media supplied to cancer cells within a toxic fluid velocity range of 0-8.3 mm s-1. We observe the velocity-dependent cell detachment rate, impedance, and death rate. We find that the cell detachment rate decreased suddenly to 2.4% at a velocity of 4.4 mm s-1, and that the change rates of cell resistance and cell capacitance showed steep decreases to 8% and 41%, respectively, at a velocity of 5.7 mm s-1. The cell death rate and impedance fell steeply to 32% at a velocity of 5.7 mm s-1. We conclude that: (1) the present device is useful in deciding on the toxic fluid velocity effective to cytotoxicity assay, since the cellular toxic response is dependent on the velocity of toxic fluid, and; (2) the cell impedance analysis facilitates a finer cellular response analysis, showing better correlation with the cell death rate, compared to conventional visual observation. The present device, capable of performing the combinational analysis of toxic fluid velocity and cell impedance, has potential for application to the fine cellular toxicity assay of drugs with proper toxic fluid velocity.

Assessing Chemical Retention Process Controls in Ponds

NASA Astrophysics Data System (ADS)

Torgersen, T.; Branco, B.; John, B.

2002-05-01

Small ponds are a ubiquitous component of the landscape and have earned a reputation as effective chemical retention devices. The most common characterization of pond chemical retention is the retention coefficient, Ri= ([Ci]inflow-[Ci] outflow)/[Ci]inflow. However, this parameter varies widely in one pond with time and among ponds. We have re-evaluated literature reported (Borden et al., 1998) monthly average retention coefficients for two ponds in North Carolina. Employing a simple first order model that includes water residence time, the first order process responsible for species removal have been separated from the water residence time over which it acts. Assuming the rate constant for species removal is constant within the pond (arguable at least), the annual average rate constant for species removal is generated. Using the annual mean rate constant for species removal and monthly water residence times results in a significantly enhanced predictive capability for Davis Pond during most months of the year. Predictive ability remains poor in Davis Pond during winter/unstratified periods when internal loading of P and N results in low to negative chemical retention. Predictive ability for Piedmont Pond (which has numerous negative chemical retention periods) is improved but not to the same extent as Davis Pond. In Davis Pond, the rate constant for sediment removal (each month) is faster than the rate constant for water and explains the good predictability for sediment retention. However, the removal rate constant for P and N is slower than the removal rate constant for sediment (longer water column residence time for P,N than for sediment). Thus sedimentation is not an overall control on nutrient retention. Additionally, the removal rate constant for P is slower than for TOC (TOC is not the dominate removal process for P) and N is removed slower than P (different in pond controls). For Piedmont Pond, sediment removal rate constants are slower than the removal rate constant for water indicating significant sediment resuspension episodes. It appears that these sediment resuspension events are aperiodic and control the loading and the chemical retention capability of Piedmont Pond for N,P,TOC. These calculated rate constants reflect the differing internal loading processes for each component and suggest means and mechanisms for the use of ponds in water quality management.

Regional evaluation of hydrologic factors and effects of pumping, St Peter-Jordan aquifer, Iowa

USGS Publications Warehouse

Burkart, M.R.; Buchmiller, Robert

1990-01-01

Pumping has caused changes in the flow system that include regional declines in the potentiometric surface of the aquifer. Simulation indicates that pumping through 1980 increased net vertical leakage into the aquifer to about double the predevelopment rate. Discharge across lateral boundaries has been substantially reduced or reversed by pumping. Aquifer storage provided about one-third of the water required to supply pumping in the 1970's. Simulation of future conditions, assuming no increase in pumping rates, indicates that the rate of decline in water levels will decrease by the year 2020. As equilibrium with pumping is approached in 2020, 75 percent of the pumpage will be balanced by vertical leakage, eight percent by water released from aquifer storage, and 17 percent by increases in boundary recharge or decreases in boundary discharge. Future pumping at an increasing rate of about 10 percent per decade of the average pumping rate in 1975 will require about one and one-half times the vertical leakage of the 1971-1980 period and about fivetimes the net inflow from lateral boundaries; however, the rate of water released from aquifer storage will be about half the 1970's rate. Under these conditions, the head in the aquifer will continue to decline at an almost constant rate until 2020.

Global Well-Posedness and Decay Rates of Strong Solutions to a Non-Conservative Compressible Two-Fluid Model

NASA Astrophysics Data System (ADS)

Evje, Steinar; Wang, Wenjun; Wen, Huanyao

2016-09-01

In this paper, we consider a compressible two-fluid model with constant viscosity coefficients and unequal pressure functions {P^+neq P^-}. As mentioned in the seminal work by Bresch, Desjardins, et al. (Arch Rational Mech Anal 196:599-629, 2010) for the compressible two-fluid model, where {P^+=P^-} (common pressure) is used and capillarity effects are accounted for in terms of a third-order derivative of density, the case of constant viscosity coefficients cannot be handled in their settings. Besides, their analysis relies on a special choice for the density-dependent viscosity [refer also to another reference (Commun Math Phys 309:737-755, 2012) by Bresch, Huang and Li for a study of the same model in one dimension but without capillarity effects]. In this work, we obtain the global solution and its optimal decay rate (in time) with constant viscosity coefficients and some smallness assumptions. In particular, capillary pressure is taken into account in the sense that {Δ P=P^+ - P^-=fneq 0} where the difference function {f} is assumed to be a strictly decreasing function near the equilibrium relative to the fluid corresponding to {P^-}. This assumption plays an key role in the analysis and appears to have an essential stabilization effect on the model in question.

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

PubMed

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

2017-10-12

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

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.

The interacting effect of cognitive and motor task demands on performance of gait, balance and cognition in young adults.

PubMed

Szturm, Tony; Maharjan, Pramila; Marotta, Jonathan J; Shay, Barbara; Shrestha, Shiva; Sakhalkar, Vedant

2013-09-01

Mobility limitations and cognitive impairments, each common with aging, reduce levels of physical and mental activity, are prognostic of future adverse health events, and are associated with an increased fall risk. The purpose of this study was to examine whether divided attention during walking at a constant speed would decrease locomotor rhythm, stability, and cognitive performance. Young healthy participants (n=20) performed a visuo-spatial cognitive task in sitting and while treadmill walking at 2 speeds (0.7 and 1.0 m/s).Treadmill speed had a significant effect on temporal gait variables and ML-COP excursion. Cognitive load did not have a significant effect on average temporal gait variables or COP excursion, but variation of gait variables increased during dual-task walking. ML and AP trunk motion was found to decrease during dual-task walking. There was a significant decrease in cognitive performance (success rate, response time and movement time) while walking, but no effect due to treadmill speed. In conclusion walking speed is an important variable to be controlled in studies that are designed to examine effects of concurrent cognitive tasks on locomotor rhythm, pacing and stability. Divided attention during walking at a constant speed did result in decreased performance of a visuo-spatial cognitive task and an increased variability in locomotor rhythm. Copyright © 2013 Elsevier B.V. All rights reserved.

Effects of temperature at constant air dew point on leaf carboxylation efficiency and CO2 compensation point of different leaf types.

PubMed

Weber, J A; Tenhunen, J D; Lange, O L

1985-09-01

The effect of temperature on photosynthesis at constant water-vapor pressure in the air was investigated using two sclerophyll species, Arbutus unedo and Quercus suber, and one mesophytic species, Spinacia oleracea. Photosynthesis and transpiration were measured over a range of temperatures, 20-39° C. The external concentration of CO2 was varied from 340 μbar to near CO2 compensation. The initial slope (carboxylation efficiency, CE) of the photosynthetic response to intercellular CO2 concentration, the CO2 compensation point (Γ), and the extrapolated rate of CO2 released into CO2-free air (R i) were calculated. At an external CO2 concentration of 320-340 μbar CO2, photosynthesis decreased with temperature in all species. The effect of temperature on Γ was similar in all species. While CE in S. oleracea changed little with temperature, CE decreased by 50% in Q. suber as temperature increased from 25 to 34° C. Arbutus unedo also exhibited a decrease in CE at higher temperatures but not as marked as Q. suber. The absolut value of R i increased with temperature in S. oleracea, while changing little or decreasing in the sclerophylls. Variations in Γ and R i of the sclerophyll species are not consistent with greater increase of respiration with temperature in the light in these species compared with S. oleracea.

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.

Performance evaluation of a dental handpiece in simulation of clinical finishing using a novel 2DOF in vitro apparatus.

PubMed

Yin, L; Song, X F; Qu, S F; Huang, T; Mei, J P; Yang, Z Y; Li, J

2006-11-01

This paper reports on the performance evaluation of a dental handpiece in simulation of clinical finishing using a novel two-degrees-of-freedom (2DOF) in vitro apparatus. The instrumented apparatus consisted of a two-dimensional computer-controlled coordinate worktable carrying a dental handpiece, a piezoelectric force dynamometer, and a high-speed data acquisition and signal conditioning system for simulating the clinical operations and monitoring the dental finishing processes. The performance of the dental handpiece was experimentally evaluated with respect to rotational speed, torque, and specific finishing energy under the applied clinical finishing conditions. The results show that the rotational speeds of the dental handpiece decreased by increasing either the depth of cut or the feed rate at a constant clinically applied air pressure and water flowrate. They also decreased when increasing both the tangential and normal finishing forces. The specific finishing energy decreased with an increase in either depth of cut or feed rate, while the finishing torque increased as either the depth of cut or the feed rate was increased. Implications of these results were to provide guidance for proper applications of dental handpieces in clinical practice.

[Disease numbers in pneumology - a projection to 2060].

PubMed

Pritzkuleit, R; Beske, F; Katalinic, A

2010-09-01

The demographic change leads to a change in the age-composition of the population. We have calculated a status quo projection of the absolute numbers for five diagnoses of the lung (COPD, CAP, lung cancer, bronchial asthma and tuberculosis) for Germany up to 2060. Based on the 12 (th) coordinated population prediction of the Federal Statistics Office, we transferred age- and sex-specific incidence and prevalence rates, respectively, to the expected population. All described developments are based solely on demographic changes. The absolute numbers of bronchial asthma and tuberculosis will experience a minor decrease. We expect at first increasing and later decreasing case numbers for COPD and lung cancer. A major increase of the case numbers for CAP will be probable. By reason of a decreasing population, the rates (burden of disease for the population) will increase considerably. The demographic change is mainly caused by increasing life expectancy, constantly low birth rates, and the entry of the baby-boom generation into the age of higher disease risks. A discussion about prioritisation of health care is needed because of the rising burdens for the health system, including diseases of the lung. Copyright Georg Thieme Verlag KG Stuttgart . New York.

An investigation of the sound field above the audience in large lecture halls with a scale model.

PubMed

Kahn, D W; Tichy, J

1986-09-01

Measurements of steady-state sound pressure levels above the audience in large lecture halls show that the classical equation for predicting the sound pressure level is not accurate. The direct field above the seats was measured on a 1:10 scale model and was found to be dependent on the incidence angle and direction of sound propagation across the audience. The reverberant field above the seats in the model was calculated by subtracting the direct field from the measured total field and was found to be dependent on the magnitude and particularly on the placement of absorption. The decrease of sound pressure level versus distance in the total field depends on the angle (controlled by absorption placement) at which the strong reflections are incident upon the audience area. Sound pressure level decreases at a fairly constant rate with distance from the sound source in both the direct and reverberant field, and the decrease rate depends strongly on the absorption placement. The lowest rate of decay occurs when the side walls are absorptive, and both the ceiling and rear wall are reflective. These consequences are discussed with respect to prediction of speech intelligibility.

Orbital period changes in Centaurus X-3

NASA Technical Reports Server (NTRS)

Kelley, R. L.; Rappaport, S.; Clark, G. W.; Petro, L. D.

1983-01-01

Two new times of mid-X-ray eclipse for Cen X-3 are presented on the basis of pulse arrival time analyses of pointed observations with SAS 3. When combined with all other published eclipse times based on Doppler delay measurements, the results show that the 2.1d binary period is decreasing at an average rate of 1.8 x 10 to the -6th/yr. The decrease, however, is seen as having significant fluctuations about a smooth, linear decrease. The changes observed in the orbital period can be accounted for by mass loss from the system through the L2 point, although the rates required are implausibly high. It is also shown that the long-term overall orbital decay can readily be interpreted as the result of torques exerted by the tidally distorted companion star (Krzeminski's star) on the orbiting neutron star. It is noted that the inferred asynchronism between the orbital frequency and the rotation frequency of the companion star may be maintained by mass and angular momentum loss in a stellar wind or by a tidal instability related to the Darwin effect. However, this would not provide a natural explanation for any short-term deviations from a constant rate of orbital decay.

Implication of surface modified NZVI particle retention in the porous media: Assessment with the help of 1-D transport model

NASA Astrophysics Data System (ADS)

Raychoudhury, Trishikhi; Surasani, Vikranth Kumar

2017-06-01

Retention of surface-modified nanoscale zero-valent iron (NZVI) particles in the porous media near the point of injection has been reported in the recent studies. Retention of excess particles in porous media can alter the media properties. The main objectives of this study are, therefore, to evaluate the effect of particle retention on the porous media properties and its implication on further NZVI particle transport under different flow conditions. To achieve the objectives, a one-dimensional transport model is developed by considering particle deposition, detachment, and straining mechanisms along with the effect of changes in porosity resulting from retention of NZVI particles. Two different flow conditions are considered for simulations. The first is a constant Darcy's flow rate condition, which assumes a change in porosity, causes a change in pore water velocity and the second, is a constant head condition, which assumes the change in porosity, influence the permeability and hydraulic conductivity (thus Darcy's flow rate). Overall a rapid decrease in porosity was observed as a result of high particle retention near the injection points resulting in a spatial distribution of deposition rate coefficient. In the case of constant head condition, the spatial distribution of Darcy's velocities is predicted due to variation in porosity and hydraulic conductivity. The simulation results are compared with the data reported from the field studies; which suggests straining is likely to happen in the real field condition.

Projected ground-water development, ground-water levels, and stream-aquifer leakage in the South Fork Solomon River Valley between Webster Reservoir and Waconda Lake, north-central Kansas, 1979-2020

USGS Publications Warehouse

Kume, Jack; Lindgren, R.J.; Stullken, L.E.

1985-01-01

A two-dimensional finite difference computer model was used to project changes in the potentiometric surface, saturated thickness, and stream aquifer leakage in an alluvial aquifer resulting from four instances of projected groundwater development. The alluvial aquifer occurs in the South Fork Solomon River valley between Webster Reservoir and Waconda Lake in north-central Kansas. In the first two projections, pumpage for irrigation was held constant at 1978 rates throughout the projection period (1979-2020). In the second two projections, the 1978 pumpage was progressively increased each yr through 2020. In the second and fourth projections, surface water diversions in the Osborne Irrigation Canal were decreased by 50 %. For the third and fourth projections, each grid-block in the modeled area was classified initially as one of six types according to whether it represented irrigable or nonirrigable land, to its saturated thickness, to its location inside or outside the canal-river area, and to its pumping rate. The projected base-flow rates (leakage from the aquifer to the river) were lower during the irrigation season (June, July, and August) than during the other months of the yr because of the decline in hydraulic head produced by groundwater pumpage. Stream depletion, calculated as a decrease below the average (1970-78) estimated winter base-flow rate of 16.5 cu ft/sec, varied inversely with base flow. For the first two projections, a constant annual cycle of well pumpage and recharge was used throughout the projection period. Aquifer leakage to the river was nearly constant by the mid-to-late 1990's, implying that flow conditions had attained a stabilized annual cycle. The third and fourth projections never attained an annual stabilized cycle because the irrigation pumpage rate was increased each year. By the early 1980's, the hydraulic head had fallen below river stage, reversing the hydraulic gradient at the stream-aquifer interface and resulting in net leakage from the river to the aquifer during the summer months. By the early 1990 's, the projected potentiometric surface of the aquifer was lower than the river stage even during the winter and spring months. (Author 's abstract)

Effect of vacuum-ultraviolet irradiation on the dielectric constant of low-k organosilicate dielectrics

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

Zheng, H.; Shohet, J. L.; Ryan, E. T.

2014-11-17

Vacuum ultraviolet (VUV) irradiation is generated during plasma processing in semiconductor fabrications, while the effect of VUV irradiation on the dielectric constant (k value) of low-k materials is still an open question. To clarify this problem, VUV photons with a range of energies were exposed on low-k organosilicate dielectrics (SiCOH) samples at room temperature. Photon energies equal to or larger than 6.0 eV were found to decrease the k value of SiCOH films. VUV photons with lower energies do not have this effect. This shows the need for thermal heating in traditional ultraviolet (UV) curing since UV light sources do notmore » have sufficient energy to change the dielectric constant of SiCOH and additional energy is required from thermal heating. In addition, 6.2 eV photon irradiation was found to be the most effective in decreasing the dielectric constant of low-k organosilicate films. Fourier Transform Infra-red Spectroscopy shows that these 6.2 eV VUV exposures removed organic porogens. This contributes to the decrease of the dielectric constant. This information provides the range of VUV photon energies that could decrease the dielectric constant of low-k materials most effectively.« less

Modulation of the erosion rate of an uplifting landscape by long-term climate change: An experimental investigation

NASA Astrophysics Data System (ADS)

Moussirou, Bérangé; Bonnet, Stéphane

2018-02-01

Whether or not climatic variations play a major role in setting the erosion rate of continental landscapes is a key factor in demonstrating the influence of climate on the tectonic evolution of mountain belts and understanding how clastic deposits preserved in sedimentary basins may record climatic variations. Here, we investigate how a change in precipitation influences the erosional dynamics of laboratory-scale landscapes that evolved under a combination of uplift and rainfall forcings. We consider here the impact of a decrease in the precipitation rate of finite duration on the erosive response of a landscape forced by a constant uplift and initially at a steady state (SS1). We performed several experiments with the same amplitude but different durations of precipitation decrease (Tp). We observe that the decrease in precipitation induces a phase of surface uplift of landscapes to a new steady state condition (SS2); however, the details of the uplift histories (timing, rate) differ between the experiments according to Tp. We also observe a decrease in the erosion rate induced by the precipitation change; however, the timing and amplitude of this decrease vary according to Tp, defining a delayed and damped erosion signal. Our data show that the landscape response to precipitation change is dictated by a critical water-to-rock ratio (ratio of precipitation over uplift) that likely corresponds to a geomorphic threshold. Our study suggests that variations in precipitation that occur at a geological time scale (> 106 years) may have a weak impact on the erosion of landscapes and on the delivery of siliciclastic material to large rivers and sedimentary basins.

Interspecific correlates of plasticity in relative growth rate following a decrease in nitrogen availability.

PubMed

Useche, Antonio; Shipley, Bill

2010-02-01

Nitrogen availability varies greatly over short time scales. This requires that a well-adapted plant modify its phenotype by an appropriate amount and at a certain speed in order to maximize growth and fitness. To determine how plastic ontogenetic changes in each trait interact and whether or not these changes are likely to maximize growth, ontogenetic changes in relative growth rate (RGR), net assimilation rate (NAR), specific leaf area (SLA) and root weight ratio (RWR), before and after a decrease in nitrogen supply, were studied in 14 herbaceous species. Forty-four plants of each species were grown in hydroponic culture under controlled conditions in a control treatment where the supply of nitrogen remained constant at 1 mm, and in a stress treatment where the nitrogen supply was abruptly decreased from 1 to 0.01 mm during the growth period. In the treatment series, and in comparison with the control, NAR and RGR decreased, RWR increased, and SLA did not change except for the timing of ontogenetic change. Species having greater increases in the maximum rate of change in RWR also had smaller reductions in RGR; plasticity in RWR is therefore adaptive. In contrast, species which showed a greater decrease in NAR showed stronger reductions in RGR; plasticity in NAR is therefore not adaptive. Plasticity in RGR was not related to plasticity in SLA. There were no significant relationships among the plasticities in NAR, RWR or SLA. Potentially fast-growing species experienced larger reductions in RGR following the nitrogen reduction. These results suggest that competitive responses to interspecific competition for nitrogen might be positively correlated with the plasticity in the maximum rate of change in RWR in response to a reduction in nitrogen supply.

Diamond deposition in a hot-filament reactor using different hydrocarbon precursor gases

NASA Astrophysics Data System (ADS)

May, P. W.; Everitt, N. M.; Trevor, C. G.; Ashfold, M. N. R.; Rosser, K. N.

1993-07-01

A hot-filament reactor was used to deposit polycrystalline diamond films upon single-crystal Si substrates using hydrocarbon/H 2 gas mixtures. We studied the effect upon the deposition process and resulting film properties by varying the hydrocarbon gas from C 1H x to C 4H x alkanes. This was done maintaining a constant carbon-to-hydrogen ratio, but using a substantially lower-than- normal filament temperature (1500°C) in order to highlight differences in activation barriers and in the chemistry of the diamond-forming step. It was found that with increasing hydrocarbon chain length the deposition rate decreased, from a value of about 0.4 μm h -1 for methane/H 2 mixtures to less than 0.07 μm h -1 for butane/H 2. This was accompanied by an increase in the relative proportion of amorphous carbon to diamond present in the films. After one hour deposition the diamond grain size remained constant at about 20 nm, irrespective of the precursor gas. The measured Knoop hardness of the films also decreased when using process gases other than methane. We also studied the effect of changing the bond order in C 2H x precursor gases (ethane, ethene, ethyne) but found that this had no effect on either the deposition rate or the film quality.

Using milk fat to reduce the irritation and bitter taste of ibuprofen

PubMed Central

Bennett, Samantha M.; Zhou, Lisa; Hayes, John E.

2012-01-01

Bitterness and irritation elicited by pharmaceutically active molecules remain problematic for pediatric medications, fortified foods and dietary supplements. Few effective methods exist for reducing these unpalatable sensations, negatively impacting medication compliance and intake of beneficial phytonutrients. A physicochemical approach to masking these sensations may be the most successful approach for generalizability to a wide range of structurally and functionally unique compounds. Here, solutions of the non-steroidal anti- inflammatory drug, ibuprofen, were prepared in milk products with varying fat content. Our hypothesis, based on other reports of similar phenomena, was that increasing the fat content would cause ibuprofen to selectively partition into the fat phase, thereby reducing interaction with sensory receptors and decreasing adversive sensations. Quantification of the aqueous concentration of ibuprofen was performed using an isocratic HPLC method coupled with an external standard curve. Sensory testing showed a modest but significant decrease (~20%) in irritation ratings between the skim milk (0% fat) and the half-and-half (11% fat) samples, indicating that increased fat may contribute to a reduced sensory response. Bitterness was not reduced, remaining constant over all fat levels. The HPLC results indicate a constant amount of ibuprofen remained in the aqueous phase regardless of fat level, so a simple partitioning hypothesis cannot explain the reduced irritancy ratings. Association of ionized ibuprofen with continuous phase solutes such as unabsorbed protein should be explored in future work. PMID:23527314

Fiber-Supported Droplet Combustion. Experiment 32

NASA Technical Reports Server (NTRS)

Dietrich, Daniel L.; Haggard, John B., Jr.; Nayagam, Vedha; Dryer, Frederick L.; Williams, Forman A.; Shaw, Ben D.

1998-01-01

Individual droplets with diameters ranging from about 2 mm to 5 mm were burned under microgravity conditions in air at 1 bar with an ambient temperature of 300 K. Each droplet was tethered by a silicon carbide fiber of 80 mm or 150 mm diameter to keep it in view of video recording, and, in some tests, a forced air flow was applied in a direction parallel to the fiber axis. Methanol, two methanol-water mixtures, two methanol-dodecanol mixtures, and two heptane-hexadecane mixtures were the fuels. Droplet diameters were measured as functions of time and compared with existing theoretical predictions. The prediction that methanol droplets extinguish at diameters that increase with increasing initial droplet diameter is verified by these experiments. In addition, the quasi-steady burning rate constant of the heptane-hexadecane mixtures appears to decrease with increasing droplet diameter; obscuration consistent with very heavy sooting, but without the formation of soot shells, is observed for the largest of these droplets. Forced convective flow around methanol droplets was found to increase the burning rate and to produce a ratio of downstream-to-upstream flame radius that remained constant as the droplet size decreased, a trend in agreement with earlier results obtained at higher convective velocities for smaller droplets having larger flame standoff ratios. There are a number of implications of the experimental results regarding droplet-combustion theory.

Is energy pooling necessary in ultraviolet matrix-assisted laser desorption/ionization?

PubMed

Lin, Hou-Yu; Song, Botao; Lu, I-Chung; Hsu, Kuo-Tung; Liao, Chih-Yu; Lee, Yin-Yu; Tseng, Chien-Ming; Lee, Yuan-Tseh; Ni, Chi-Kung

2014-01-15

Energy pooling has been suggested as the key process for generating the primary ions during ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI). In previous studies, decreases in fluorescence quantum yields as laser fluence increased for 2-aminobenzoic acid, 2,5-dihydroxybenzoic acid (2,5-DHB), and 3-hydroxypicolinic acid were used as evidence of energy pooling. This work extends the research to other matrices and addresses whether energy pooling is a universal property in UV-MALDI. Energy pooling was investigated in a time-resolved fluorescence experiment by using a short laser pulse (355 nm, 20 ps pulse width) for excitation and a streak camera (1 ps time resolution) for fluorescence detection. The excited-state lifetime of 2,5-DHB decreased with increases in laser fluence. This suggests that a reaction occurs between two excited molecules, and that energy pooling may be one of the possible reactions. However, the excited-state lifetime of 2,4,6-trihydroxyacetophenone (THAP) did not change with increases in laser fluence. The upper limit of the energy pooling rate constant for THAP is estimated to be approximately 100-500 times smaller than that of 2,5-DHB. The small energy pooling rate constant for THAP indicates that the potential contribution of the energy pooling mechanism to the generation of THAP matrix primary ions should be reconsidered. Copyright © 2013 John Wiley & Sons, Ltd.

Effect of bacterial growth rate on bacteriophage population growth rate.

PubMed

Nabergoj, Dominik; Modic, Petra; Podgornik, Aleš

2018-04-01

It is important to understand how physiological state of the host influence propagation of bacteriophages (phages), due to the potential higher phage production needs in the future. In our study, we tried to elucidate the effect of bacterial growth rate on adsorption constant (δ), latent period (L), burst size (b), and bacteriophage population growth rate (λ). As a model system, a well-studied phage T4 and Escherichia coli K-12 as a host was used. Bacteria were grown in a continuous culture operating at dilution rates in the range between 0.06 and 0.98 hr -1 . It was found that the burst size increases linearly from 8 PFU·cell -1 to 89 PFU·cell -1 with increase in bacteria growth rate. On the other hand, adsorption constant and latent period were both decreasing from 2.6∙10 -9  ml·min -1 and 80 min to reach limiting values of 0.5 × 10 -9  ml·min -1 and 27 min at higher growth rates, respectively. Both trends were mathematically described with Michaelis-Menten based type of equation and reasons for such form are discussed. By applying selected equations, a mathematical equation for prediction of bacteriophage population growth rate as a function of dilution rate was derived, reaching values around 8 hr -1 at highest dilution rate. Interestingly, almost identical description can be obtained using much simpler Monod type equation and possible reasons for this finding are discussed. © 2017 The Authors. MicrobiologyOpen published by John Wiley & Sons Ltd.

Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

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

Soudackov, Alexander V.; Hammes-Schiffer, Sharon

2015-11-21

Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at highmore » temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes.« less

Pronounced non-Arrhenius behaviour of hydrogen-abstractions from toluene and derivatives by phthalimide-N-oxyl radicals: a theoretical study.

PubMed

Hermans, Ive; Jacobs, Pierre; Peeters, Jozef

2008-02-28

Abstraction of hydrogen atoms by pthalimide-N-oxyl radicals is an important step in the N-hydroxyphthalimide catalyzed autoxidation of hydrocarbons. In this contribution, the temperature dependency of this reaction is evaluated by a detailed transition state theory based kinetic analysis for the case of toluene. Tunneling was found to play a very important role, enhancing the rate constant by a factor of 20 at room temperature. As a result, tunneling, in combination with the existence of two distinct rotamers of the transition state, causes a pronounced temperature dependency of the pre-exponential frequency factor, and, as a consequence, marked curvature of the Arrhenius plot. This explains why earlier experimental studies over a limited temperature range around 300 K found formal Arrhenius activation energies and pre-factors that are 4 kcal mol(-1) and three orders of magnitude smaller than the actual energy barrier and the corresponding frequency factor, respectively. Also as a consequence of tunneling, substitution of a deuterium atom for a hydrogen atom causes a large decrease in the rate constant, in agreement with the measured kinetic isotope effects. The present theoretical analysis, complementary to the experimental rate coefficient data, allows for a reliable prediction of the rate coefficient at higher temperatures, relevant for actual autoxidation processes.

Formability behavior studies on CP-Al sheets processed through the helical tool path of incremental forming process

NASA Astrophysics Data System (ADS)

Markanday, H.; Nagarajan, D.

2018-02-01

Incremental sheet forming (ISF) is a novel die-less sheet metal forming process, which can produce components directly from the CAD geometry using a CNC milling machine at less production time and cost. The formability of the sheet material used is greatly affected by the process parameters involved and tool path adopted, and the present study is aimed to investigate the influence of different process parameter values using the helical tool path strategy on the formability of a commercial pure Al and to achieve maximum formability in the material. ISF experiments for producing an 80 mm diameter axisymmetric dome were carried out on 2 mm thickness commercially pure Al sheets for different tool speeds and feed rates in a CNC milling machine with a 10 mm hemispherical forming tool. The obtained parts were analyzed for springback, amount of thinning and maximum forming depth. The results showed that when the tool speed was increased by keeping the feed rate constant, the forming depth and thinning were also increased. On contrary, when the feed rate was increased by keeping the tool speed constant, the forming depth and thinning were decreased. Springback was found to be higher when the feed rate was increased rather than the tool speed was increased.

Solar UV irradiances modulate effects of ocean acidification on the coccolithophorid Emiliania huxleyi.

PubMed

Xu, Kai; Gao, Kunshan

2015-01-01

Emiliania huxleyi, the most abundant coccolithophorid in the oceans, is naturally exposed to solar UV radiation (UVR, 280-400 nm) in addition to photosynthetically active radiation (PAR). We investigated the physiological responses of E. huxleyi to the present day and elevated CO2 (390 vs 1000 μatm; with pH(NBS) 8.20 vs 7.86) under indoor constant PAR and fluctuating solar radiation with or without UVR. Enrichment of CO2 stimulated the production rate of particulate organic carbon (POC) under constant PAR, but led to unchanged POC production under incident fluctuating solar radiation. The production rates of particulate inorganic carbon (PIC) as well as PIC/POC ratios were reduced under the elevated CO2, ocean acidification (OA) condition, regardless of PAR levels, and the presence of UVR. However, moderate levels of UVR increased PIC production rates and PIC/POC ratios. OA treatment interacted with UVR to influence the alga's physiological performance, leading to reduced specific growth rate in the presence of UVA (315-400 nm) and decreased quantum yield, along with enhanced nonphotochemical quenching, with addition of UVB (280-315 nm). The results clearly indicate that UV radiation needs to be invoked as a key stressor when considering the impacts of ocean acidification on E. huxleyi. © 2014 The American Society of Photobiology.

Synthesis and characterization of nanoporous anodic oxide film on aluminum in H3PO4 + KMnO4 electrolyte mixture at different anodization conditions

NASA Astrophysics Data System (ADS)

Verma, Naveen; Jindal, Jitender; Singh, Krishan Chander; Mari, Bernabe

2016-04-01

The micro structural properties of nanoporous anodic oxide film formed in H3PO4 were highly influenced by addition of a low concentration of KMnO4 (0.0005 M) in 1 M H3PO4 solution. The KMnO4 as additive enhanced the growth rate of oxide film formation as well as thickness of pore walls. Furthermore the growth rate was found increased with increase in applied current density. The increase in temperature and lack of stirring during anodization causes the thinness of pore wall which leads to increase in pore volume. With the decrease in concentration of H3PO4 in anodizing electrolyte from 1M to 0.3 M, keeping all other conditions constant, the decrease in porosity was observed. This might be due to the dissolution of aluminium oxide film in highly concentrated acidic solution.

Familial secondary erythrocytosis due to increased oxygen affinity is caused by destabilization of the T state of hemoglobin Brigham (α2β2Pro100Leu)

PubMed Central

Mollan, Todd L; Abraham, Bindu; Strader, Michael Brad; Jia, Yiping; Lozier, Jay N; Olson, John S; Alayash, Abdu I

2012-01-01

Hemoglobin Brigham (β Pro100 to Leu) was first reported in a patient with familial erythrocytosis. Erythrocytes of an affected individual from the same family contain both HbA and Hb Brigham and exhibit elevated O2 affinity compared with normal cells (P50 = 23 mm Hg vs. 31 mmHg at pH 7.4 at 37°C). O2 affinities measured for hemolysates were sensitive to changes in pH or chloride concentrations, indicating little change in the Bohr and Chloride effects. Hb Brigham was separated from normal HbA by nondenaturing cation exchange liquid chromatography, and the amino acid substitution was verified by mass spectrometry. The properties of Hb Brigham isolated from the patient's blood were then compared with those of recombinant Hb Brigham expressed in Escherichia coli. Kinetic experiments suggest that the rate constants for ligand binding and release in the high (R) and low (T) affinity quaternary states of Hb Brigham are similar to those of native hemoglobin. However, the Brigham mutation decreases the T to R equilibrium constant (L) which accelerates the switch to the R state during ligand binding to deoxy-Hb, increasing the rate of association by approximately twofold, and decelerates the switch during ligand dissociation from HbO2, decreasing the rate approximately twofold. These kinetic data help explain the high O2 affinity characteristics of Hb Brigham and provide further evidence for the importance of the contribution of Pro100 to intersubunit contacts and stabilization of the T quaternary structure. PMID:22821886

RadNuc: A graphical user interface to deliver dose rate patterns encountered in nuclear medicine with a 137Cs irradiator

PubMed Central

Pasternack, Jordan B.; Howell, Roger W.

2012-01-01

The temporal variations in absorbed dose rates to organs and tissues in the body are very large in diagnostic and therapeutic nuclear medicine. The response of biological endpoints of relevance to radiation safety and therapeutic efficacy are generally modulated by dose rate. Therefore, it is important to understand how the complex dose rate patterns encountered in nuclear medicine impact relevant biological responses. Accordingly, a graphical user interface (GUI) was created to control a cesium-137 irradiator to deliver such dose rate patterns. Methods Visual Basic 6.0 was used to create a user-friendly GUI to control the dose rate by varying the thickness of a mercury attenuator. The GUI facilitates the delivery of a number of dose rate patterns including constant, exponential increase or decrease, and multi-component exponential. Extensive visual feedback is provided by the GUI during both the planning and delivery stages. Results The GUI controlled irradiator can achieve a maximum dose rate of 40 cGy/hr and a minimum dose rate of 0.01 cGy/hr. Addition of machined lead blocks can be used to further reduce the minimum dose rate to 0.0001 cGy/hr. Measured dose rate patterns differed from programmed dose rate patterns in total dose by 3.2% to 8.4%. Conclusion The GUI controlled irradiator is able to accurately create dose rate patterns encountered in nuclear medicine and other related fields. This makes it an invaluable tool for studying the effects of chronic constant and variable low dose rates on biological tissues in the contexts of both radiation protection and clinical administration of internal radionuclides. PMID:23265668

RadNuc: a graphical user interface to deliver dose rate patterns encountered in nuclear medicine with a 137Cs irradiator.

PubMed

Pasternack, Jordan B; Howell, Roger W

2013-02-01

The temporal variations in absorbed dose rates to organs and tissues in the body are very large in diagnostic and therapeutic nuclear medicine. The response of biological endpoints of relevance to radiation safety and therapeutic efficacy is generally modulated by dose rate. Therefore, it is important to understand how the complex dose rate patterns encountered in nuclear medicine impact relevant biological responses. Accordingly, a graphical user interface (GUI) was created to control a cesium-137 irradiator to deliver such dose rate patterns. Visual Basic 6.0 was used to create a user-friendly GUI to control the dose rate by varying the thickness of a mercury attenuator. The GUI facilitates the delivery of a number of dose rate patterns including constant, exponential increase or decrease, and multi-component exponential. Extensive visual feedback is provided by the GUI during both the planning and delivery stages. The GUI controlled irradiator can achieve a maximum dose rate of 40 cGy/h and a minimum dose rate of 0.01 cGy/h. Addition of machined lead blocks can be used to further reduce the minimum dose rate to 0.0001 cGy/h. Measured dose rate patterns differed from programmed dose rate patterns in total dose by 3.2% to 8.4%. The GUI controlled irradiator is able to accurately create dose rate patterns encountered in nuclear medicine and other related fields. This makes it an invaluable tool for studying the effects of chronic constant and variable low dose rates on biological tissues in the contexts of both radiation protection and clinical administration of internal radionuclides. Copyright © 2013 Elsevier Inc. All rights reserved.

Quantifying enzymatic lysis: estimating the combined effects of chemistry, physiology and physics.

PubMed

Mitchell, Gabriel J; Nelson, Daniel C; Weitz, Joshua S

2010-10-04

The number of microbial pathogens resistant to antibiotics continues to increase even as the rate of discovery and approval of new antibiotic therapeutics steadily decreases. Many researchers have begun to investigate the therapeutic potential of naturally occurring lytic enzymes as an alternative to traditional antibiotics. However, direct characterization of lytic enzymes using techniques based on synthetic substrates is often difficult because lytic enzymes bind to the complex superstructure of intact cell walls. Here we present a new standard for the analysis of lytic enzymes based on turbidity assays which allow us to probe the dynamics of lysis without preparing a synthetic substrate. The challenge in the analysis of these assays is to infer the microscopic details of lysis from macroscopic turbidity data. We propose a model of enzymatic lysis that integrates the chemistry responsible for bond cleavage with the physical mechanisms leading to cell wall failure. We then present a solution to an inverse problem in which we estimate reaction rate constants and the heterogeneous susceptibility to lysis among target cells. We validate our model given simulated and experimental turbidity assays. The ability to estimate reaction rate constants for lytic enzymes will facilitate their biochemical characterization and development as antimicrobial therapeutics.

[Degradation Kinetics and Formation of Disinfection By-products During Linuron Chlorination in Drinking Water].

PubMed

Ling, Xiao; Hu, Chen-yan; Cheng, Ming; Gu, Jian

2015-05-01

Chlorination degradation of linuron was studied using the common disinfectant sodium hypochlorite, the effects of chlorine dosage, pH value, bromine ion concentrationand temperature were systematically investigated, and the formation characteristics of disinfection by-products (DBPs) during the chlorination reaction was analyzed. The results showed that the chlorination degradation kinetics of linuron by sodium hypochlorite could be well described by the second-order kinetic model. Moreover, pH values had a great impact on the degradation reaction, and the rate constant reached the maximum level at pH 7, and the base elementary reaction rate constants of HOCl and OCl- with linuron were 4.84 x 10(2) L · (mol · h)(-1) and 3.80 x 10(2) L · (mol · h)(-1), respectively. The reaction rate decreased with the addition of bromide ion and increased with increasing temperature. Furthermore, many kinds of disinfection by- products were produced during the chlorination degradation of linuron, including CF, DCAN, TCNM and halogen acetone. Under conditions of different solution pH and different bromide ion concentrations, there would be significant difference in the types and concentrations of disinfection by-products.

Numerical investigation of the influence of electromagnetic treatment on calcium carbonate scaling rate in non-isothermal pipe flow

NASA Astrophysics Data System (ADS)

Kireev, Victor; Kovaleva, Liana; Isakov, Andrey; Alimbekova, Sofya

2017-11-01

In the present paper, an attempt to explain the mechanisms of the electromagnetic field influence on the process of formation and deposition of calcium carbonate from supersaturated brine solution has been made using numerical modeling. The one-dimensional mathematical model of the brine laminar flow through a cylindrical tube with non-uniform temperature field is written in the form of the system of transient convection-diffusion-reaction partial differential equations describing temperature field and chemical components concentrations (Ca2+, HCO3-, CaCO3). The influence of the temperature on the kinetics of formation of calcium carbonate is taken into account and it is described in accordance with the Arrhenius equation. The kinetics of the calcium carbonate precipitation on the wall of the pipe is given on the basis of the Henry isotherm. It has been established that the electromagnetic treatment of brine solution leads to a decrease of the adsorption rate constant and Henry's constant but it does not significantly influence on the chemical reaction rate of calcium carbonate formation. It also has been shown that treatment with electromagnetic field significantly reduces the amount of calcium carbonate deposits on the wall of the pipe.

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

PubMed

Yang, Jiao; Grey, Kristin; Doney, John

2010-01-15

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

On an aggregation in birth-and-death stochastic dynamics

NASA Astrophysics Data System (ADS)

Finkelshtein, Dmitri; Kondratiev, Yuri; Kutoviy, Oleksandr; Zhizhina, Elena

2014-06-01

We consider birth-and-death stochastic dynamics of particle systems with attractive interaction. The heuristic generator of the dynamics has a constant birth rate and density-dependent decreasing death rate. The corresponding statistical dynamics is constructed. Using the Vlasov-type scaling we derive the limiting mesoscopic evolution and prove that this evolution propagates chaos. We study a nonlinear non-local kinetic equation for the first correlation function (density of population). The existence of uniformly bounded solutions as well as solutions growing inside of a bounded domain and expanding in the space are shown. These solutions describe two regimes in the mesoscopic system: regulation and aggregation.

THE EFFECT OF STRAIN RATE ON FRACTURE TOUGHNESS OF HUMAN CORTICAL BONE: A FINITE ELEMENT STUDY

PubMed Central

Ural, Ani; Zioupos, Peter; Buchanan, Drew; Vashishth, Deepak

2011-01-01

Evaluating the mechanical response of bone under high loading rates is crucial to understanding fractures in traumatic accidents or falls. In the current study, a computational approach based on cohesive finite element modeling was employed to evaluate the effect of strain rate on fracture toughness of human cortical bone. Two-dimensional compact tension specimen models were simulated to evaluate the change in initiation and propagation fracture toughness with increasing strain rate (range: 0.08 to 18 s−1). In addition, the effect of porosity in combination with strain rate was assessed using three-dimensional models of microcomputed tomography-based compact tension specimens. The simulation results showed that bone’s resistance against the propagation of fracture decreased sharply with increase in strain rates up to 1 s−1 and attained an almost constant value for strain rates larger than 1 s−1. On the other hand, initiation fracture toughness exhibited a more gradual decrease throughout the strain rates. There was a significant positive correlation between the experimentally measured number of microcracks and the fracture toughness found in the simulations. Furthermore, the simulation results showed that the amount of porosity did not affect the way initiation fracture toughness decreased with increasing strain rates, whereas it exacerbated the same strain rate effect when propagation fracture toughness was considered. These results suggest that strain rates associated with falls lead to a dramatic reduction in bone’s resistance against crack propagation. The compromised fracture resistance of bone at loads exceeding normal activities indicates a sharp reduction and/or absence of toughening mechanisms in bone during high strain conditions associated with traumatic fracture. PMID:21783112

Minimization of the Renyi entropy production in the stationary states of the Brownian process with matched death and birth rates.

PubMed

Cybulski, Olgierd; Babin, Volodymyr; Hołyst, Robert

2004-01-01

We analyze the Fleming-Viot process. The system is confined in a box, whose boundaries act as a sink of Brownian particles. The death rate at the boundaries is matched by the branching (birth) rate in the system and thus the number of particles is kept constant. We show that such a process is described by the Renyi entropy whose production is minimized in the stationary state. The entropy production in this process is a monotonically decreasing function of time irrespective of the initial conditions. The first Laplacian eigenvalue is shown to be equal to the Renyi entropy production in the stationary state. As an example we simulate the process in a two-dimensional box.

GROUND WATER ISSUE - CALCULATION AND USE OF FIRST-ORDER RATE CONSTANTS FOR MONITORED NATURAL ATTENUATION STUDIES

EPA Science Inventory

This issue paper explains when and how to apply first-order attenuation rate constant calculations in monitored natural attenuation (MNA) studies. First-order attenuation rate constant calculations can be an important tool for evaluating natural attenuation processes at ground-wa...

Trends in electron-ion dissociative recombination of benzene analogs with functional group substitutions: Negative Hammett σpara values

NASA Astrophysics Data System (ADS)

Osborne, David; Lawson, Patrick Andrew; Adams, Nigel; Dotan, Itzhak

2014-06-01

An in-depth study of the effects of functional group substitution on benzene's electron-ion dissociative recombination (e-IDR) rate constant has been conducted. The e-IDR rate constants for benzene, biphenyl, toluene, ethylbenzene, anisole, phenol, and aniline have been measured using a Flowing Afterglow equipped with an electrostatic Langmuir probe (FALP). These measurements have been made over a series of temperatures from 300 to 550 K. A relationship between the Hammett σpara values for each compound and rate constant has indicated a trend in the e-IDR rate constants and possibly in their temperature dependence data. The Hammett σpara value is a method to describe the effect a functional group substituted to a benzene ring has upon the reaction rate constant.

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

NASA Astrophysics Data System (ADS)

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

2012-09-01

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

Kinetics of force recovery following length changes in active skinned single fibres from rabbit psoas muscle

PubMed Central

Burton, Kevin; Simmons, Robert M; Sleep, John; Smith, David A

2006-01-01

Redevelopment of isometric force following shortening of skeletal muscle is thought to result from a redistribution of cross-bridge states. We varied the initial force and cross-bridge distribution by applying various length-change protocols to active skinned single fibres from rabbit psoas muscle, and observed the effect on the slowest phase of recovery (‘late recovery’) that follows transient changes. In response to step releases that reduced force to near zero (∼8 nm (half sarcomere)−1) or prolonged shortening at high velocity, late recovery was well described by two exponentials of approximately equal amplitude and rate constants of ∼2 s−1 and ∼9 s−1 at 5°C. When a large restretch was applied at the end of rapid shortening, recovery was accelerated by (1) the introduction of a slow falling component that truncated the rise in force, and (2) a relative increase in the contribution of the fast exponential component. The rate of the slow fall was similar to that observed after a small isometric step stretch, with a rate of 0.4–0.8 s−1, and its effects could be reversed by reducing force to near zero immediately after the stretch. Force at the start of late recovery was varied in a series of shortening steps or ramps in order to probe the effect of cross-bridge strain on force redevelopment. The rate constants of the two components fell by 40–50% as initial force was raised to 75–80% of steady isometric force. As initial force increased, the relative contribution of the fast component decreased, and this was associated with a length constant of about 2 nm. The results are consistent with a two-state strain-dependent cross-bridge model. In the model there is a continuous distribution of recovery rate constants, but two-exponential fits show that the fast component results from cross-bridges initially at moderate positive strain and the slow component from cross-bridges at high positive strain. PMID:16497718

Kinetic modeling of ion conduction in KcsA potassium channel.

PubMed

Mafé, Salvador; Pellicer, Julio; Cervera, Javier

2005-05-22

KcsA constitutes a potassium channel of known structure that shows both high conduction rates and selectivity among monovalent cations. A kinetic model for ion conduction through this channel that assumes rapid ion transport within the filter has recently been presented by Nelson. In a recent, brief communication, we used the model to provide preliminary explanations to the experimental current-voltage J-V and conductance-concentration g-S curves obtained for a series of monovalent ions (K(+),Tl(+), and Rb(+)). We did not assume rapid ion transport in the calculations, since ion transport within the selectivity filter could be rate limiting for ions other than native K(+). This previous work is now significantly extended to the following experimental problems. First, the outward rectification of the J-V curves in K(+) symmetrical solutions is analyzed using a generalized kinetic model. Second, the J-V and g-S curves for NH(4) (+) are obtained and compared with those of other ions (the NH(4) (+) J-V curve is qualitatively different from those of Rb(+) and Tl(+)). Third, the effects of Na(+) block on K(+) and Rb(+) currents through single KcsA channels are studied and the different blocking behavior is related to the values of the translocation rate constants characteristic of ion transport within the filter. Finally, the significantly decreased K(+) conductance caused by mutation of the wild-type channel is also explained in terms of this rate constant. In order to keep the number of model parameters to a minimum, we do not allow the electrical distance (an empirical parameter of kinetic models that controls the exponential voltage dependence of the dissociation rate) to vary with the ionic species. Without introducing the relatively high number of adjustable parameters of more comprehensive site-based models, we show that ion association to the filter is rate controlling at low concentrations, but ion dissociation from the filter and ion transport within the filter could limit conduction at high concentration. Although some experimental data from other authors were included to allow qualitative comparison with model calculations, the absolute values of the effective rate constants obtained are only tentative. However, the relative changes in these constants needed to explain qualitatively the experiments should be of significance.

Reduction and conversion of 2,4,6-trinitrotoluene (TNT) by sulfide under simulated anaerobic conditions.

PubMed

Qiao, Hua; Wang, He-ling; Feng, Hua-jun; Yao, Jun; Shen, Dong-sheng; Tang, Zhi-jian

2010-07-15

To account for the fast disappearance of TNT in anaerobic fermentative liquid, we investigated TNT (TNT(0)=50 mg/L) reduction by Na(2)S at 30+/-1 degrees C in two types of buffer systems, a phosphate buffer (PB, system A) and a CH(3)COOH-NaHCO(3) buffer (system B). The effects of pH, sulfide concentration and buffer system on the conversion and reaction rate of TNT were investigated. The effect of different variables on the conversion of TNT decreased in the following order: Na(2)S concentration>pH>buffer system. A kinetics study showed that TNT reduction by Na(2)S occurred in two stages separated by a change point. The observed rate constants of the first stage K(obs-1) were 1 order of magnitude lower than those of the second stage. The TNT conversion rate increased and the time to reach the change point became shorter with increasing Na(2)S concentration and pH. A 5-fold increase in Na(2)S concentration above the theoretical stoichiometric concentration was optimum. Observed rate constants of the first stage K(obs-1) were proportional to the hydrosulfide ion concentration and the conversion rate of TNT was greater and faster in buffer system B than in system A. 2010 Elsevier B.V. All rights reserved.

Focused Flow During Infiltration Into Ethanol-Contaminated Unsaturated Porous Media

NASA Astrophysics Data System (ADS)

Jazwiec, A.; Smith, J. E.

2017-12-01

The increasing commercial and industrial use of ethanol, e.g. in biofuels, has generated increased incidents of vadose zone contamination by way of ethanol spills and releases. This has increased the interest in better understanding behaviors of ethanol in unsaturated porous media and it's multiphase interactions in the vadose zone. This study uses highly controlled laboratory experiments in a 2-D (0.6mx0.6mx0.01m) flow cell to investigate water infiltration behaviors into ethanol-contaminated porous media. Ethanol and water were applied by either constant head or constant flux methods onto the surface of sands homogenously packed into the flow cell. The constant flux experiments at both low and high application rates were conducted using a rainulator with a row of hypodermic needles connected to a peristaltic pump. The constant head experiments were conducted using an 8cm diameter tension disk infiltrometer set to both low and high tensions. The presence of ethanol contamination generated solute-dependent capillarity induced focused flow (SCIFF) of water infiltration, which was primarily due to decreases in interfacial tensions at the air-liquid interfaces in the unsaturated sands as a function of ethanol concentration. SCIFF was clearly expressed as an unsaturated water flow phenomenon comprised of narrowly focused vertical flow fingers of water within the initially ethanol contaminated porous media. Using analyses of photos and video, comparisons were made between constant flux and constant head application methods. Further comparisons were made between low and high infiltration rates and the two sand textures used. A high degree of sensitivity to minor heterogeneity in relatively homogeneous sands was also observed. The results of this research have implications for rainfall infiltration into ethanol contaminated vadose zones expressing SCIFF, including implications for associated mass fluxes and the nature of flushing of ethanol from the unsaturated zone to groundwaters.

[Effect of SO2 volume fraction in flue gas on the adsorption behaviors adsorbed by ZL50 activated carbon and kinetic analysis].

PubMed

Gao, Ji-xian; Wang, Tie-feng; Wang, Jin-fu

2010-05-01

The influence of SO2 dynamic adsorption behaviors using ZL50 activated carbon for flue gas desulphurization and denitrification under different SO2 volume fraction was investigated experimentally, and the kinetic analysis was conducted by kinetic models. With the increase of SO2 volume fraction in flue gas, the SO2 removal ratio and the activity ratio of ZL50 activated carbon decreased, respectively, and SO2 adsorption rate and capacity increased correspondingly. The calculated results indicate that Bangham model has the best prediction effect, the chemisorption processes of SO2 was significantly affected by catalytic oxidative reaction. The adsorption rate constant of Lagergren's pseudo first order model increased with the increase of inlet SO, volume fraction, which indicated that catalytic oxidative reaction of SO2 adsorbed by ZL50 activated carbon may be the rate controlling step in earlier adsorption stage. The Lagergren's and Bangham's initial adsorption rate were deduced and defined, respectively. The Ho's and Elovich's initial adsorption rate were also deduced in this paper. The Bangham's initial adsorption rate values were defined in good agreement with those of experiments. The defined Bangham's adsorptive reaction kinetic model can describe the SO2 dynamic adsorption rate well. The studied results indicated that the SO2 partial order of initial reaction rate was one or adjacent to one, while the O2 and water vapor partial order of initial reaction rate were constants ranging from 0.15-0.20 and 0.45-0.50, respectively.

Thermal decay of a metastable state: Influence of rescattering on the quasistationary dynamical rate

NASA Astrophysics Data System (ADS)

Chushnyakova, M. V.; Gontchar, I. I.

2018-03-01

We study the effect of backscattering of the Brownian particles as they escape out of a metastable state overcoming the potential barrier. For this aim, we model this process numerically using the Langevin equations. This modeling is performed for the wide range of the friction constant covering both the energy and spatial diffusion regimes. It is shown how the influence of the descent stage on the quasistationary decay rate gradually disappears as the friction constant decreases. It is found that, in the energy diffusion regime, the rescattering absents and the descent stage does not influence the decay rate. As the value of friction increases, the descent alters the value of the rate by more than 50% for different values of thermal energy and different shapes of the potential. To study the influence of the backscattering on the decay rate, four potentials have been considered which coincide near the potential well and the barrier but differ beyond the barrier. It is shown that the potential for which the well and the barrier are described by two smoothly joined parabolas ("the parabolic potential") plays a role of a dividing range for the mutual layout of the quasistationary dynamical rate and the widely used in the literature Kramers rate. Namely, for the potentials with steeper tails, the Kramers rate RKM underestimates the true quasistationary dynamical rate RD, whereas for the less steep tails the opposite holds (inversion of RD/RKM ). It is demonstrated that the mutual layout of the values of RD for different potentials is explained by the rescattering of the particles from the potential tail.

Equilibrium muscle cross-bridge behavior. Theoretical considerations.

PubMed Central

Schoenberg, M

1985-01-01

We have developed a model for the equilibrium attachment and detachment of myosin cross-bridges to actin that takes into account the possibility that a given cross-bridge can bind to one of a number of actin monomers, as seems likely, rather than to a site on only a single actin monomer, as is often assumed. The behavior of this multiple site model in response to constant velocity, as well as instantaneous stretches, was studied and the influence of system parameters on the force response explored. It was found that in the multiple site model the detachment rate constant has considerably greater influence on the mechanical response than the attachment rate constant. It is shown that one can obtain information about the detachment rate constants either by examining the relationship between the apparent stiffness and duration of stretch for constant velocity stretches or by examining the force-decay rate constants following an instantaneous stretch. The main effect of the attachment rate constant is to scale the mechanical response by influencing the number of attached cross-bridges. The significance of the modeling for the interpretation of experimental results is discussed. PMID:4041539

Electron-ion dissociative recombination rate constants relevant to the Titan atmosphere and the Interstellar Medium

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

Osborne, David; Lawson, Patrick; Adams, Nigel, E-mail: ngadams@uga.edu

Following the arrival of Cassini at Titan in 2004, the Titan atmosphere has been shown to contain large complex polycyclic-aromatic hydrocarbons. Since Cassini has provided a great deal of data, there exists a need for kinetic rate data to help with modeling this atmosphere. One type of kinetic data needed is electron-ion dissociative recombination (e-IDR) rate constants. These data are not readily available for larger compounds, such as naphthalene, or oxygen containing compounds, such as 1,4 dioxane or furan. Here, the rate constants for naphthalene, 1,4 dioxane, and furan have been measured and their temperature dependencies are determined when possible,more » using the University of Georgia's Variable Temperature Flowing Afterglow. The rate constants are compared with those previously published for other compounds; these show trends which illustrate the effects which multi-rings and oxygen heteroatoms substitutions have upon e-IDR rate constants.« less

Electron-ion dissociative recombination rate constants relevant to the Titan atmosphere and the Interstellar Medium

NASA Astrophysics Data System (ADS)

Osborne, David; Lawson, Patrick; Adams, Nigel

2014-01-01

Following the arrival of Cassini at Titan in 2004, the Titan atmosphere has been shown to contain large complex polycyclic-aromatic hydrocarbons. Since Cassini has provided a great deal of data, there exists a need for kinetic rate data to help with modeling this atmosphere. One type of kinetic data needed is electron-ion dissociative recombination (e-IDR) rate constants. These data are not readily available for larger compounds, such as naphthalene, or oxygen containing compounds, such as 1,4 dioxane or furan. Here, the rate constants for naphthalene, 1,4 dioxane, and furan have been measured and their temperature dependencies are determined when possible, using the University of Georgia's Variable Temperature Flowing Afterglow. The rate constants are compared with those previously published for other compounds; these show trends which illustrate the effects which multi-rings and oxygen heteroatoms substitutions have upon e-IDR rate constants.

Variations of iron flux and organic carbon remineralization in a subterranean estuary caused by inter-annual variations in recharge

NASA Astrophysics Data System (ADS)

Roy, Moutusi; Martin, Jonathan B.; Cable, Jaye E.; Smith, Christopher G.

2013-02-01

We determine the inter-annual variations in diagenetic reaction rates of sedimentary iron (Fe) in an east Florida subterranean estuary and evaluate the connection between metal fluxes and recharge to the coastal aquifer. Over the three years study period (from 2004 to 2007), the amount of Fe-oxides reduced at the study site decreased from 192 to 153 g/yr and associated organic carbon (OC) remineralization decreased from 48 to 38 g/yr. These reductions occurred although the Fe-oxide reduction rates remained constant around 1 mg/cm2/yr. These results suggest that changes in flow rates of submarine groundwater discharge (SGD) related to changes in precipitation may be important to fluxes of the diagenetic reaction products. Rainfall at a weather station approximately 5 km from the field area decreased from 12.6 to 8.4 cm/month from 2004 to 2007. Monthly potential evapotranspiration (PET) calculated from Thornthwaite's method indicated potential evapotranspiration cycled from about 3 cm/month in the winter to about 15 cm/month in the summer so that net annual recharge to the aquifer decreased from 40 cm in 2004 to -10 cm in 2007. Simultaneously with the decrease in recharge of groundwater, freshwater SGD decreased by around 20% and caused the originally 25 m wide freshwater seepage face to decrease in width by about 5 m. The smaller seepage face reduced the area under which Fe-oxides were undergoing reductive dissolution. Consequently, the observed decrease in Fe flux is controlled by hydrology of the subterranean estuary. These results point out the need to better understand linkages between temporal variations in diagenetic reactions and changes in flow within subterranean estuaries in order to accurately constrain their contribution to oceanic fluxes of solutes from subterranean estuaries.

Stochastic response of human blood platelets to stimulation of shape changes and secretion.

PubMed Central

Deranleau, D A; Lüthy, R; Lüscher, E F

1986-01-01

Stopped-flow turbidimetric data indicate that platelets stimulated with low levels of thrombin undergo a shape transformation from disc to "sphere" to smaller spiny sphere that is indistinguishable from the shape change induced by ADP through different membrane receptor sites and a dissimilar receptor trigger mechanism. Under conditions where neither secretion nor aggregation occur, the extinction coefficients for total scattering by each of the three platelet forms are independent of the stimulus applied, and both reaction mechanisms can be described as stochastic (Poisson) processes in which the rate constant for the formation of the transient species is equal to the rate constant for its disappearance. This observation is independent of the shape assignment, and as the concentration of thrombin is increased and various storage organelles secrete increasing amounts of their contents into the external medium, the stochastic pattern persists. Progressively larger decreases in the extinction coefficients of the intermediate and final platelet forms, over and above those that reflect shape alterations alone, accompany or parallel the reaction induced by the higher thrombin concentrations. The excess turbidity decrease observed when full secretion occurs can be wholly accounted for by a decrease in platelet volume equal in magnitude to the fraction of the total platelet volume occupied by alpha granules. Platelet activation, as reported by the whole body light scattering of either shape changes alone or shape changes plus parallel (but not necessarily also stochastic) alpha granule secretion, thus manifests itself as a random series of transient events conceivably with its origins in the superposition of a set of more elementary stochastic processes that could include microtubule depolymerization, actin polymerization, and possibly diffusion. Although the real nature of the control mechanism remains obscure, certain properties of pooled stochastic processes suggest that a reciprocal connection between microtubule fragmentation and the assembly of actin-containing pseudopodal structures and contractile elements--processes that may exhibit reciprocal requirements for calcium--might provide a hypothetical basis for a rate-limiting step. PMID:3457375

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.

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

PubMed

Rolandi, Carmen; Schilman, Pablo E

2018-05-01

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

(210)Pb and compositional data of sediments from Rondonian lakes, Madeira River basin, Brazil.

PubMed

Bonotto, Daniel Marcos; Vergotti, Marcelo

2015-05-01

Gold exploration has been intensive in Brazilian Amazon over the last 40 years, where the use of mercury as an amalgam has caused abnormal Hg concentrations in water bodies. Special attention has been directed to Madeira River due to fact it is a major tributary of Amazon River and that since 1986, gold exploration has been officially permitted along a 350km sector of the river. The (21)(0)Pb method has been used to date sediments taken from nine lakes situated in Madeira River basin, Rondônia State, and to verify where anthropogenic Hg might exist due to gold exploitation in Madeira River. Activity profiles of excess (21)(0)Pb determined in the sediment cores provided a means to evaluate the sedimentation rates using a Constant Flux: Constant Sedimentation (CF:CS) and Constant Rate of Supply (CRS) of unsupported/excess (21)(0)Pb models. A significant relationship was found between the CF:CS sedimentation rates and the mean values of the CRS sedimentation rates (Pearson correlation coefficient r=0.59). Chemical data were also determined in the sediments for identifying possible relationships with Hg occurring in the area. Significant values were found in statistical correlation tests realized among the Hg, major oxides and Total Organic Carbon (TOC) content in the sediments. The TOC increased in the sediment cores accompanied by a loss on ignition (LOI) increment, whereas silica decreased following a specific surface area raising associated to the TOC increase. The CRS model always provided ages within the permitted range of the (21)(0)Pb-method in the studied lakes, whereas the CF:CS model predicted two values above 140 years. Copyright © 2015 Elsevier Ltd. All rights reserved.

Medium-high frequency ultrasound and ozone based advanced oxidation for amoxicillin removal in water.

PubMed

Kıdak, Rana; Doğan, Şifa

2018-01-01

In this study, treatment of an antibiotic compound amoxicillin by medium-high frequency ultrasonic irradiation and/or ozonation has been studied. Ultrasonic irradiation process was carried out in a batch reactor for aqueous amoxicillin solutions at three different frequencies (575, 861 and 1141kHz). The applied ultrasonic power was 75W and the diffused power was calculated as 14.6W/L. The highest removal was achieved at 575kHz ultrasonic frequency (>99%) with the highest pseudo first order reaction rate constant 0.04min -1 at pH 10 but the mineralization achieved was around 10%. Presence of alkalinity and humic acid species had negative effect on the removal efficiency (50% decrease). To improve the poor outcomes, ozonation had been applied with or without ultrasound. Ozone removed the amoxicillin at a rate 50 times faster than ultrasound. Moreover, due to the synergistic effect, coupling of ozone and ultrasound gave rise to rate constant of 2.5min -1 (625 times higher than ultrasound). In the processes where ozone was used, humic acid did not show any significant effect because the rate constant was so high that ozone has easily overcome the scavenging effects of natural water constituents. Furthermore, the intermediate compounds, after the incomplete oxidation mechanisms, has been analyzed to reveal the possible degradation pathways of amoxicillin through ultrasonic irradiation and ozonation applications. The outcomes of the intermediate compounds experiments and the toxicity was investigated to give a clear explanation about the safety of the resulting solution. The relevance of all the results concluded that hybrid advanced oxidation system was the best option for amoxicillin removal. Copyright © 2017 Elsevier B.V. All rights reserved.

A Computational Framework for Analyzing Stochasticity in Gene Expression

PubMed Central

Sherman, Marc S.; Cohen, Barak A.

2014-01-01

Stochastic fluctuations in gene expression give rise to distributions of protein levels across cell populations. Despite a mounting number of theoretical models explaining stochasticity in protein expression, we lack a robust, efficient, assumption-free approach for inferring the molecular mechanisms that underlie the shape of protein distributions. Here we propose a method for inferring sets of biochemical rate constants that govern chromatin modification, transcription, translation, and RNA and protein degradation from stochasticity in protein expression. We asked whether the rates of these underlying processes can be estimated accurately from protein expression distributions, in the absence of any limiting assumptions. To do this, we (1) derived analytical solutions for the first four moments of the protein distribution, (2) found that these four moments completely capture the shape of protein distributions, and (3) developed an efficient algorithm for inferring gene expression rate constants from the moments of protein distributions. Using this algorithm we find that most protein distributions are consistent with a large number of different biochemical rate constant sets. Despite this degeneracy, the solution space of rate constants almost always informs on underlying mechanism. For example, we distinguish between regimes where transcriptional bursting occurs from regimes reflecting constitutive transcript production. Our method agrees with the current standard approach, and in the restrictive regime where the standard method operates, also identifies rate constants not previously obtainable. Even without making any assumptions we obtain estimates of individual biochemical rate constants, or meaningful ratios of rate constants, in 91% of tested cases. In some cases our method identified all of the underlying rate constants. The framework developed here will be a powerful tool for deducing the contributions of particular molecular mechanisms to specific patterns of gene expression. PMID:24811315

Class Projects in Physical Organic Chemistry: The Hydrolysis of Aspirin

ERIC Educational Resources Information Center

Marrs, Peter S.

2004-01-01

An exercise that provides a hands-on demonstration of the hydrolysis of aspirin is presented. The key to understanding the hydrolysis is recognizing that all six process may occur simultaneously and that the observed rate constant is the sum of the rate constants that one rate constant dominates the overall process.

Evaluation of the Circulatory Dynamics by using the Windkessel Model in Different Body Positions

NASA Astrophysics Data System (ADS)

Kotani, Kiyoshi; Iida, Fumiaki; Ogawa, Yutaro; Takamasu, Kiyoshi; Jimbo, Yasuhiko

Autonomic nervous system is important in maintaining homeostasis by the opposing effects of sympathetic and parasympathetic nervous activity on organs. However, it is known that they are at times simultaneously increased or decreased in cases of strong fear or depression. Therefore, it is required to evaluate sympathetic and parasympathetic nervous activity independently. In this paper, we propose a method to evaluate sympathetic nervous activity by analyzing the decreases in blood pressure by utilizing the Windkessel model. Experiments are performed in sitting and standing positions for 380 s, respectively. First, we evaluate the effects of length for analysis on the Windkessel time constant. We shorten the length for analysis by multiplying constant coefficients (1.0, 0.9, and 0.8) to the length of blood pressure decrease and then cut-out the waveform for analysis. Then it is found that the Windkessel time constant is decreased as the length for analysis is shortened. This indicates that the length for analysis should be matched when the different experiments are compared. Second, we compare the Windkessel time constant of sitting to that of standing by matching their length for analysis. With statistically significant difference (P<0.05) the results indicate that the Windkessel time constant is larger in the sitting position. Through our observations this difference in the Windkessel time constant is caused by sympathetic nervous activity on vascular smooth muscle.

Moisture effects on greenhouse gases generation in nitrifying gas-phase compost biofilters.

PubMed

Maia, Guilherme D N; Day, George B; Gates, Richard S; Taraba, Joseph L; Coyne, Mark S

2012-06-01

Gas-phase compost biofilters are extensively used in concentrated animal feeding operations to remove odors and, in some cases, ammonia from air sources. The expected biochemical pathway for these predominantly aerobic systems is nitrification. However, non-uniform media with low oxygen levels can shift biofilter microbial pathways to denitrification, a source of greenhouse gases. Several factors contribute to the formation of anoxic/anaerobic zones: media aging, media and particle structure, air velocity distribution, compaction, biofilm thickness, and moisture content (MC) distribution. The present work studies the effects of media moisture conditions on ammonia (NH(3)) removal and greenhouse gas generation (nitrous oxide, N(2)O and methane, CH(4)) for gas-phase compost biofilters subject to a 100-day controlled drying process. Continuous recordings were made for the three gases and water vapor (2.21-h sampling cycle, each cycle consisted of three gas species, and water vapor, for a total of 10,050 data points). Media moisture conditions were classified into three corresponding media drying rate (DR) stages: Constant DR (wetter media), falling DR, and stable-dry system. The first-half of the constant DR period (0-750 h; MC=65-52%, w.b.) facilitated high NH(3) removal rates, but higher N(2)O generation and no CH(4) generation. At the drier stages of the constant DR (750-950 h; MC=52-48%, w.b.) NH(3) removal remained high but N(2)O net generation decreased to near zero. In the falling DR stage (1200-1480 h; MC=44-13%) N(2)O generation decreased, CH(4) increased, and NH(3) was no longer removed. No ammonia removal or greenhouse gas generation was observed in the stable-dry system (1500-2500 h; MC=13%). These results indicate that media should remain toward the drier region of the constant DR (in close proximity to the falling DR stage; MC=50%, approx.), to maintain high levels of NH(3) removal, reduced levels of N(2)O generation, and nullify levels of CH(4) generation. Copyright © 2012 Elsevier Ltd. All rights reserved.

The Multiphase Rheology of Monte Nuovo's Eruption (Campi Flegrei, Italy)

NASA Astrophysics Data System (ADS)

Vona, A.; Romano, C.; Giordano, D.; Russell, K.

2011-12-01

We present a study of high-temperature, uniaxial deformation experiments of natural, partially crystallized samples from the Monte Nuovo (1538 AD) trachytic eruption. The experiments were performed at dry atmospheric conditions and controlled deformation rate using a high-temperature uniaxial Geocomp LoadTrac II press. Experiments were performed isothermally by deforming cores of the natural (i.e., crystal- and vesicle-bearing) samples at constant displacement rates (CDR) corresponding to constant strain rates between 10-7 and 10-4 s-1. The measurements were all performed in the viscous-flow regime and showed non-Newtonian shear thinning behavior. Measured viscosities vary between 1010 and 1013 Pa s. As no yield stress was detected, the flow behavior of the investigated specimens could be described with a simplified Herschel-Bulkley equation in terms of consistency K and flow index n. As the pure liquid and the liquid+crystal rheology of these samples were already measured in previous studies, we were able to estimate the net effects of crystals and vesicles on the rheology of the multiphase suspensions. The results revealed that the presence of vesicles has a major impact on the rheological response of magmas leading to a marked decrease of their viscosity, which partially balances the increase of viscosity due to the presence of crystals. At the same time, the presence of bubbles leads to a strong decrease in the shear strength of the magma inducing local and temporal variation in the deformation regimes (viscous vs. brittle). Brittle and ductile failure were in fact observed at T=600°C and strain rates of 10-5 s-1 and at T=800°C for the higher applied strain rate (10-4 s-1), respectively. During lava flow emplacement, this may explain the origin of the flow banding textures frequently observed in many silicic obsidian lava flows.

Experiments on the rheology of vesicle-bearing magmas

NASA Astrophysics Data System (ADS)

Vona, Alessandro; Ryan, Amy G.; Russell, James K.; Romano, Claudia

2016-04-01

We present a series of high temperature uniaxial deformation experiments designed to investigate the effect of bubbles on the magma bulk viscosity. Starting materials having variable vesicularity (φ = 0 - 66%) were synthesized by high-temperature foaming (T = 900 - 1050 ° C and P = 1 bar) of cores of natural rhyolitic obsidian from Hrafntinnuhryggur, Krafla, Iceland. These cores were subsequently deformed using a high-temperature uniaxial press at dry atmospheric conditions. Each experiment involved deforming vesicle-bearing cores isothermally (T = 750 ° C), at constant displacement rates (strain rates between 0.5-1 x 10-4 s-1), and to total strains (ɛ) of 10-40%. The viscosity of the bubble-free melt (η0) was measured by micropenetration and parallel plate methods and establishes a baseline for comparing data derived from experiments on vesicle rich cores. At the experimental conditions, the presence of vesicles has a major impact on the rheological response, producing a marked decrease of bulk viscosity (maximum decrease of 2 log units Pa s) that is best described by a two-parameter empirical equation: log ηBulk = log η0 - 1.47 * [φ/(1-φ)]0.48. Our model provides a means to compare the diverse behaviour of vesicle-bearing melts reported in the literature and reflecting material properties (e.g., analogue vs. natural), geometry and distribution of pores (e.g. foamed/natural vs. unconsolidated/sintered materials), and flow regime. Lastly, we apply principles of Maxwell relaxation theory, combined with our parameterization of bubble-melt rheology, to map the potential onset of non-Newtonian behaviour (strain localization) in vesiculated magmas and lavas as a function of melt viscosity, vesicularity, strain rate, and geological condition. Increasing vesicularity in magmas can initiate non-Newtonian behaviour at constant strain rates. Lower melt viscosity sustains homogeneous Newtonian flow in vesiculated magmas even at relatively high strain rates.

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.

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.

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.

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.

Cultivation of an L-lactate dehydrogenase mutant of Bacillus stearothermophilus in continuous culture with cell recycle

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

Martin, R.S.; Bushell, D.; Leak, D.J.

1994-06-05

Continuous fermentation with cell recycle proved very effective in increasing the ethanol volumetric productivity of the thermophilic facultative anaerobe, Bacillus stearothermophilus strain LLD-15, on sucrose at 70 C. When complete cell recycle was used, cell viability decreased after a few residence times and sucrose consumption was reduced. Operation using a constant bleed rate resulted in greater stability and higher ethanol volumetric productivities. A mathematical model based on maintenance energy requirements provided an adequate description of the system.

Solution of elliptic partial differential equations by fast Poisson solvers using a local relaxation factor. 2: Two-step method

NASA Technical Reports Server (NTRS)

Chang, S. C.

1986-01-01

A two-step semidirect procedure is developed to accelerate the one-step procedure described in NASA TP-2529. For a set of constant coefficient model problems, the acceleration factor increases from 1 to 2 as the one-step procedure convergence rate decreases from + infinity to 0. It is also shown numerically that the two-step procedure can substantially accelerate the convergence of the numerical solution of many partial differential equations (PDE's) with variable coefficients.

Reaction of SO2 with OH in the atmosphere.

PubMed

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

2017-03-15

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

Degradation rate of lyophilized insulin, exhibiting an apparent Arrhenius behavior around glass transition temperature regardless of significant contribution of molecular mobility.

PubMed

Yoshioka, Sumie; Miyazaki, Tamaki; Aso, Yukio

2006-12-01

The relative influences of chemical activation energy and molecular mobility in determining chemical reactivity were evaluated for insulin lyophilized with alpha,beta-poly(N-hydroxyethyl)-L-aspartamide (PHEA), and compared with that for insulin lyophilized with trehalose, which had been found to have the ability to decrease the molecular mobility of insulin at low humidity. The ratio of the observed rate constant k(obs) to the chemical activation energy-controlled rate constant k(act) (k(obs)/k(act)) at glass transition temperature (T(g)) was estimated to be approximately 0.6 and 0.8 at 6% RH and 12% RH, respectively, indicating that the degradation rate is significantly affected by molecular mobility at lower humidity conditions. However, these k(obs)/k(act) values at T(g) were larger than those for the insulin-trehalose system, and changes in the temperature-dependent slope around T(g) were less obvious than those for the insulin-trehalose system. Thus, the contribution of molecular mobility to the degradation rate in the insulin-PHEA system appeared to be less intense than that in the insulin-trehalose system. The subtle change in the temperature-dependent slope around T(g) observed in the insulin-PHEA system brought about a significant bias in shelf-life estimation when the reaction rate was extrapolated from temperatures above T(g) according to the Arrhenius equation. (c) 2006 Wiley-Liss, Inc. and the American Pharmacists Association

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.

Effect of temperature on postillumination isoprene emission in oak and poplar.

PubMed

Li, Ziru; Ratliff, Ellen A; Sharkey, Thomas D

2011-02-01

Isoprene emission from broadleaf trees is highly temperature dependent, accounts for much of the hydrocarbon emission from plants, and has a profound effect on atmospheric chemistry. We studied the temperature response of postillumination isoprene emission in oak (Quercus robur) and poplar (Populus deltoides) leaves in order to understand the regulation of isoprene emission. Upon darkening a leaf, isoprene emission fell nearly to zero but then increased for several minutes before falling back to nearly zero. Time of appearance of this burst of isoprene was highly temperature dependent, occurring sooner at higher temperatures. We hypothesize that this burst represents an intermediate pool of metabolites, probably early metabolites in the methylerythritol 4-phosphate pathway, accumulated upstream of dimethylallyl diphosphate (DMADP). The amount of this early metabolite(s) averaged 2.9 times the amount of plastidic DMADP. DMADP increased with temperature up to 35°C before starting to decrease; in contrast, the isoprene synthase rate constant increased up to 40°C, the highest temperature at which it could be assessed. During a rapid temperature switch from 30°C to 40°C, isoprene emission increased transiently. It was found that an increase in isoprene synthase activity is primarily responsible for this transient increase in emission levels, while DMADP level stayed constant during the switch. One hour after switching to 40°C, the amount of DMADP fell but the rate constant for isoprene synthase remained constant, indicating that the high temperature falloff in isoprene emission results from a reduction in the supply of DMADP rather than from changes in isoprene synthase activity.

Study on Corrosion-induced Crack Initiation and Propagation of Sustaining Loaded RCbeams

NASA Astrophysics Data System (ADS)

Zhong, X. P.; Li, Y.; Yuan, C. B.; Yang, Z.; Chen, Y.

2018-05-01

For 13 pieces of reinforced concrete beams with HRB500 steel bars under long-term sustained loads, at time of corrosion-induced initial crack of concrete, and corrosion-induced crack widths of 0.3mm and 1mm, corrosion of steel bars and time-varying behavior of corrosion-induced crack width were studied by the ECWD (Electro-osmosis - constant Current – Wet and Dry cycles) accelerated corrosion method. The results show that when cover thickness was between 30 and 50mm,corrosion rates of steel bars were between 0.8% and 1.7% at time of corrosion-induced crack, and decreased with increasing concrete cover thickness; when corrosion-induced crack width was 0.3mm, the corrosion rate decreased with increasing steel bar diameter, and increased with increasing cover thickness; its corrosion rate varied between 0.98% and 4.54%; when corrosion-induced crack width reached 1mm, corrosion rate of steel bars was between 4% and 4.5%; when corrosion rate of steel bars was within 5%, the maximum and average corrosion-induced crack and corrosion rate of steel bars had a good linear relationship. The calculation model predicting the maximum and average width of corrosion-induced crack is given in this paper.

Application of dielectric constant measurement in microwave sludge disintegration and wastewater purification processes.

PubMed

Kovács, Petra Veszelovszki; Lemmer, Balázs; Keszthelyi-Szabó, Gábor; Hodúr, Cecilia; Beszédes, Sándor

2018-05-01

It has been numerously verified that microwave radiation could be advantageous as a pre-treatment for enhanced disintegration of sludge. Very few data related to the dielectric parameters of wastewater of different origins are available; therefore, the objective of our work was to measure the dielectric constant of municipal and meat industrial wastewater during a continuous flow operating microwave process. Determination of the dielectric constant and its change during wastewater and sludge processing make it possible to decide on the applicability of dielectric measurements for detecting the organic matter removal efficiency of wastewater purification process or disintegration degree of sludge. With the measurement of dielectric constant as a function of temperature, total solids (TS) content and microwave specific process parameters regression models were developed. Our results verified that in the case of municipal wastewater sludge, the TS content has a significant effect on the dielectric constant and disintegration degree (DD), as does the temperature. The dielectric constant has a decreasing tendency with increasing temperature for wastewater sludge of low TS content, but an adverse effect was found for samples with high TS and organic matter contents. DD of meat processing wastewater sludge was influenced significantly by the volumetric flow rate and power level, as process parameters of continuously flow microwave pre-treatments. It can be concluded that the disintegration process of food industry sludge can be detected by dielectric constant measurements. From technical purposes the applicability of dielectric measurements was tested in the purification process of municipal wastewater, as well. Determination of dielectric behaviour was a sensitive method to detect the purification degree of municipal wastewater.

Evaporation kinetics of sessile water droplets on micropillared superhydrophobic surfaces.

PubMed

Xu, Wei; Leeladhar, Rajesh; Kang, Yong Tae; Choi, Chang-Hwan

2013-05-21

Evaporation modes and kinetics of sessile droplets of water on micropillared superhydrophobic surfaces are experimentally investigated. The results show that a constant contact radius (CCR) mode and a constant contact angle (CCA) mode are two dominating evaporation modes during droplet evaporation on the superhydrophobic surfaces. With the decrease in the solid fraction of the superhydrophobic surfaces, the duration of a CCR mode is reduced and that of a CCA mode is increased. Compared to Rowan's kinetic model, which is based on the vapor diffusion across the droplet boundary, the change in a contact angle in a CCR (pinned) mode shows a remarkable deviation, decreasing at a slower rate on the superhydrophobic surfaces with less-solid fractions. In a CCA (receding) mode, the change in a contact radius agrees well with the theoretical expectation, and the receding speed is slower on the superhydrophobic surfaces with lower solid fractions. The discrepancy between experimental results and Rowan's model is attributed to the initial large contact angle of a droplet on superhydrophobic surfaces. The droplet geometry with a large contact angle results in a narrow wedge region of air along the contact boundary, where the liquid-vapor diffusion is significantly restricted. Such an effect becomes minor as the evaporation proceeds with the decrease in a contact angle. In both the CCR and CCA modes, the evaporative mass transfer shows the linear relationship between mass(2/3) and evaporation time. However, the evaporation rate is slower on the superhydrophobic surfaces, which is more significant on the surfaces with lower solid fractions. As a result, the superhydrophobic surfaces slow down the drying process of a sessile droplet on them.

Effective degradation of methylisothiazolone biocide using ozone: Kinetics, mechanisms, and decreases in toxicity.

PubMed

Li, Ang; Wu, Qian-Yuan; Tian, Gui-Peng; Hu, Hong-Ying

2016-12-01

Methylisothiazolone (MIT) is a common biocide that is widely used in water-desalination reverse-osmosis processes. The transformation of MIT during water treatment processes is poorly understood. The kinetics and mechanisms involved in the degradation of MIT during ozonation were investigated in this study. Ozonation was found to be a useful way of degrading MIT in water, and the degradation rate constant was 0.11 (±0.1) × 10 3  L/(mol·s). The degradation rate constant did not change when the pH was increased from 3 to 9. The pre-exponential factor A and the activation energy E a for the ozonation process were 7.564 × 10 13  L/(mol·s) and 66.74 kJ/mol, respectively. The decrease in the MIT concentration and the amount of ozone consumed were measured, and the stoichiometric factor α for the ozone consumption to MIT removal ratio was found to be 1.8. Several ozonation products were detected using time-of-flight mass spectrometry. Almost 32% of the organic sulfur in the MIT was oxidized to release sulfate ions, which caused a decrease in pH. Sulfur atoms were oxidized to sulfone species and then hydrolyzed to give sulfate during ozonation. Addition reactions involving carbon-carbon double bonds and the oxidation of α-carbon atoms also occurred. MIT was found to be lethal to Daphnia magna Straus (D. magna) with a median lethal concentration of 18.2 μmol/L. Even though the primary ozonation products of MIT still showed some toxicity to D. magna, ozone could minimize the toxic effect after a long reaction time. Copyright © 2016 Elsevier Ltd. All rights reserved.

Anisotropic cosmological solutions in massive vector theories

NASA Astrophysics Data System (ADS)

Heisenberg, Lavinia; Kase, Ryotaro; Tsujikawa, Shinji

2016-11-01

In beyond-generalized Proca theories including the extension to theories higher than second order, we study the role of a spatial component v of a massive vector field on the anisotropic cosmological background. We show that, as in the case of the isotropic cosmological background, there is no additional ghostly degrees of freedom associated with the Ostrogradski instability. In second-order generalized Proca theories we find the existence of anisotropic solutions on which the ratio between the anisotropic expansion rate Σ and the isotropic expansion rate H remains nearly constant in the radiation-dominated epoch. In the regime where Σ/H is constant, the spatial vector component v works as a dark radiation with the equation of state close to 1/3. During the matter era, the ratio Σ/H decreases with the decrease of v. As long as the conditions |Σ| ll H and v2 ll phi2 are satisfied around the onset of late-time cosmic acceleration, where phi is the temporal vector component, we find that the solutions approach the isotropic de Sitter fixed point (Σ = 0 = v) in accordance with the cosmic no-hair conjecture. In the presence of v and Σ the early evolution of the dark energy equation of state wDE in the radiation era is different from that in the isotropic case, but the approach to the isotropic value wDE(iso) typically occurs at redshifts z much larger than 1. Thus, apart from the existence of dark radiation, the anisotropic cosmological dynamics at low redshifts is similar to that in isotropic generalized Proca theories. In beyond-generalized Proca theories the only consistent solution to avoid the divergence of a determinant of the dynamical system corresponds to v = 0, so Σ always decreases in time.

Viscous flux flow velocity and stress distribution in the Kim model of a long rectangular slab superconductor

NASA Astrophysics Data System (ADS)

Yang, Yong; Chai, Xueguang

2018-05-01

When a bulk superconductor endures the magnetization process, enormous mechanical stresses are imposed on the bulk, which often leads to cracking. In the present work, we aim to resolve the viscous flux flow velocity υ 0/w, i.e. υ 0 (because w is a constant) and the stress distribution in a long rectangular slab superconductor for the decreasing external magnetic field (B a ) after zero-field cooling (ZFC) and field cooling (FC) using the Kim model and viscous flux flow equation simultaneously. The viscous flux flow velocity υ 0/w and the magnetic field B* at which the body forces point away in all of the slab volumes during B a reduction, are determined by both B a and the decreasing rate (db a /dt) of the external magnetic field normalized by the full penetration field B p . In previous studies, υ 0/w obtained by the Bean model with viscous flux flow is only determined by db a /dt, and the field B* that is derived only from the Kim model is a positive constant when the maximum external magnetic field is chosen. This means that the findings in this paper have more physical contents than the previous results. The field B* < 0 can be kept for any value of B a when the rate db a /dt is greater than a certain value. There is an extreme value for any curve of maximum stress changing with decreasing field B a after ZFC if B* ≤ 0. The effect of db a /dt on the stress is significant in the cases of both ZFC and FC.

Anisotropic cosmological solutions in massive vector theories

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

Heisenberg, Lavinia; Kase, Ryotaro; Tsujikawa, Shinji, E-mail: Lavinia.heisenberg@googlemail.com, E-mail: r.kase@rs.tus.ac.jp, E-mail: shinji@rs.kagu.tus.ac.jp

In beyond-generalized Proca theories including the extension to theories higher than second order, we study the role of a spatial component v of a massive vector field on the anisotropic cosmological background. We show that, as in the case of the isotropic cosmological background, there is no additional ghostly degrees of freedom associated with the Ostrogradski instability. In second-order generalized Proca theories we find the existence of anisotropic solutions on which the ratio between the anisotropic expansion rate Σ and the isotropic expansion rate H remains nearly constant in the radiation-dominated epoch. In the regime where Σ/ H is constant,more » the spatial vector component v works as a dark radiation with the equation of state close to 1/3. During the matter era, the ratio Σ/ H decreases with the decrease of v . As long as the conditions |Σ| || H and v {sup 2} || φ{sup 2} are satisfied around the onset of late-time cosmic acceleration, where φ is the temporal vector component, we find that the solutions approach the isotropic de Sitter fixed point (Σ = 0 = v ) in accordance with the cosmic no-hair conjecture. In the presence of v and Σ the early evolution of the dark energy equation of state w {sub DE} in the radiation era is different from that in the isotropic case, but the approach to the isotropic value w {sub DE}{sup (iso)} typically occurs at redshifts z much larger than 1. Thus, apart from the existence of dark radiation, the anisotropic cosmological dynamics at low redshifts is similar to that in isotropic generalized Proca theories. In beyond-generalized Proca theories the only consistent solution to avoid the divergence of a determinant of the dynamical system corresponds to v = 0, so Σ always decreases in time.« less